van der Waals interactions are critical in Car-Parrinello molecular dynamics simulations of porphyrin-fullerene dyads.

PubMed

Karilainen, Topi; Cramariuc, Oana; Kuisma, Mikael; Tappura, Kirsi; Hukka, Terttu I

2015-04-05

The interplay between electrostatic and van der Waals (vdW) interactions in porphyrin-C60 dyads is still under debate despite its importance in influencing the structural characteristics of such complexes considered for various applications in molecular photovoltaics. In this article, we sample the conformational space of a porphyrin-C60 dyad using Car-Parrinello molecular dynamics simulations with and without empirical vdW corrections. Long-range vdW interactions, which are poorly described by the commonly used density functional theory functionals, prove to be essential for a proper dynamics of the dyad moieties. Inclusion of vdW corrections brings porphyrin and C60 close together in an orientation that is in agreement with experimental observations. The structural differences arising from the vdW corrections are shown to be significant for several properties and potentially less important for others. Additionally, our Mulliken population analysis reveals that contrary to the common belief, porphyrin is not the primary electron donating moiety for C60 . In the considered dyad, fullerene's affinity for electrons is primarily satisfied by charge transfer from the amide group of the linker. However, we show that in the absence of another suitable bound donor, C60 can withdraw electrons from porphyrin if it is sufficiently close. © 2015 Wiley Periodicals, Inc.

Predicting elastic properties of β-HMX from first-principles calculations.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; Grimme, Stefan; De, Suvranu

2015-05-07

We investigate the performance of van der Waals (vdW) functions in predicting the elastic constants of β cyclotetramethylene tetranitramine (HMX) energetic molecular crystals using density functional theory (DFT) calculations. We confirm that the accuracy of the elastic constants is significantly improved using the vdW corrections with environment-dependent C6 together with PBE and revised PBE exchange-correlation functionals. The elastic constants obtained using PBE-D3(0) calculations yield the most accurate mechanical response of β-HMX when compared with experimental stress-strain data. Our results suggest that PBE-D3 calculations are reliable in predicting the elastic constants of this material.

Communication: Accurate higher-order van der Waals coefficients between molecules from a model dynamic multipole polarizability

DOE PAGES

Tao, Jianmin; Rappe, Andrew M.

2016-01-20

Due to the absence of the long-range van der Waals (vdW) interaction, conventional density functional theory (DFT) often fails in the description of molecular complexes and solids. In recent years, considerable progress has been made in the development of the vdW correction. However, the vdW correction based on the leading-order coefficient C 6 alone can only achieve limited accuracy, while accurate modeling of higher-order coefficients remains a formidable task, due to the strong non-additivity effect. Here, we apply a model dynamic multipole polarizability within a modified single-frequency approximation to calculate C 8 and C 10 between small molecules. We findmore » that the higher-order vdW coefficients from this model can achieve remarkable accuracy, with mean absolute relative deviations of 5% for C 8 and 7% for C 10. As a result, inclusion of accurate higher-order contributions in the vdW correction will effectively enhance the predictive power of DFT in condensed matter physics and quantum chemistry.« less

Ab-initio adsorption study of chitosan on functionalized graphene: critical role of van der Waals interactions.

PubMed

Rahman, R; Mazumdar, D

2012-03-01

We investigate the adsorption process of an organic biomolecule (chitosan) on epoxy-functionalized graphene using ab-initio density functional methods incorporating van-der-waals (vdW) interactions. The role of London dispersion force on the cohesive energy and conformal preference of the molecule is quantitatively elucidated. Functionalizing graphene with epoxy leads to weak hydrogen-bond interactions with chitosan. Binding energy values increase by over an order of magnitude after including vdW corrections, implying that dispersive interactions dominate the physisorption process. Conformal study show binding upto 30 kcal/mol when the molecule is oriented with the hydroxyl group approaching the functionalized graphene. Our study advances the promise of functionalized graphene for a variety of applications.

The nature of the interlayer interaction in bulk and few-layer phosphorus

DOE PAGES

Shulenburger, Luke; Baczewski, A. D.; Zhu, Z.; ...

2015-11-02

Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called van der Waals (vdW) solids . We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. Lastly, these findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.

The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus.

PubMed

Shulenburger, L; Baczewski, A D; Zhu, Z; Guan, J; Tománek, D

2015-12-09

Sensitive dependence of the electronic structure on the number of layers in few-layer phosphorene raises a question about the true nature of the interlayer interaction in so-called "van der Waals (vdW) solids". We performed quantum Monte Carlo calculations and found that the interlayer interaction in bulk black phosphorus and related few-layer phosphorene is associated with a significant charge redistribution that is incompatible with purely dispersive forces and not captured by density functional theory calculations with different vdW corrected functionals. These findings confirm the necessity of more sophisticated treatment of nonlocal electron correlation in total energy calculations.

Evaluation of van der Waals density functionals for layered materials

NASA Astrophysics Data System (ADS)

Tawfik, Sherif Abdulkader; Gould, Tim; Stampfl, Catherine; Ford, Michael J.

2018-03-01

In 2012, Björkman et al. posed the question "Are we van der Waals ready?" [T. Björkman et al., J. Phys.: Condens. Matter 24, 424218 (2012), 10.1088/0953-8984/24/42/424218] about the ability of ab initio modeling to reproduce van der Waals (vdW) dispersion forces in layered materials. The answer at that time was no, however. Here we report on a new generation of vdW dispersion models and show that one, i.e., the fractionally ionic atom theory with many-body dispersions, offers close to quantitative predictions for layered structures. Furthermore, it does so from a qualitatively correct picture of dispersion forces. Other methods, such as D3 and optB88vdW, also work well, albeit with some exceptions. We thus argue that we are nearly vdW ready and that some modern dispersion methods are accurate enough to be used for nanomaterial prediction, albeit with some caution required.

Predicting vapor liquid equilibria using density functional theory: A case study of argon

NASA Astrophysics Data System (ADS)

Goel, Himanshu; Ling, Sanliang; Ellis, Breanna Nicole; Taconi, Anna; Slater, Ben; Rai, Neeraj

2018-06-01

Predicting vapor liquid equilibria (VLE) of molecules governed by weak van der Waals (vdW) interactions using the first principles approach is a significant challenge. Due to the poor scaling of the post Hartree-Fock wave function theory with system size/basis functions, the Kohn-Sham density functional theory (DFT) is preferred for systems with a large number of molecules. However, traditional DFT cannot adequately account for medium to long range correlations which are necessary for modeling vdW interactions. Recent developments in DFT such as dispersion corrected models and nonlocal van der Waals functionals have attempted to address this weakness with a varying degree of success. In this work, we predict the VLE of argon and assess the performance of several density functionals and the second order Møller-Plesset perturbation theory (MP2) by determining critical and structural properties via first principles Monte Carlo simulations. PBE-D3, BLYP-D3, and rVV10 functionals were used to compute vapor liquid coexistence curves, while PBE0-D3, M06-2X-D3, and MP2 were used for computing liquid density at a single state point. The performance of the PBE-D3 functional for VLE is superior to other functionals (BLYP-D3 and rVV10). At T = 85 K and P = 1 bar, MP2 performs well for the density and structural features of the first solvation shell in the liquid phase.

Modulation of band gap by an applied electric field in BN-based heterostructures

NASA Astrophysics Data System (ADS)

Luo, M.; Xu, Y. E.; Zhang, Q. X.

2018-05-01

First-principles density functional theory (DFT) calculations are performed on the structural and electronic properties of the SiC/BN van der Waals (vdW) heterostructures under an external electric field (E-field). Our results reveal that the SiC/BN vdW heterostructure has a direct band gap of 2.41 eV in the raw. The results also imply that electrons are likely to transfer from BN to SiC monolayer due to the deeper potential of BN monolayer. It is also observed that, by applying an E-field, ranging from -0.50 to +0.65 V/Å, the band gap decreases from 2.41 eV to zero, which presents a parabola-like relationship around 0.0 V/Å. Through partial density of states (PDOS) plots, it is revealed that, p orbital of Si, C, B, and N atoms are responsible for the significant variations of band gap. These obtained results predict that, the electric field tunable band gap of the SiC/BN vdW heterostructures carries potential applications for nanoelectronics and spintronic device applications.

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

DOE PAGES

Han, Dan; Zhang, Tao; Huang, Menglin; ...

2018-05-24

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Dan; Zhang, Tao; Huang, Menglin

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

The direct-to-indirect band gap crossover in two-dimensional van der Waals Indium Selenide crystals

PubMed Central

Mudd, G. W.; Molas, M. R.; Chen, X.; Zólyomi, V.; Nogajewski, K.; Kudrynskyi, Z. R.; Kovalyuk, Z. D.; Yusa, G.; Makarovsky, O.; Eaves, L.; Potemski, M.; Fal’ko, V. I.; Patanè, A.

2016-01-01

The electronic band structure of van der Waals (vdW) layered crystals has properties that depend on the composition, thickness and stacking of the component layers. Here we use density functional theory and high field magneto-optics to investigate the metal chalcogenide InSe, a recent addition to the family of vdW layered crystals, which transforms from a direct to an indirect band gap semiconductor as the number of layers is reduced. We investigate this direct-to-indirect bandgap crossover, demonstrate a highly tuneable optical response from the near infrared to the visible spectrum with decreasing layer thickness down to 2 layers, and report quantum dot-like optical emissions distributed over a wide range of energy. Our analysis also indicates that electron and exciton effective masses are weakly dependent on the layer thickness and are significantly smaller than in other vdW crystals. These properties are unprecedented within the large family of vdW crystals and demonstrate the potential of InSe for electronic and photonic technologies. PMID:28008964

The direct-to-indirect band gap crossover in two-dimensional van der Waals Indium Selenide crystals.

PubMed

Mudd, G W; Molas, M R; Chen, X; Zólyomi, V; Nogajewski, K; Kudrynskyi, Z R; Kovalyuk, Z D; Yusa, G; Makarovsky, O; Eaves, L; Potemski, M; Fal'ko, V I; Patanè, A

2016-12-23

The electronic band structure of van der Waals (vdW) layered crystals has properties that depend on the composition, thickness and stacking of the component layers. Here we use density functional theory and high field magneto-optics to investigate the metal chalcogenide InSe, a recent addition to the family of vdW layered crystals, which transforms from a direct to an indirect band gap semiconductor as the number of layers is reduced. We investigate this direct-to-indirect bandgap crossover, demonstrate a highly tuneable optical response from the near infrared to the visible spectrum with decreasing layer thickness down to 2 layers, and report quantum dot-like optical emissions distributed over a wide range of energy. Our analysis also indicates that electron and exciton effective masses are weakly dependent on the layer thickness and are significantly smaller than in other vdW crystals. These properties are unprecedented within the large family of vdW crystals and demonstrate the potential of InSe for electronic and photonic technologies.

Vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 clusters

NASA Astrophysics Data System (ADS)

Nimlos, M. R.; Young, M. A.; Bernstein, E. R.; Kelley, D. F.

1989-11-01

The first excited electronic state (S1) vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 van der Waals (vdW) clusters have been studied using molecular jet and time resolved emission spectroscopic techniques. The rates of intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) as functions of vibrational energy are reported for both clusters. For vibrational energy in excess of the cluster binding energy, both clusters are observed to dissociate. The dispersed emission spectra of these clusters demonstrate that aniline(Ar)1 dissociates to all energetically accessible bare molecule states and that aniline(CH4)1 dissociates selectively to only the bare molecule vibrationless state. The emission kinetics show that in the aniline(Ar)1 case, the initially excited states have nanosecond lifetimes, and intermediate cluster states have very short lifetimes. In contrast, the initially excited aniline(CH4)1 states and other intermediate vibrationally excited cluster states are very short lived (<100 ps), and the intermediate cluster 00 state is observed. These results can be understood semiquantitatively in terms of an overall serial IVR/VP mechanism which consists of the following: (1) the rates of chromophore to vdW mode IVR are given by Fermi's golden rule, and the density of vdW vibrational states is the most important factor in determining the relative [aniline(Ar)1 vs aniline(CH4)1] rates of IVR; (2) IVR among the vdW modes is rapid; and (3) VP rates can be calculated by a restricted vdW mode phase space Rice-Ramsberger-Kassel-Marcus theory. Since the density of vdW states is three orders of magnitude greater for aniline(CH4)1 than aniline(Ar)1 at 700 cm-1, the model predicts that IVR is slow and rate limiting in aniline(Ar)1, whereas VP is slow and rate limiting in aniline(CH4)1. The agreement of these predictions with the experimental results is very good and is discussed in detail.

Accurate van der Waals coefficients from density functional theory

PubMed Central

Tao, Jianmin; Perdew, John P.; Ruzsinszky, Adrienn

2012-01-01

The van der Waals interaction is a weak, long-range correlation, arising from quantum electronic charge fluctuations. This interaction affects many properties of materials. A simple and yet accurate estimate of this effect will facilitate computer simulation of complex molecular materials and drug design. Here we develop a fast approach for accurate evaluation of dynamic multipole polarizabilities and van der Waals (vdW) coefficients of all orders from the electron density and static multipole polarizabilities of each atom or other spherical object, without empirical fitting. Our dynamic polarizabilities (dipole, quadrupole, octupole, etc.) are exact in the zero- and high-frequency limits, and exact at all frequencies for a metallic sphere of uniform density. Our theory predicts dynamic multipole polarizabilities in excellent agreement with more expensive many-body methods, and yields therefrom vdW coefficients C6, C8, C10 for atom pairs with a mean absolute relative error of only 3%. PMID:22205765

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Correlational Effects of the Molecular-Tilt Configuration and the Intermolecular van der Waals Interaction on the Charge Transport in the Molecular Junction.

PubMed

Shin, Jaeho; Gu, Kyungyeol; Yang, Seunghoon; Lee, Chul-Ho; Lee, Takhee; Jang, Yun Hee; Wang, Gunuk

2018-06-25

Molecular conformation, intermolecular interaction, and electrode-molecule contacts greatly affect charge transport in molecular junctions and interfacial properties of organic devices by controlling the molecular orbital alignment. Here, we statistically investigated the charge transport in molecular junctions containing self-assembled oligophenylene molecules sandwiched between an Au probe tip and graphene according to various tip-loading forces ( F L ) that can control the molecular-tilt configuration and the van der Waals (vdW) interactions. In particular, the molecular junctions exhibited two distinct transport regimes according to the F L dependence (i.e., F L -dependent and F L -independent tunneling regimes). In addition, the charge-injection tunneling barriers at the junction interfaces are differently changed when the F L ≤ 20 nN. These features are associated to the correlation effects between the asymmetry-coupling factor (η), the molecular-tilt angle (θ), and the repulsive intermolecular vdW force ( F vdW ) on the molecular-tunneling barriers. A more-comprehensive understanding of these charge transport properties was thoroughly developed based on the density functional theory calculations in consideration of the molecular-tilt configuration and the repulsive vdW force between molecules.

Polymorphism and Elastic Response of Molecular Materials from First Principles: How Hard Can it Be?

NASA Astrophysics Data System (ADS)

Reilly, Anthony; Tkatchenko, Alexandre

2014-03-01

Molecular materials are of great fundamental and applied importance in science and industry, with numerous applications in pharmaceuticals, electronics, sensing, and catalysis. A key challenge for theory has been the prediction of their stability, polymorphism and response to perturbations. While pairwise models of van der Waals (vdW) interactions have improved the ability of density functional theory (DFT) to model these systems, substantial quantitative and even qualitative failures remain. In this contribution we show how a many-body description of vdW interactions can dramatically improve the accuracy of DFT for molecular materials, yielding quantitative description of stabilities and polymorphism for these challenging systems. Moreover, the role of many-body vdW interactions goes beyond stabilities to response properties. In particular, we have studied the elastic properties of a series of molecular crystals, finding that many-body vdW interactions can account for up to 30% of the elastic response, leading to quantitative and qualitative changes in elastic behavior. We will illustrate these crucial effects with the challenging case of the polymorphs of aspirin, leading to a better understanding of the conflicting experimental and theoretical studies of this system.

Computational screening of high-performance optoelectronic materials using OptB88vdW and TB-mBJ formalisms.

PubMed

Choudhary, Kamal; Zhang, Qin; Reid, Andrew C E; Chowdhury, Sugata; Van Nguyen, Nhan; Trautt, Zachary; Newrock, Marcus W; Congo, Faical Yannick; Tavazza, Francesca

2018-05-08

We perform high-throughput density functional theory (DFT) calculations for optoelectronic properties (electronic bandgap and frequency dependent dielectric function) using the OptB88vdW functional (OPT) and the Tran-Blaha modified Becke Johnson potential (MBJ). This data is distributed publicly through JARVIS-DFT database. We used this data to evaluate the differences between these two formalisms and quantify their accuracy, comparing to experimental data whenever applicable. At present, we have 17,805 OPT and 7,358 MBJ bandgaps and dielectric functions. MBJ is found to predict better bandgaps and dielectric functions than OPT, so it can be used to improve the well-known bandgap problem of DFT in a relatively inexpensive way. The peak positions in dielectric functions obtained with OPT and MBJ are in comparable agreement with experiments. The data is available on our websites http://www.ctcms.nist.gov/~knc6/JVASP.html and https://jarvis.nist.gov.

Dispersion interactions in room-temperature ionic liquids: Results from a non-empirical density functional

NASA Astrophysics Data System (ADS)

Kohanoff, Jorge; Pinilla, Carlos; Youngs, Tristan G. A.; Artacho, Emilio; Soler, José M.

2011-10-01

The role of dispersion or van de Waals (VDW) interactions in imidazolium-based room-temperature ionic liquids is studied within the framework of density functional theory, using a recently developed non-empirical functional [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004), 10.1103/PhysRevLett.92.246401], as efficiently implemented in the SIESTA code [G. Román-Pérez and J. M. Soler, Phys. Rev. Lett. 103, 096102 (2009), 10.1103/PhysRevLett.103.096102]. We present results for the equilibrium structure and lattice parameters of several crystalline phases, finding a general improvement with respect to both the local density (LDA) and the generalized gradient approximations (GGA). Similar to other systems characterized by VDW bonding, such as rare gas and benzene dimers as well as solid argon, equilibrium distances and volumes are consistently overestimated by ≈7%, compared to -11% within LDA and 11% within GGA. The intramolecular geometries are retained, while the intermolecular distances and orientations are significantly improved relative to LDA and GGA. The quality is superior to that achieved with tailor-made empirical VDW corrections ad hoc [M. G. Del Pópolo, C. Pinilla, and P. Ballone, J. Chem. Phys. 126, 144705 (2007), 10.1063/1.2715571]. We also analyse the performance of an optimized version of this non-empirical functional, where the screening properties of the exchange have been tuned to reproduce high-level quantum chemical calculations [J. Klimes, D. Bowler, and A. Michaelides, J. Phys.: Condens. Matter 22, 074203 (2010), 10.1088/0953-8984/22/7/074203]. The results for solids are even better with volumes and geometries reproduced within 2% of experimental data. We provide some insight into the issue of polymorphism of [bmim][Cl] crystals, and we present results for the geometry and energetics of [bmim][Tf] and [mmim][Cl] neutral and charged clusters, which validate the use of empirical force fields.

van der Waals Heterostructures with High Accuracy Rotational Alignment.

PubMed

Kim, Kyounghwan; Yankowitz, Matthew; Fallahazad, Babak; Kang, Sangwoo; Movva, Hema C P; Huang, Shengqiang; Larentis, Stefano; Corbet, Chris M; Taniguchi, Takashi; Watanabe, Kenji; Banerjee, Sanjay K; LeRoy, Brian J; Tutuc, Emanuel

2016-03-09

We describe the realization of van der Waals (vdW) heterostructures with accurate rotational alignment of individual layer crystal axes. We illustrate the approach by demonstrating a Bernal-stacked bilayer graphene formed using successive transfers of monolayer graphene flakes. The Raman spectra of this artificial bilayer graphene possess a wide 2D band, which is best fit by four Lorentzians, consistent with Bernal stacking. Scanning tunneling microscopy reveals no moiré pattern on the artificial bilayer graphene, and tunneling spectroscopy as a function of gate voltage reveals a constant density of states, also in agreement with Bernal stacking. In addition, electron transport probed in dual-gated samples reveals a band gap opening as a function of transverse electric field. To illustrate the applicability of this technique to realize vdW heterostructuctures in which the functionality is critically dependent on rotational alignment, we demonstrate resonant tunneling double bilayer graphene heterostructures separated by hexagonal boron-nitride dielectric.

Two-Dimensional Graphene-Gold Interfaces Serve as Robust Templates for Dielectric Capacitors.

PubMed

Teshome, Tamiru; Datta, Ayan

2017-10-04

The electronic structures of novel heterostructures, namely, graphene-Au van der Waals (vdW) interfaces, have been studied using density functional theory. Dispersion-corrected PBE-D2 functionals are used to describe the phonon spectrum and binding energies. Ab initio molecular dynamics simulations reveal that the vdW framework is preserved till 1200 K. Beyond T = 1200 K, a transition of the quasiplanar Au into the three-dimensional cluster-like structure is observed. A dielectric capacitor is designed by placing 1-4 hexagonal boron nitride (h-BN) monolayers between graphene and Au conductive plates. Charge separation between the Au and graphene plates is carried out under the effect of an external field normal to the graphene-h-BN-Au interface. The gravimetric capacitances are computed as C 1 = 7.6 μF/g and C 2 = 3.2 μF/g for h-BN bilayers with the Au-graphene heterostructures. The capacitive behavior shows strong deviations from the classical charging models and exemplifies the importance of quantum phenomenon at short contacts, which eventually nullifies at large interelectrode distances. The graphene-Au interface is predicted to be an exciting vdW heterostructure with a potential application as a dielectric capacitor.

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

DOE PAGES

Wang, Han; Bang, Junhyeok; Sun, Yiyang; ...

2016-05-10

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.« less

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Han; Bang, Junhyeok; Sun, Yiyang

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.« less

Nonlocal van der Waals functionals: The case of rare-gas dimers and solids

NASA Astrophysics Data System (ADS)

Tran, Fabien; Hutter, Jürg

2013-05-01

Recently, the nonlocal van der Waals (vdW) density functionals [M. Dion, H. Rydberg, E. Schröder, D. C. Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004), 10.1103/PhysRevLett.92.246401] have attracted considerable attention due to their good performance for systems where weak interactions are important. Since the physics of dispersion is included in these functionals, they are usually more accurate and show less erratic behavior than the semilocal and hybrid methods. In this work, several variants of the vdW functionals have been tested on rare-gas dimers (from He2 to Kr2) and solids (Ne, Ar, and Kr) and their accuracy compared to standard semilocal approximations, supplemented or not by an atom-pairwise dispersion correction [S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010), 10.1063/1.3382344]. An analysis of the results in terms of energy decomposition is also provided.

EDITORIAL: Van der Waals interactions in advanced materials, in memory of David C Langreth Van der Waals interactions in advanced materials, in memory of David C Langreth

NASA Astrophysics Data System (ADS)

Hyldgaard, Per; Rahman, Talat S.

2012-10-01

The past decade has seen a dramatic rise in interest in exploring the role that van der Waals (vdW) or dispersion forces play in materials and in material behavior. Part of this stems from the obvious fact that vdW interactions (and other weak forces, such as Casimir) underpin molecular recognition, i.e., nature's approach to search for a match between genes and anti-genes and hence enable biological function. Less obvious is the recognition that vdW interactions affect a multitude of properties of a vast variety of materials in general, some of which also have strong technological applications. While for two atom- or orbital-sized material fragments the dispersive contributions to binding are small compared to those from the better known forms (ionic, covalent, metallic), those between sparse materials (spread over extended areas) can be of paramount importance. For example, an understanding of binding in graphite cannot arise solely from a study of the graphene layers individually, but also requires insight from inter-sheet graphene vdW bonding. It is the extended-area vdW bonding that provides sufficient cohesion to make graphite a robust, naturally occurring material. In fact, it is the vdW-bonded graphite, and not the all-covalently bonded diamond, that is the preferred form of pure carbon under ambient conditions. Also important is the understanding that vdW attraction can attain a dramatic relevance even if the material fragments, the building blocks, are not necessarily parallel from the outset or smooth when viewed in isolation (such as a graphene sheet or a carbon nanotube). This can happen if the building blocks have some softness and flexibility and allow an internal relative alignment to emerge. The vdW forces can then cause increasingly larger parts of the interacting fragments to line up at sub-nanometer separations and thus beget more areas with a sizable vdW bonding contribution. The gecko can scale a wall because it can bring its flexible hairs sufficiently close to any corrugated—and/or any smooth—surface and thus enforce a strong vdW-type adhesion; it exploits what is then essentially a contact force (dominated by the attraction exerted in the near-surface regions) to defy the pull of gravity on its own bulk. This Journal of Physics: Condensed Matter special issue is dedicated to the memory of David C Langreth. David is a dearly missed friend and mentor who inspired many of us. He was an outstanding condensed matter theorist and a scholar who greatly influenced us through his many-particle-physics based insights into density functional theory (DFT), surface science and related areas. His seminal works range from conserving formulations of interacting nonequilibrium transport [1] and formal-scattering theory [2] to an explicit formulation [3] of the exact DFT exchange-correlation energy in the adiabatic connection formula (ACF), the latter also being derived independently by Gunnarsson and Lundqvist [4]. David's portfolio also includes an analysis [5] that helped catalyze and guide the development of DFT from the local-density approximation (LDA) to the formulations of generalized gradient approximations (GGAs). Another salient contribution of David's is in the area of vdW interactions in materials. He was a key architect of the vdW density functional (vdW-DF) method [6, 7]. This method was developed in a long-standing Rutgers-Chalmers collaboration between David's group and that of Bengt I Lundqvist, later extending to a wider group of researchers on both sides of the Atlantic. Plasmons are collective excitations that depend on electron-density variation. The plasmon response can be seen as defining the nature of the LDA [4] and their description can thus also be seen as contributing to the success of GGA. The vdW-DF method is a regular constraint-based density functional (for ground-state DFT) which is derived within the ACF framework and which emphasizes the electrodynamical nature of the coupling between these collective plasmon excitations. The vdW-DF method thus seeks to utilise the implicit plasmon nature of the LDA/GGA success to also provide a nonempirical account of the fully nonlocal correlations that underpin the vdW bond [8]. The method retains a seamless integration [6] with the semilocal density functional components. We know that David was pleased to see how this quantitative, material-specific theory helped address problems in a broad class of materials that are sparse, i.e., that contain low electron density regions which are of significant consequence in determining material characteristics [9]. In a DFT framework, the vdW-DF method supplements other nonlocal functional descriptions [10] and the DFT-dispersion class of methods, extending GGA-DFT with an atom-based asymptotic description which relies on the vdW interaction coefficients [11]. The recent quest to understand the role of vdW forces in materials has certainly been facilitated and intensified by the set of recent developments in DFT itself. This is because these vdW-aware methods provide an opportunity to deliver a computationally effective account of the quantum-physical behavior even when the materials are sparse. It is the expectation that with such new-found theoretical capability, one may further extend the immense progress already attained by traditional (GGA) DFT calculations in reliably predicting the characteristics of materials and phenomena in materials, nanoscience, chemistry and other related fields [12]. This special issue contains a wealth of exciting contributions, mostly on vdW forces in materials. The special issue was suggested following the well-attended first focused vdW and materials session arranged by the Division of Materials Physics (DMP) of the American Physical Society (APS) at the March Meeting in 2011. The sad and unexpected passing of David in the spring of 2011 caused some rethinking and at the memorial symposium, held by David's colleagues at Rutgers in November 2011, we proposed to dedicate this special issue to David's contributions to the field. We are delighted with the overwhelmingly positive reaction that we received in response to our call for papers. We are also delighted to now be able to bring so many exciting contributions to you. The papers included in this special issue focus, in general, either through experiments or through theoretical characterization, on material properties in which vdW forces represent a central component. These articles contain arguments for and against a broader usage of DFT with vdW to account for material description, as well as establishing benchmarks which measure progress in the field. This special issue also includes fundamental theoretical analysis and suggestions for sensitive experiments that can resolve outstanding issues underlying the nature and role of the interaction. We believe that these papers will help stimulate further material-theory developments and, even more importantly, more discussions and feedback between theory and experiment. Physisorption is important to enable lubrication. This is because physisorption keeps the lubricating molecules at the interface at which a pair of internal surfaces must be free to move relative to each other. In turn, physisorbed (or perhaps weakly chemisorbed) lubricants prevent, for example, the formation of stronger bonding that will impede mechanical operation. However, it is also important to further characterize the nature and dynamics of the vdW bonding of lubricants: while physisorption means a weak binding further from the surface, there are still important friction effects. Walker et al present an experimental study, along with theoretical analysis, that directly determines the frictional heating of a Kr overlayer on graphene through quartz crystal microbalance measurements. The properties of materials reflect their atomic structure and hence indirectly their bonding nature and character. We can explore the role of dispersion forces by examining the impact their inclusion has on predictions of material properties. On the other hand, the experimental and theoretical study of Casimir forces also plays a vital role in the exploration of material behavior. vdW forces are related to the Casimir force but lack retardation effects. While the vdW bonding depends on additional effects (for example, the multipole contributions that reflect image-plane effects), the study of Casimir forces provides direct (and not indirect) measurements of the nature of interactions. Klimchitskaya et al note that to reconcile explicit measurements of the Casmir forces between semiconductor fragments within the Lifshitz description, it is relevant to question the Drude-like description of the contributions from free carriers and instead proceed with a formulation based only on optical observations of the permittivity. This optical response can be seen as a reflection of a more plasmon-like behavior. The authors suggest an experiment involving the study of the impact on the Casimir forces by a Mott transition in doped semiconductors. Such an experiment would permit explicit testing of the validity of the present model for Casimir forces and hence provide additional perspectives on the nature of dispersive interactions. There is an effort to store energy, e.g. H2 or CO2, inside a range of open cage-like structures, such as metal organics frameworks (MOF) or clathrates. The fact that the internal molecular adhesion is dominated by vdW forces suggests that the storage and retrieval costs could perhaps be lowered as compared to an approach that involves more traditional chemical compounds. Nijem et al have provided spectroscopic characterization of vdW interactions of both hydrogen molecules and CO in a specific MOF. The study includes a vdW-DF calculation of structure and a theoretical prediction of expected infrared activity. The potential applications to energy materials have motivated more theoretical characterizations. Li and Thonhauser use the vdW-DF method to investigate the limitations and hydrogen storage potential of hydrogen-methane compounds in a MOF. Similarly, Ihm et al combine vdW-DF studies with a thermodynamics argument to characterize the potential for molecular hydrogen uptake in expanded graphite, for example, through intercalation. The relevance of vdW-aware DFT calculations and the usefulness of such methods reaches beyond the study of molecules, surfaces and adsorption/absorption problems. Moellmann et al present a dispersion-DFT study of TiO2 bulk and surfaces, which illustrates that vdW forces can also play a prominent role when comparing the energies of different oxide structures. Perdew et al present a spherical-shell model and a simplified classical electrodynamical determination of the vdW interaction coefficients that describes the asymptotic interaction between fullerenes or other nearly spherical nanoclusters. The overall modeling framework also permits a formal expression of multipole contributions. Dappe et al used a combination of DFT and second-order perturbation theory to analyze the interactions between graphene layers, thus also exploring the role of dynamical screening in the vdW binding. The work of Sabatini et al extends the vdW-DF description with accounts of the stress tensor, providing the method with the same versatility as one has grown to expect in traditional LDA/GGA-DFT calculations. The method is illustrated with investigations of amino acid crystals under various pressures. The vdW-DF method was originally perceived as computationally more expensive than other approaches. It has now benefited from the development of efficient algorithms so the computational cost is comparable to that of traditional GGA-DFT calculations. As is also the case for some of the dispersion-DFT methods, there is an overhead when these are implemented self-consistently. Noting that sparse-matter structure determination and relaxations may well employ a sequence of methods, Le et al have suggested a simplified (cost-free relative to GGA) formulation of self-consistent dispersion-DFT calculations that is cost-free in the evaluation of forces and yet adapts the atom-centered pair-wise interaction coefficients through the change in local electron distributions. There is a need for continued testing of accuracy in the description of material properties and of the robustness and transferability of predictions across systems and length scales. This need is widely appreciated and is also reflected in the fact that many of the contributions touch on, suggest, or pursue a systematic benchmarking. There is an interest in careful analysis of detailed experiments on the physisorption of inert atoms, light molecules and organic molecules on smooth surfaces. Chen et al investigated the role of vdW forces in noble gas adsorption on various metal surfaces. Londero et al analyzed a set of experimental results for the desorption of n-alkanes from graphene in a program that had undergraduate participation. Lee et al benchmarked the performance of the vdW-DF2 functional and other methods against the physisorption potential curve that can be established from a rich data set of resonant backscattering of hydrogen molecules on various facets of Cu crystals. A few of the investigations included here noted that the vdW-DF method permits a more detailed analysis of the nature of strong physisorption and/or weak chemisorption cases than do DFT-dispersion methods and discussed the ramifications of the fact that GGA-DFT often, and vdW-aware DFT sometimes, pose difficulties for systems with a partial vdW component in the binding. Caciuc et al thus present a combined ab initio and semi-empirical vdW study comparing benzene/triazine/broazine adsorption on graphene and on boron-nitride sheets. On a more strategic note, Lazic et al broadened the discussion of a graphene/Ir(111) system and used the documented limitation of a GGA description to discuss a rationale for considering a more general switch to nonlocal functionals. Graziano et al note that the accuracy in the description of some soft layered systems like graphene and boron-nitride can be increased by changing the exchange description away from what was suggested in the original vdW-DF method. Hanke et al focused on the weak chemisorption of ethene on the various Cu facets that have an increasing degree of openness and provide a method for benchmarking through comparison with experimental observations. Finally, Björkman et al raise the question 'Are we van der Waals ready?' and proceed to test our readiness by benchmarking the performance of a range of vdW-aware methods for the group of 96 known layered structures. We have also included in this special issue one study of nonequilibrium transport which is linked to David's work in formal scattering theory [1, 2] and which observes that vdW forces (and possible generalizations to nonequilibrium transport conditions) will be of central importance in a richer computational characterization of molecular electronics under operational conditions. David was always keen to spearhead the development of tools that improved descriptions of nature and addressed actual experiments. We know that he was happy that DMP started the focused session on vdW and materials in 2011. We know that he would have thoroughly appreciated the articles in this special issue. He would have hoped, as we do, that materials theory may continue to learn how to tackle even more exciting experimental problems and that we may continue to deepen our understanding of materials and their functionality. Bibliography [1]Langreth D C 1976 1975 Nato Advanced Study Institute on Linear and Nonlinear Transport in Solids, Antwerben vol B17 (New York: Plenum) pp 3-32 [2]Langreth D C 1966 Friedel sum rule for Anderson's model of localized impurity states Phys. Rev. 150 516 [3]Langreth D C and Perdew J P 1975 The exchange-correlation energy of a metallic surface Solid State Commun. 17 1425 [4]Gunnarsson O and Lundqvist B I 1976 Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism Phys. Rev. B 13 4274 [5]Langreth D C and Mehl M J 1981 Beyond the local-density approximation in calculations of ground-state electronic properties Phys. Rev. B 47 446 [6]Dion M, Rydberg H, Schröder E, Langreth D C and Lundqvist B I 2004 Van der Waals density functional for general geometries Phys. Rev. Lett. 92 246401 Thonhauser T, Cooper V R, Li S, Puzder A, Hyldgaard P and Langreth D C 2007 Van der Waals density functional: self-consistent potential and the nature of the van der Waals bond Phys. Rev. B 76 125112 [7]Lee K, Murray E D, Kong L, Lundqvist B I and Langreth D C 2010 A higher-accuracy van der Waals density functional Phys. Rev. B 82 081101 [8]Rapcewicz K and Ashcroft N W 1991 Fluctuation attraction in condensed matter: a nonlocal functional approach Phys. Rev. B 44 4032 Lundqvist B I, Andersson Y, Shao H, Chan S and Langreth D C 1995 Density functional theory including van der Waals forces Int. J. Quant. Chem. 56 247 [9]Langreth D C et al 2009 A density functional for sparse matter J. Phys.: Condens. Matter 21 084203 [10]For example, Kohn W, Meir Y and Makarov D E 1998 The exchange-correlation energy of a metallic surface Phys. Rev. Lett. 80 4153 Kurth S and Perdew J P 1999 Phys. Rev. B 59 10461 Dobson J F and Wang J 1999 Phys. Rev. Lett. 82 2123 Pitarke J M and Perdew J P 2003 Phys. Rev. B 67 045101 Vydrov O A and van Voorhi T 2009 Phys. Rev. Lett. 103 063004 [11]For example, Grimme S 2004 J. Comput. Phys. 25 1463 Tkatchenko A and Scheffler M 2009 Phys. Rev. Lett. 102 073005 Grimme S, Antony J, Ehrlich S and Krieg H 2010 J. Chem. Phys. 132 154004 [12]Burke K 2012 Perspectives on density functional theory J. Chem. Phys. 136 150901 Van der Waals interactions in advanced materials contents Van der Waals interactions in advanced materials, in memory of David C LangrethPer Hyldgaard and Talat S Rahman Frictional temperature rise in a sliding physisorbed monolayer of Kr/grapheneM Walker, C Jaye, J Krim and Milton W Cole How to modify the van der Waals and Casimir forces without change of the dielectric permittivityG L Klimchitskaya, U Mohideen and V M Mostepanenko Spectroscopic characterization of van der Waals interactions in a metal organic framework with unsaturated metal centers: MOF-74-MgNour Nijem, Pieremanuele Canepa, Lingzhu Kong, Haohan Wu, Jing Li, Timo Thonhauser and Yves J Chabal A theoretical study of the hydrogen-storage potential of (H2)4CH4 in metal organic framework materials and carbon nanotubesQ Li and T Thonhauser The influence of dispersion interactions on the hydrogen adsorption properties of expanded graphiteYungok Ihm, Valentino R Cooper, Lujian Peng and James R Morris A DFT-D study of structural and energetic properties of TiO2 modificationsJonas Moellmann, Stephan Ehrlich, Ralf Tonner and Stefan Grimme Spherical-shell model for the van der Waals coefficients between fullerenes and/or nearly spherical nanoclustersJohn P Perdew, Jianmin Tao, Pan Hao, Adrienn Ruzsinszky, Gábor I Csonka and J M Pitarke Dynamical screening of the van der Waals interaction between graphene layersY J Dappe, P G Bolcatto, J Ortega and F Flores Structural evolution of amino acid crystals under stress from a non-empirical density functionalRiccardo Sabatini, Emine Küçükbenli, Brian Kolb, T Thonhauser and Stefano de Gironcoli Physisorption of nucleobases on graphene: a comparative van der Waals studyDuy Le, Abdelkader Kara, Elsebeth Schröder, Per Hyldgaard and Talat S Rahman The role of van der Waals interactions in the adsorption of noble gases on metal surfacesDe-Li Chen, W A Al-Saidi and J Karl Johnson Desorption of n-alkanes from graphene: a van der Waals density functional studyElisa Londero, Emma K Karlson, Marcus Landahl, Dimitri Ostrovskii, Jonatan D Rydberg and Elsebeth Schröder Benchmarking van der Waals density functionals with experimental data: potential-energy curves for H2 molecules on Cu(111), (100) and (110) surfacesKyuho Lee, Kristian Berland, Mina Yoon, Stig Andersson, Elsebeth Schröder, Per Hyldgaard and Bengt I Lundqvist Ab initio and semi-empirical van der Waals study of graphene-boron nitride interaction from a molecular point of viewVasile Caciuc, Nicolae Atodiresei, Martin Callsen, Predrag Lazić and Stefan Blügel Rationale for switching to nonlocal functionals in density functional theoryP Lazić, N Atodiresei, V Caciuc, R Brako, B Gumhalter and S Blügel Improved description of soft layered materials with van der Waals density functional theoryGabriella Graziano, Jiří Klimeš, Felix Fernandez-Alonso and Angelos Michaelides Structure and stability of weakly chemisorbed ethene adsorbed on low-index Cu surfaces: performance of density functionals with van der Waals interactionsFelix Hanke, Matthew S Dyer, Jonas Björk and Mats Persson Are we van der Waals ready?T Björkman, A Gulans, A V Krasheninnikov and R M Nieminen Nonequilibrium thermodynamics of interacting tunneling transport: variational grand potential, density functional formulation and nature of steady-state forcesP Hyldgaard

Structural, electronic, and dynamical properties of liquid water by ab initio molecular dynamics based on SCAN functional within the canonical ensemble

NASA Astrophysics Data System (ADS)

Zheng, Lixin; Chen, Mohan; Sun, Zhaoru; Ko, Hsin-Yu; Santra, Biswajit; Dhuvad, Pratikkumar; Wu, Xifan

2018-04-01

We perform ab initio molecular dynamics (AIMD) simulation of liquid water in the canonical ensemble at ambient conditions using the strongly constrained and appropriately normed (SCAN) meta-generalized-gradient approximation (GGA) functional approximation and carry out systematic comparisons with the results obtained from the GGA-level Perdew-Burke-Ernzerhof (PBE) functional and Tkatchenko-Scheffler van der Waals (vdW) dispersion correction inclusive PBE functional. We analyze various properties of liquid water including radial distribution functions, oxygen-oxygen-oxygen triplet angular distribution, tetrahedrality, hydrogen bonds, diffusion coefficients, ring statistics, density of states, band gaps, and dipole moments. We find that the SCAN functional is generally more accurate than the other two functionals for liquid water by not only capturing the intermediate-range vdW interactions but also mitigating the overly strong hydrogen bonds prescribed in PBE simulations. We also compare the results of SCAN-based AIMD simulations in the canonical and isothermal-isobaric ensembles. Our results suggest that SCAN provides a reliable description for most structural, electronic, and dynamical properties in liquid water.

Mechanical Properties of a vdW molecular monolayer at a metal surface: Structural Polymorphism leading to facile compression

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Daeho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jon; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat; Hyldgaard, Per; Bartels, Ludwig

2011-03-01

Intermolecular force plays an important role in self-assembly and surface pattern formation. Anthracene and similar unsubstituted arenes attach to a metallic substrate predominantly through van der Waals interaction leading. In this contribution we present images how anthracene on Cu(111) forms a large number of highly ordered patterns that feature a broad array of structural motifs. Density functional theory modeling including vdW interactions allows us to model the energetic of the pattern formation at high fidelity. Moreover, it allows us to deduce the strain energy associated with films of varying coverage. From this work, we obtain the Young's modulus and Poisson Ratio of a molecular monolayer, which resemble properties conventionally found for porous materials. These patterns are in marked contrast to those found after introduction of functional groups in the molecules, such as carbonyls or thiols.

van der Waals Interactions in Hadron Resonance Gas: From Nuclear Matter to Lattice QCD.

PubMed

Vovchenko, Volodymyr; Gorenstein, Mark I; Stoecker, Horst

2017-05-05

An extension of the ideal hadron resonance gas (HRG) model is constructed which includes the attractive and repulsive van der Waals (VDW) interactions between baryons. This VDW-HRG model yields the nuclear liquid-gas transition at low temperatures and high baryon densities. The VDW parameters a and b are fixed by the ground state properties of nuclear matter, and the temperature dependence of various thermodynamic observables at zero chemical potential are calculated within the VDW-HRG model. Compared to the ideal HRG model, the inclusion of VDW interactions between baryons leads to a qualitatively different behavior of second and higher moments of fluctuations of conserved charges, in particular in the so-called crossover region T∼140-190  MeV. For many observables this behavior resembles closely the results obtained from lattice QCD simulations. This hadronic model also predicts nontrivial behavior of net-baryon fluctuations in the region of phase diagram probed by heavy-ion collision experiments. These results imply that VDW interactions play a crucial role in the thermodynamics of hadron gas. Thus, the commonly performed comparisons of the ideal HRG model with the lattice and heavy-ion data may lead to misconceptions and misleading conclusions.

Computational phase diagrams of noble gas hydrates under pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teeratchanan, Pattanasak, E-mail: s1270872@sms.ed.ac.uk; Hermann, Andreas, E-mail: a.hermann@ed.ac.uk

2015-10-21

We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-I{sub h}, ice-I{sub c}, ice-II, and C{sub 0} interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogenmore » hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C{sub 0} water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C{sub 0} hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.« less

Electric field modulation of Schottky barrier height in graphene/MoSe{sub 2} van der Waals heterointerface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sata, Yohta; Moriya, Rai, E-mail: moriyar@iis.u-tokyo.ac.jp, E-mail: tmachida@iis.u-tokyo.ac.jp; Morikawa, Sei

2015-07-13

We demonstrate a vertical field-effect transistor based on a graphene/MoSe{sub 2} van der Waals (vdW) heterostructure. The vdW interface between the graphene and MoSe{sub 2} exhibits a Schottky barrier with an ideality factor of around 1.3, suggesting a high-quality interface. Owing to the low density of states in graphene, the position of the Fermi level in the graphene can be strongly modulated by an external electric field. Therefore, the Schottky barrier height at the graphene/MoSe{sub 2} vdW interface is also modulated. We demonstrate a large current ON-OFF ratio of 10{sup 5}. These results point to the potential high performance ofmore » the graphene/MoSe{sub 2} vdW heterostructure for electronics applications.« less

Valley density-wave (VDW) and Superconductivity in Iron-Pnictides

NASA Astrophysics Data System (ADS)

Cvetkovic, Vladimir; Tesanovic, Zlatko

2009-03-01

One of the experimentally observed features of iron-pnictide superconductors is the structural transition and SDW ordering occurring at almost the same temperature. Starting from a tight-binding model [1], we construct an effective theory for iron-pnictides with the distinctive two hole and two electron Fermi surfaces. This theory is then mapped onto a negative-U Hubbard model with additional orbital and spin flavors [2]. We demonstrate that the superconducting instability of the attractive Hubbard model --- valley density-wave (VDW) --- corresponds to the observed structural and SDW orders. The deviations from perfect nesting between the hole and electron Fermi surfaces are mapped onto the Zeeman field which causes portions of Fermi surface to remain ungapped. The origin of pnictide superconductivity in this model, and its ties to the VDW are discussed. [1] V. Cvetkovic and Z. Tesanovic, http://arxiv.org/abs/0804.4678. [2] V. Cvetkovic and Z. Tesanovic, http://arxiv.org/abs/0808.3742.

Structural evolution of gypsum under high pressure: single-crystal X-ray experiments revisited

NASA Astrophysics Data System (ADS)

Li, Tsung-Lung; Lee, Pei-Lun

2018-05-01

The structures of gypsum at pressures up to approximately 4 GPa are studied with density functional theory (DFT) and thoroughly compared with single-crystal X-ray diffraction experiments reported in the literature [Comodi et al. in (Am Miner 93:1530-1537, 2008)]. It is found that the exchange-correlation density functional revPBE (revised Perdew-Burke-Ernzerhof) in conjunction with a nonlocal van der Waals (vdW) correction is capable of modeling the lattice constants, axial compressibility, and bulk modulus with good accuracy, suggesting that the inclusion of the vdW functional is crucially important for understanding the structure of hydrous minerals. To gain further physical insights, the geometric parameters associated with the constituting components of gypsum (water molecules, SO4 tetrahedra, and CaO8 polyhedra) are analyzed and compared with the experimental values. DFT simulations show that, under pressure, the polyhedral layers remain as nearly planar sheets of interconnecting SO4 tetrahedra and CaO8 polyhedra without further crinkling. DFT analysis on the layer compressibility along the major crystal axis reveals that, in contrast to experimental reports, the hydrous interlayer is less compressible than the polyhedral layer. Squeezed by the lateral pressure, the water molecules in the hydrous interlayer become better affixed along the major axis, making the interlayer harder to compress along this axis.

Many-body van der Waals interactions in molecules and condensed matter.

PubMed

DiStasio, Robert A; Gobre, Vivekanand V; Tkatchenko, Alexandre

2014-05-28

This work reviews the increasing evidence that many-body van der Waals (vdW) or dispersion interactions play a crucial role in the structure, stability and function of a wide variety of systems in biology, chemistry and physics. Starting with the exact expression for the electron correlation energy provided by the adiabatic connection fluctuation-dissipation theorem, we derive both pairwise and many-body interatomic methods for computing the long-range dispersion energy by considering a model system of coupled quantum harmonic oscillators within the random-phase approximation. By coupling this approach to density functional theory, the resulting many-body dispersion (MBD) method provides an accurate and efficient scheme for computing the frequency-dependent polarizability and many-body vdW energy in molecules and materials with a finite electronic gap. A select collection of applications are presented that ascertain the fundamental importance of these non-bonded interactions across the spectrum of intermolecular (the S22 and S66 benchmark databases), intramolecular (conformational energies of alanine tetrapeptide) and supramolecular (binding energy of the 'buckyball catcher') complexes, as well as molecular crystals (cohesive energies in oligoacenes). These applications demonstrate that electrodynamic response screening and beyond-pairwise many-body vdW interactions--both captured at the MBD level of theory--play a quantitative, and sometimes even qualitative, role in describing the properties considered herein. This work is then concluded with an in-depth discussion of the challenges that remain in the future development of reliable (accurate and efficient) methods for treating many-body vdW interactions in complex materials and provides a roadmap for navigating many of the research avenues that are yet to be explored.

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

DFT-based method for more accurate adsorption energies: An adaptive sum of energies from RPBE and vdW density functionals

DOE PAGES

Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin; ...

2017-01-26

In recent years, the popularity of density functional theory with periodic boundary conditions (DFT) has surged for the design and optimization of functional materials. However, no single DFT exchange–correlation functional currently available gives accurate adsorption energies on transition metals both when bonding to the surface is dominated by strong covalent or ionic bonding and when it has strong contributions from van der Waals interactions (i.e., dispersion forces). Here we present a new, simple method for accurately predicting adsorption energies on transition-metal surfaces based on DFT calculations, using an adaptively weighted sum of energies from RPBE and optB86b-vdW (or optB88-vdW) densitymore » functionals. This method has been benchmarked against a set of 39 reliable experimental energies for adsorption reactions. Our results show that this method has a mean absolute error and root mean squared error relative to experiments of 13.4 and 19.3 kJ/mol, respectively, compared to 20.4 and 26.4 kJ/mol for the BEEF-vdW functional. For systems with large van der Waals contributions, this method decreases these errors to 11.6 and 17.5 kJ/mol. Furthermore, this method provides predictions of adsorption energies both for processes dominated by strong covalent or ionic bonding and for those dominated by dispersion forces that are more accurate than those of any current standard DFT functional alone.« less

van der Waals Layered Materials: Opportunities and Challenges.

PubMed

Duong, Dinh Loc; Yun, Seok Joon; Lee, Young Hee

2017-12-26

Since graphene became available by a scotch tape technique, a vast class of two-dimensional (2D) van der Waals (vdW) layered materials has been researched intensively. What is more intriguing is that the well-known physics and chemistry of three-dimensional (3D) bulk materials are often irrelevant, revealing exotic phenomena in 2D vdW materials. By further constructing heterostructures of these materials in the planar and vertical directions, which can be easily achieved via simple exfoliation techniques, numerous quantum mechanical devices have been demonstrated for fundamental research and technological applications. It is, therefore, necessary to review the special features in 2D vdW materials and to discuss the remaining issues and challenges. Here, we review the vdW materials library, technology relevance, and specialties of vdW materials covering the vdW interaction, strong Coulomb interaction, layer dependence, dielectric screening engineering, work function modulation, phase engineering, heterostructures, stability, growth issues, and the remaining challenges.

Diagrams for comprehensive molecular orbital-based chemical reaction analyses: reactive orbital energy diagrams.

PubMed

Tsuneda, Takao; Singh, Raman Kumar; Chattaraj, Pratim Kumar

2018-05-15

Reactive orbital energy diagrams are presented as a tool for comprehensively performing orbital-based reaction analyses. The diagrams rest on the reactive orbital energy theory, which is the expansion of conceptual density functional theory (DFT) to an orbital energy-based theory. The orbital energies on the intrinsic reaction coordinates of fundamental reactions are calculated by long-range corrected DFT, which is confirmed to provide accurate orbital energies of small molecules, combining with a van der Waals (vdW) correlation functional, in order to examine the vdW effect on the orbital energies. By analysing the reactions based on the reactive orbital energy theory using these accurate orbital energies, it is found that vdW interactions significantly affect the orbital energies in the initial reaction processes and that more than 70% of reactions are determined to be initially driven by charge transfer, while the remaining structural deformation (dynamics)-driven reactions are classified into identity, cyclization and ring-opening, unimolecular dissociation, and H2 reactions. The reactive orbital energy diagrams, which are constructed using these results, reveal that reactions progress so as to delocalize the occupied reactive orbitals, which are determined as contributing orbitals and are usually not HOMOs, by hybridizing the unoccupied reactive orbitals, which are usually not LUMOs. These diagrams also raise questions about conventional orbital-based diagrams such as frontier molecular orbital diagrams, even for the well-established interpretation of Diels-Alder reactions.

van der Waals forces in density functional theory: a review of the vdW-DF method.

PubMed

Berland, Kristian; Cooper, Valentino R; Lee, Kyuho; Schröder, Elsebeth; Thonhauser, T; Hyldgaard, Per; Lundqvist, Bengt I

2015-06-01

A density functional theory (DFT) that accounts for van der Waals (vdW) interactions in condensed matter, materials physics, chemistry, and biology is reviewed. The insights that led to the construction of the Rutgers-Chalmers van der Waals density functional (vdW-DF) are presented with the aim of giving a historical perspective, while also emphasizing more recent efforts which have sought to improve its accuracy. In addition to technical details, we discuss a range of recent applications that illustrate the necessity of including dispersion interactions in DFT. This review highlights the value of the vdW-DF method as a general-purpose method, not only for dispersion bound systems, but also in densely packed systems where these types of interactions are traditionally thought to be negligible.

Vibrational mode frequencies of H2S and H2O adsorbed on Ge(0 0 1)-(2 × 1) surfaces

NASA Astrophysics Data System (ADS)

Hartnett, M.; Fahy, S.

2015-02-01

The equilibrium geometry and vibrational modes of H2S and H2O-terminated Ge(0 0 1)-(2 × 1) surfaces are calculated in a supercell approach using first-principles density functional theory in the local density (LDA), generalized gradient (GGA) approximations and van der Waals (vdW) interactions. Mode frequencies are found using the frozen phonon method. For the H2S-passivated surface, the calculated frequencies in LDA (GGA) are 2429 cm-1 (2490) for the Hsbnd S stretch mode, 712 cm-1 (706) for the Hsbnd S bond bending mode, 377 cm-1 (36) for the Gesbnd S stretch mode and 328 cm-1 (337) for Hsbnd S wag mode. Frequencies for the H2O passivated surface are 3590 cm-1 (3600) for the Hsbnd O stretch mode, 921 cm-1 (947) for the bending mode, 609 cm-1 (559) for the Gesbnd O stretch, 1995 cm-1 (1991) for the Gesbnd H stretch mode, 498 cm-1 (478) for the Gesbnd H bending mode and 342 cm-1 (336) for the Hsbnd O wag mode. The differences between the functionals including vdW terms and the LDA or GGA are less than the differences between LDA and GGA for the vibrational mode frequencies.

Tuning the Schottky barrier in the arsenene/graphene van der Waals heterostructures by electric field

NASA Astrophysics Data System (ADS)

Li, Wei; Wang, Tian-Xing; Dai, Xian-Qi; Wang, Xiao-Long; Ma, Ya-Qiang; Chang, Shan-Shan; Tang, Ya-Nan

2017-04-01

Using density functional theory calculations, we investigate the electronic properties of arsenene/graphene van der Waals (vdW) heterostructures by applying external electric field perpendicular to the layers. It is demonstrated that weak vdW interactions dominate between arsenene and graphene with their intrinsic electronic properties preserved. We find that an n-type Schottky contact is formed at the arsenene/graphene interface with a Schottky barrier of 0.54 eV. Moreover, the vertical electric field can not only control the Schottky barrier height but also the Schottky contacts (n-type and p-type) and Ohmic contacts (n-type) at the interface. Tunable p-type doping in graphene is achieved under the negative electric field because electrons can transfer from the Dirac point of graphene to the conduction band of arsenene. The present study would open a new avenue for application of ultrathin arsenene/graphene heterostructures in future nano- and optoelectronics.

Ab-initio study of structural and electronic properties of WS2/h-BN van der Waals heterostructure

NASA Astrophysics Data System (ADS)

Ghasemi majd, Zahra; Amiri, Peiman; Taghizadeh, Seyed Fardin

2018-06-01

First-principle calculations with different exchange-correlation functionals, including LDA, GGA, semi-empirical and ab-initio van der Waals in the forms of vdW-DF2B86R and vdW-DF2 were performed to evaluate the performance of different functionals in describing the bonding mechanism, adsorption energy and interlayer distance of WS2 monolayer on and between h-BN layers. The finding was that the vdW-DF2B86R seems to be the approach best lending itself to this purpose. In order to include the van der Waals (vdW) interactions in our calculations, we used the DFT-D2 and vdW methods, which gave rise to a physical adsorption with no net charge transfer between the WS2 layer and the corresponding substrates. In addition, we investigated the electronic and structural properties of WS2 and h-BN heterolayers, using vdW-DF2B86R functional. Based on density functional theory calculations, WS2 on and between h-BN layers showed a direct band gap at the K-point, which was experimentally observed.

Long-Range Repulsion Between Spatially Confined van der Waals Dimers

NASA Astrophysics Data System (ADS)

Sadhukhan, Mainak; Tkatchenko, Alexandre

2017-05-01

It is an undisputed textbook fact that nonretarded van der Waals (vdW) interactions between isotropic dimers are attractive, regardless of the polarizability of the interacting systems or spatial dimensionality. The universality of vdW attraction is attributed to the dipolar coupling between fluctuating electron charge densities. Here, we demonstrate that the long-range interaction between spatially confined vdW dimers becomes repulsive when accounting for the full Coulomb interaction between charge fluctuations. Our analytic results are obtained by using the Coulomb potential as a perturbation over dipole-correlated states for two quantum harmonic oscillators embedded in spaces with reduced dimensionality; however, the long-range repulsion is expected to be a general phenomenon for spatially confined quantum systems. We suggest optical experiments to test our predictions, analyze their relevance in the context of intermolecular interactions in nanoscale environments, and rationalize the recent observation of anomalously strong screening of the lateral vdW interactions between aromatic hydrocarbons adsorbed on metal surfaces.

Characterizing water-metal interfaces and machine learning potential energy surfaces

NASA Astrophysics Data System (ADS)

Ryczko, Kevin

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

Low-Dimensional Materials for Optoelectronic and Bioelectronic Applications

NASA Astrophysics Data System (ADS)

Hong, Tu

In this thesis, we first discuss the fundamentals of ab initio electronic structure theory and density functional theory (DFT). We also discuss statistics related to computing thermodynamic averages of molecular dynamics (MD). We then use this theory to analyze and compare the structural, dynamical, and electronic properties of liquid water next to prototypical metals including platinum, graphite, and graphene. Our results are built on Born-Oppenheimer molecular dynamics (BOMD) generated using density functional theory (DFT) which explicitly include van der Waals (vdW) interactions within a first principles approach. All calculations reported use large simulation cells, allowing for an accurate treatment of the water-electrode interfaces. We have included vdW interactions through the use of the optB86b-vdW exchange correlation functional. Comparisons with the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional are also shown. We find an initial peak, due to chemisorption, in the density profile of the liquid water-Pt interface not seen in the liquid water-graphite interface, liquid watergraphene interface, nor interfaces studied previously. To further investigate this chemisorption peak, we also report differences in the electronic structure of single water molecules on both Pt and graphite surfaces. We find that a covalent bond forms between the single water molecule and the platinum surface, but not between the single water molecule and the graphite surface. We also discuss the effects that defects and dopants in the graphite and graphene surfaces have on the structure and dynamics of liquid water. Lastly, we introduce artificial neural networks (ANNs), and demonstrate how they can be used to machine learn electronic structure calculations. As a proof of principle, we show the success of an ANN potential energy surfaces for a dimer molecule with a Lennard-Jones potential.

van der Waals forces in density functional theory: a review of the vdW-DF method

DOE PAGES

Berland, Kristian; Cooper, Valentino R.; Lee, Kyuho; ...

2015-05-15

We review a density functional theory (DFT) that accounts for van der Waals (vdW) interactions in condensed matter, materials physics, chemistry, and biology. The insights that led to the construction of the Rutgers–Chalmers van der Waals density functional (vdW-DF) are presented with the aim of giving a historical perspective, while also emphasizing more recent efforts which have sought to improve its accuracy. In addition to technical details, we discuss a range of recent applications that illustrate the necessity of including dispersion interactions in DFT. This review highlights the value of the vdW-DF method as a general-purpose method, not only formore » dispersion bound systems, but also in densely packed systems where these types of interactions are traditionally thought to be negligible.« less

Modification of the electronic properties of hexagonal boron-nitride in BN/graphene vertical heterostructures

DOE PAGES

Pan, Minghu; Liang, Liangbo; Lin, Wenzhi; ...

2016-09-28

Van der Waals (vdW) heterostructures consist of isolated atomic planar structures, assembled layer- by-layer into desired structures in a well-defined sequence. Graphene deposited on hexagonal boron nitride (h-BN) has been first considered as a testbed system for vdW heterostructures, and many others have been demonstrated both theoretically and experimentally, revealing many attractive properties and phenomena. However, much less emphasis has been placed on how graphene actively affects h-BN properties. Here, we perform local probe measurements on single-layer h-BN grown over graphene and highlight the manifestation of a proximity effect that significantly affects the electronic properties of h-BN due to itsmore » coupling with the underlying graphene. We find electronic states originating from the graphene layer and the Cu substrate to be injected into the wide electronic gap of the h-BN top layer. Such proximity effect is further confirmed in a study of the variation of h-BN in-gap states with interlayer couplings, elucidated using a combination of topographical/ spectroscopic measurements and first-principles density functional theory calculations. In conclusion, the findings of this work indicate the potential of mutually engineering electronic properties of the components of vdW heterostructures.« less

One-step synthesis of van der Waals heterostructures of graphene and two-dimensional superconducting α -M o2C

NASA Astrophysics Data System (ADS)

Qiao, Jia-Bin; Gong, Yue; Zuo, Wei-Jie; Wei, Yi-Cong; Ma, Dong-Lin; Yang, Hong; Yang, Ning; Qiao, Kai-Yao; Shi, Jin-An; Gu, Lin; He, Lin

2017-05-01

Assembling different two-dimensional (2D) crystals, covering a very broad range of properties, into van der Waals (vdW) heterostructures enables unprecedented possibilities for combining the best of different ingredients in one objective material. So far, metallic, semiconducting, and insulating 2D crystals have been used successfully in making functional vdW heterostructures with properties by design. Here, we expand 2D superconducting crystals as a building block of vdW hererostructures. One-step growth of large-scale high-quality vdW heterostructures of graphene and 2D superconducting α -M o2C by using chemical vapor deposition is reported. The superconductivity and its 2D nature of the heterostructures are characterized by our scanning tunneling microscopy measurements. This adds 2D superconductivity, the most attractive property of condensed matter physics, to vdW heterostructures.

van der Waals torque and force between anisotropic topological insulator slabs

NASA Astrophysics Data System (ADS)

Lu, Bing-Sui

2018-01-01

We investigate the character of the van der Waals (vdW) torque and force between two coplanar and dielectrically anisotropic topological insulator (TI) slabs separated by a vacuum gap in the nonretardation regime, where the optic axes of the slabs are each perpendicular to the normal direction to the slab-gap interface and also generally differently oriented from each other. We find that in addition to the magnetoelectric coupling strength, the anisotropy can also influence the sign of the vdW force, viz., a repulsive vdW force can become attractive if the anisotropy is increased sufficiently. In addition, the vdW force oscillates as a function of the angular difference between the optic axes of the TI slabs, being most repulsive/least attractive (least repulsive/most attractive) for angular differences that are integer (half-integer) multiples of π . Our third finding is that the vdW torque for TI slabs is generally weaker than that for ordinary dielectric slabs. Our work provides an instance in which the vector potential appears in a calculation of the vdW interaction for which the limit is nonretarded or static.

Surface chemistry of oxygen on aluminum--Performance of the density functionals: PBE, PBE0, M06, and M06-L.

PubMed

Lousada, Cláudio M; Korzhavyi, Pavel A

2016-04-05

We investigated the performance of the density functional theory (DFT) functionals PBE, PBE0, M06, and M06-L for describing the molecular and dissociative adsorption of O2 onto pure and doped Al(111) surfaces. Adsorption of O2 was studied at the perfect Al(111) surface and compared with the case where an additional Al atom was present as an adatom. Additionally, we studied how these functionals perform when different dopants are present at the Al(111) surface in two distinct geometries: as an adatom or as a substitutional atom replacing an Al atom. The performance of the different functionals is greatly affected by the surface geometry. The inclusion of Hartree-Fock exchange in the functional leads to slight differences in adsorption energies for molecular adsorption of O2 . These differences become very pronounced for dissociative adsorption, with the hybrids PBE0 and M06 predicting more exergonic adsorption than PBE and M06-L. Furthermore, PBE0 and M06 predicted trends in adsorption energies for defective and perfect surfaces which are in line with the experimental knowledge of the effects of surface defects in adsorption energies. The predictions of the non-hybrids PBE and M06-L point in the opposite direction. The analysis of the contributions of the van der Waals (vdW) forces to the adsorption energies reveals that the PBE and PBE0 functionals have similar difficulties in describing vdW interactions for molecular adsorption of O2 while the M06 functional can give a description of these forces with an accuracy which is at least similar to that of the correction of the D3 type. © 2015 Wiley Periodicals, Inc.

Dispersion interactions with linear scaling DFT: a study of planar molecules on charged polar surfaces

NASA Astrophysics Data System (ADS)

Andrinopoulos, Lampros; Hine, Nicholas; Haynes, Peter; Mostofi, Arash

2010-03-01

The placement of organic molecules such as CuPc (copper phthalocyanine) on wurtzite ZnO (zinc oxide) charged surfaces has been proposed as a way of creating photovoltaic solar cellsfootnotetextG.D. Sharma et al., Solar Energy Materials & Solar Cells 90, 933 (2006) ; optimising their performance may be aided by computational simulation. Electronic structure calculations provide high accuracy at modest computational cost but two challenges are encountered for such layered systems. First, the system size is at or beyond the limit of traditional cubic-scaling Density Functional Theory (DFT). Second, traditional exchange-correlation functionals do not account for van der Waals (vdW) interactions, crucial for determining the structure of weakly bonded systems. We present an implementation of recently developed approachesfootnotetextP.L. Silvestrelli, P.R.L. 100, 102 (2008) to include vdW in DFT within ONETEPfootnotetextC.-K. Skylaris, P.D. Haynes, A.A. Mostofi and M.C. Payne, J.C.P. 122, 084119 (2005) , a linear-scaling package for performing DFT calculations using a basis of localised functions. We have applied this methodology to simple planar organic molecules, such as benzene and pentacene, on ZnO surfaces.

Van der Waals epitaxial growth of two-dimensional single-crystalline GaSe domains on graphene

DOE PAGES

Li, Xufan; Basile, Leonardo; Huang, Bing; ...

2015-07-22

Two-dimensional (2D) van der Waals (vdW) heterostructures are a family of artificially-structured materials that promise tunable optoelectronic properties for devices with enhanced functionalities. Compared to stamping, direct epitaxy of vdW heterostructures is ideal for clean interlayer interfaces and scalable device fabrication. Here, we explore the synthesis and preferred orientations of 2D GaSe atomic layers on graphene (Gr) by vdW epitaxy. Guided by the wrinkles on graphene, GaSe nuclei form that share a predominant lattice orientation. Due to vdW epitaxial growth many nuclei grow as perfectly aligned crystals and coalesce to form large (tens of microns), single-crystal flakes. Through theoretical investigationsmore » of interlayer energetics, and measurements of preferred orientations by atomic-resolution STEM and electron diffraction, a 10.9 interlayer rotation of the GaSe lattice with respect to the underlying graphene is found to be the most energetically preferred vdW heterostructure with the largest binding energy and the longest-range ordering. These GaSe/Gr vdW heterostructures exhibit an enhanced Raman E 2 1g band of monolayer GaSe along with highly-quenched photoluminescence due to strong charge transfer. Despite the very large lattice mismatch of GaSe/Gr through vdW epitaxy, the predominant orientation control and convergent formation of large single-crystal flakes demonstrated here is promising for the scalable synthesis of large-area vdW heterostructures for the development of new optical and optoelectronic devices.« less

Van der Waals epitaxial growth of two-dimensional single-crystalline GaSe domains on graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xufan; Basile, Leonardo; Huang, Bing

Two-dimensional (2D) van der Waals (vdW) heterostructures are a family of artificially-structured materials that promise tunable optoelectronic properties for devices with enhanced functionalities. Compared to stamping, direct epitaxy of vdW heterostructures is ideal for clean interlayer interfaces and scalable device fabrication. Here, we explore the synthesis and preferred orientations of 2D GaSe atomic layers on graphene (Gr) by vdW epitaxy. Guided by the wrinkles on graphene, GaSe nuclei form that share a predominant lattice orientation. Due to vdW epitaxial growth many nuclei grow as perfectly aligned crystals and coalesce to form large (tens of microns), single-crystal flakes. Through theoretical investigationsmore » of interlayer energetics, and measurements of preferred orientations by atomic-resolution STEM and electron diffraction, a 10.9 interlayer rotation of the GaSe lattice with respect to the underlying graphene is found to be the most energetically preferred vdW heterostructure with the largest binding energy and the longest-range ordering. These GaSe/Gr vdW heterostructures exhibit an enhanced Raman E 2 1g band of monolayer GaSe along with highly-quenched photoluminescence due to strong charge transfer. Despite the very large lattice mismatch of GaSe/Gr through vdW epitaxy, the predominant orientation control and convergent formation of large single-crystal flakes demonstrated here is promising for the scalable synthesis of large-area vdW heterostructures for the development of new optical and optoelectronic devices.« less

Communication: Effect of accidental mode degeneracy on Raman intensity in 2D materials: Hybrid functional study of bilayer phosphorene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yi-Yang; Zhang, Shengbai

2016-07-14

Bulk black phosphorus has two optical phonon modes labeled as A{sub g}{sup 2} and B{sub 2u}, respectively, that are nearly degenerate in frequency. However, density functional theory calculations using local or semi-local functionals cannot reproduce this degeneracy. Here, we propose a hybrid functional approach aided by van der Waals (vdW) force fields, which can accurately describe the lattice dynamic and electronic properties of both bulk and few-layer black phosphorus (phosphorene). Using this approach we show that in bilayer phosphorene, the two Raman modes derived from the B{sub 2u} and A{sub g}{sup 2} modes could exhibit strong resonance as a resultmore » of the accidental degeneracy so that both modes could be observed in Raman experiment. Without the mode degeneracy, however, the Raman intensity of the B{sub 2u}-derived mode would be too weak to be observed. We further show that the accidental degeneracy is correlated to the applied strain, which enables Raman spectroscopy to be a powerful tool for characterizing built-in strains in 2D materials, e.g., due to the interaction with substrates, which has emerged as an important issue in vdW epitaxy.« less

Modeling Adsorption and Reactions of Organic Molecules at Metal Surfaces

PubMed Central

2014-01-01

Conspectus The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdWsurf method that accurately accounts for the collective electronic response effects enables reliable modeling of structure and stability for a broad class of organic molecules adsorbed on metal surfaces. This method was demonstrated to achieve quantitative accuracy for aromatic hydrocarbons (benzene, naphthalene, anthracene, and diindenoperylene), C60, and sulfur/oxygen-containing molecules (thiophene, NTCDA, and PTCDA) on close-packed and stepped metal surfaces, leading to an overall accuracy of 0.1 Å in adsorption heights and 0.1 eV in binding energies with respect to state-of-the-art experiments. An unexpected finding is that vdW interactions contribute more to the binding of strongly bound molecules on transition-metal surfaces than for molecules physisorbed on coinage metals. The accurate inclusion of vdW interactions also significantly improves tilting angles and adsorption heights for all the studied molecules, and can qualitatively change the potential-energy surface for adsorbed molecules with flexible functional groups. Activation barriers for molecular switches and reaction precursors are modified as well. PMID:24915492

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals.

PubMed

Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-28

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H(+)/H2 level defining the standard hydrogen electrode, the OH(-)/OH(∗) level corresponding to the oxidation of the hydroxyl ion, and the H2O/OH(∗) level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

NASA Astrophysics Data System (ADS)

Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-01

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H+/H2 level defining the standard hydrogen electrode, the OH-/OH∗ level corresponding to the oxidation of the hydroxyl ion, and the H2O/OH∗ level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.

Assembly of Nanowire Arrays: Exploring Interparticle Interactions, Particle Orientation, and Mixed Particle Arrays

NASA Astrophysics Data System (ADS)

Kirby, David J.

This dissertation explores the fundamental interparticle and particle-substrate forces that contribute to nanowire assembly. Nanowires have a large aspect ratio which has made them favorable materials for applications in energy and sensing technologies. However, this anisotropy means that nanowires must be positioned and oriented during an assembly process. Within this work, the roles of gravity, van der Waals (VDW) attractions, and electrostatic repulsions are explored when different nanowire assemblies are created. Particles were synthesized by the template electrodeposition process so that stripes of different materials and therefore different VDW interactions could be patterned along the particle length. Electrostatic repulsions were provided by a small molecule coating or a porous silica shell to prevent aggregation during the assembly process. Chapters 2, 3, 5, 6, and 8 all used particles whose asymmetry was further adjusted by removal of a sacrificial segment to leave a partially etched nanowire (PEN), a rigid silica shell partially filled with a metal core. For these particles, the role of gravity was amplified due to the drastic density differences between the two segments. Topographic and high VDW surface interactions were patterned onto assembly substrates using photolithographic processing. These forces served as a passive template to direct nanowire assembly. The segment anisotropy of PENs allowed gravity to drive their sedimentation with the long axis perpendicular to the surface. The density difference between the two ends allowed them to convert between the horizontal and vertical orientation as they diffused on the substrate. Vertical arrays formed as particle concentrations increased while VDW attractions from neighboring PENs or the physical barrier of a microwell wall supported this structure. While vertical arrays were typically PENs, microwell walls were also able to enforce a vertical orientation on solid Au nanowires. These particles typically formed horizontal arrays on planar surfaces, but careful design of the microwell and nanowire dimensions enabled these particles to take on the vertical orientation. Solid nanowires and PENs with greater segment symmetry aligned parallel to the surface as gravity did not allow a conversion to the vertical orientation. When concentrated, these particles formed smectic row arrangements which were previously shown to originate from a balance of VDW attractions and electrostatic repulsions. Within rows of segmented particles, a preference was observed for like orientation of nearest neighbor particles (Chapter 6). With the aid of Monte Carlo simulations, it was determined that this observation was the result of small differences in VDW attractions between the two nanowire ends. Differences in VDW attraction were also applied to patterned surfaces (Chapter 7). Stripes of high VDW material (Au) were placed on a silica surface (a low VDW material). When relatively low surface concentrations were used, the high VDW regions collected Au nanowires and organized them into rows that were reminiscent of those observed on un-patterned surfaces at high particle concentrations. VDW and the gravitational force were explored as they combined to influence array orientation in binary PEN mixtures. Depending on the geometries of the particles combined, the contributions of gravity and interparticle interactions exhibited different balance in creating the final array. VDW and gravitational forces could also act as a force for reconfigurable nanowire assembly. In chapter 8, fluid flow was used to concentrate PENs and force them into horizontal arrangements. When fluid flow was stopped, van der Waals forces and gravity were responsible for a reorientation of the assembled particles into a standing array. These studies represent early steps into the future of nanowire assembly methods. I conclude this dissertation by discussing the implications of my work and providing perspective on their importance to the scientific community. I also offer suggestions for future work in nanowire assembly. These areas focus on the development of assembled nanowire devices, mixed nanowire assembly techniques, and potential stimuli responsive reconfigurable assemblies.

Rotational superstructure in van der Waals heterostructure of self-assembled C 60 monolayer on the WSe 2 surface

DOE PAGES

Santos, Elton J. G.; Scullion, Declan; Chu, Ximo S.; ...

2017-08-23

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C 60 molecules self-assembled on the surface of WSe 2 in well-ordered arrays with large grain sizes (~5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure inmore » the C 60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate–adsorbate and adsorbate–substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. Furthermore, this rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.« less

Rotational superstructure in van der Waals heterostructure of self-assembled C 60 monolayer on the WSe 2 surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santos, Elton J. G.; Scullion, Declan; Chu, Ximo S.

Hybrid van der Waals (vdW) heterostructures composed of two-dimensional (2D) layered materials and self-assembled organic molecules are promising systems for electronic and optoelectronic applications with enhanced properties and performance. Control of molecular assembly is therefore paramount to fundamentally understand the nucleation, ordering, alignment, and electronic interaction of organic molecules with 2D materials. Here, we report the formation and detailed study of highly ordered, crystalline monolayers of C 60 molecules self-assembled on the surface of WSe 2 in well-ordered arrays with large grain sizes (~5 μm). Using high-resolution scanning tunneling microscopy (STM), we observe a periodic 2 × 2 superstructure inmore » the C 60 monolayer and identify four distinct molecular appearances. Using vdW-corrected ab initio density functional theory (DFT) simulations, we determine that the interplay between vdW and Coulomb interactions as well as adsorbate–adsorbate and adsorbate–substrate interactions results in specific rotational arrangements of the molecules forming the superstructure. The orbital ordering through the relative positions of bonds in adjacent molecules creates a charge redistribution that links the molecule units in a long-range network. Furthermore, this rotational superstructure extends throughout the self-assembled monolayer and opens a pathway towards engineering aligned hybrid organic/inorganic vdW heterostructures with 2D layered materials in a precise and controlled way.« less

Electronic properties of blue phosphorene/graphene and blue phosphorene/graphene-like gallium nitride heterostructures.

PubMed

Sun, Minglei; Chou, Jyh-Pin; Yu, Jin; Tang, Wencheng

2017-07-05

Blue phosphorene (BlueP) is a graphene-like phosphorus nanosheet which was synthesized very recently for the first time [Nano Lett., 2016, 16, 4903-4908]. The combination of electronic properties of two different two-dimensional materials in an ultrathin van der Waals (vdW) vertical heterostructure has been proved to be an effective approach to the design of novel electronic and optoelectronic devices. Therefore, we used density functional theory to investigate the structural and electronic properties of two BlueP-based heterostructures - BlueP/graphene (BlueP/G) and BlueP/graphene-like gallium nitride (BlueP/g-GaN). Our results showed that the semiconducting nature of BlueP and the Dirac cone of G are well preserved in the BlueP/G vdW heterostructure. Moreover, by applying a perpendicular electric field, it is possible to tune the position of the Dirac cone of G with respect to the band edge of BlueP, resulting in the ability to control the Schottky barrier height. For the BlueP/g-GaN vdW heterostructure, BlueP forms an interface with g-GaN with a type-II band alignment, which is a promising feature for unipolar electronic device applications. Furthermore, we discovered that both G and g-GaN can be used as an active layer for BlueP to facilitate charge injection and enhance the device performance.

Density-Dependent Formulation of Dispersion-Repulsion Interactions in Hybrid Multiscale Quantum/Molecular Mechanics (QM/MM) Models.

PubMed

Curutchet, Carles; Cupellini, Lorenzo; Kongsted, Jacob; Corni, Stefano; Frediani, Luca; Steindal, Arnfinn Hykkerud; Guido, Ciro A; Scalmani, Giovanni; Mennucci, Benedetta

2018-03-13

Mixed multiscale quantum/molecular mechanics (QM/MM) models are widely used to explore the structure, reactivity, and electronic properties of complex chemical systems. Whereas such models typically include electrostatics and potentially polarization in so-called electrostatic and polarizable embedding approaches, respectively, nonelectrostatic dispersion and repulsion interactions are instead commonly described through classical potentials despite their quantum mechanical origin. Here we present an extension of the Tkatchenko-Scheffler semiempirical van der Waals (vdW TS ) scheme aimed at describing dispersion and repulsion interactions between quantum and classical regions within a QM/MM polarizable embedding framework. Starting from the vdW TS expression, we define a dispersion and a repulsion term, both of them density-dependent and consistently based on a Lennard-Jones-like potential. We explore transferable atom type-based parametrization strategies for the MM parameters, based on either vdW TS calculations performed on isolated fragments or on a direct estimation of the parameters from atomic polarizabilities taken from a polarizable force field. We investigate the performance of the implementation by computing self-consistent interaction energies for the S22 benchmark set, designed to represent typical noncovalent interactions in biological systems, in both equilibrium and out-of-equilibrium geometries. Overall, our results suggest that the present implementation is a promising strategy to include dispersion and repulsion in multiscale QM/MM models incorporating their explicit dependence on the electronic density.

General theoretical description of angle-resolved photoemission spectroscopy of van der Waals structures

NASA Astrophysics Data System (ADS)

Amorim, B.

2018-04-01

We develop a general theory to model the angle-resolved photoemission spectroscopy (ARPES) of commensurate and incommensurate van der Waals (vdW) structures, formed by lattice mismatched and/or misaligned stacked layers of two-dimensional materials. The present theory is based on a tight-binding description of the structure and the concept of generalized umklapp processes, going beyond previous descriptions of ARPES in incommensurate vdW structures, which are based on continuous, low-energy models, being limited to structures with small lattice mismatch/misalignment. As applications of the general formalism, we study the ARPES bands and constant energy maps for two structures: twisted bilayer graphene and twisted bilayer MoS2. The present theory should be useful in correctly interpreting experimental results of ARPES of vdW structures and other systems displaying competition between different periodicities, such as two-dimensional materials weakly coupled to a substrate and materials with density wave phases.

Toward Accurate Adsorption Energetics on Clay Surfaces

PubMed Central

2016-01-01

Clay minerals are ubiquitous in nature, and the manner in which they interact with their surroundings has important industrial and environmental implications. Consequently, a molecular-level understanding of the adsorption of molecules on clay surfaces is crucial. In this regard computer simulations play an important role, yet the accuracy of widely used empirical force fields (FF) and density functional theory (DFT) exchange-correlation functionals is often unclear in adsorption systems dominated by weak interactions. Herein we present results from quantum Monte Carlo (QMC) for water and methanol adsorption on the prototypical clay kaolinite. To the best of our knowledge, this is the first time QMC has been used to investigate adsorption at a complex, natural surface such as a clay. As well as being valuable in their own right, the QMC benchmarks obtained provide reference data against which the performance of cheaper DFT methods can be tested. Indeed using various DFT exchange-correlation functionals yields a very broad range of adsorption energies, and it is unclear a priori which evaluation is better. QMC reveals that in the systems considered here it is essential to account for van der Waals (vdW) dispersion forces since this alters both the absolute and relative adsorption energies of water and methanol. We show, via FF simulations, that incorrect relative energies can lead to significant changes in the interfacial densities of water and methanol solutions at the kaolinite interface. Despite the clear improvements offered by the vdW-corrected and the vdW-inclusive functionals, absolute adsorption energies are often overestimated, suggesting that the treatment of vdW forces in DFT is not yet a solved problem. PMID:27917256

Smoothed particle hydrodynamics simulations of evaporation and explosive boiling of liquid drops in microgravity.

PubMed

Sigalotti, Leonardo Di G; Troconis, Jorge; Sira, Eloy; Peña-Polo, Franklin; Klapp, Jaime

2015-07-01

The rapid evaporation and explosive boiling of a van der Waals (vdW) liquid drop in microgravity is simulated numerically in two-space dimensions using the method of smoothed particle hydrodynamics. The numerical approach is fully adaptive and incorporates the effects of surface tension, latent heat, mass transfer across the interface, and liquid-vapor interface dynamics. Thermocapillary forces are modeled by coupling the hydrodynamics to a diffuse-interface description of the liquid-vapor interface. The models start from a nonequilibrium square-shaped liquid of varying density and temperature. For a fixed density, the drop temperature is increased gradually to predict the point separating normal boiling at subcritical heating from explosive boiling at the superheat limit for this vdW fluid. At subcritical heating, spontaneous evaporation produces stable drops floating in a vapor atmosphere, while at near-critical heating, a bubble is nucleated inside the drop, which then collapses upon itself, leaving a smaller equilibrated drop embedded in its own vapor. At the superheat limit, unstable bubble growth leads to either fragmentation or violent disruption of the liquid layer into small secondary drops, depending on the liquid density. At higher superheats, explosive boiling occurs for all densities. The experimentally observed wrinkling of the bubble surface driven by rapid evaporation followed by a Rayleigh-Taylor instability of the thin liquid layer and the linear growth of the bubble radius with time are reproduced by the simulations. The predicted superheat limit (T(s)≈0.96) is close to the theoretically derived value of T(s)=1 at zero ambient pressure for this vdW fluid.

Vibrations of double-nanotube systems with mislocation via a newly developed van der Waals model

NASA Astrophysics Data System (ADS)

Kiani, Keivan

2015-06-01

This study deals with transverse vibrations of two adjacent-parallel-mislocated single-walled carbon nanotubes (SWCNTs) under various end conditions. These tubes interact with each other and their surrounding medium through the intertube van der Waals (vdW) forces, and existing bonds between their atoms and those of the elastic medium. The elastic energy of such forces due to the deflections of nanotubes is appropriately modeled by defining a vdW force density function. In the previous works, vdW forces between two identical tubes were idealized by a uniform form of this function. The newly introduced function enables us to investigate the influences of both intertube free distance and longitudinal mislocation on the natural transverse frequencies of the nanosystem which consists of two dissimilar tubes. Such crucial issues have not been addressed yet, even for simply supported tubes. Using nonlocal Timoshenko and higher-order beam theories as well as Hamilton's principle, the strong form of the equations of motion is established. Seeking for an explicit solution to these integro-partial differential equations is a very problematic task. Thereby, an energy-based method in conjunction with an efficient meshfree method is proposed and the nonlocal frequencies of the elastically embedded nanosystem are determined. For simply supported nanosystems, the predicted first five frequencies of the proposed model are checked with those of assumed mode method, and a reasonably good agreement is achieved. Through various studies, the roles of the tube's length ratio, intertube free space, mislocation, small-scale effect, slenderness ratio, radius of SWCNTs, and elastic constants of the elastic matrix on the natural frequencies of the nanosystem with various end conditions are explained. The limitations of the nonlocal Timoshenko beam theory are also addressed. This work can be considered as a vital step towards better realizing of a more complex system that consists of vertically aligned SWCNTs of various lengths.

Unconventional Behavior of Friction at the Nanoscale beyond Amontons' Law.

PubMed

Chen, Jingrun; Gao, Wang

2017-08-05

By means of a many-body van der Waals (vdW)-corrected density functional theory approach, the atomic-scale friction of a prototypical tip-substrate system consisting of an Si tip and a graphene substrate is studied. In a loading-sliding process, the tip-substrate distance is found to be essential for nanofrictional behavior, through determining the competition between vdW contributions and electronic contributions. As the tip approaches the substrate, this competition results in a smooth transition of normal forces from attraction to repulsion, and the friction coefficient in turn undergoes a sign change from negative to positive with possible giant magnitude and strong anisotropy. The loading-sliding process does not introduce any chemical modification of the underlying system. These findings reveal the boundary of validity of Amontons' law, unify negative and giant friction coefficients, rationalize the experimentally observed anisotropy of nanofriction, and are universal when vdW interactions are crucial, all of which are helpful to establish a comprehensive picture of nanofriction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First Principles Studies for Lithium Intercalation and Diffusion Behaviors in MoS2 treated with the Compressive Sensing Cluster Expansion

NASA Astrophysics Data System (ADS)

Liu, Chi-Ping; Zhou, Fei; Ozolins, Vidvuds

2014-03-01

Molybdenum disulfide (MoS2) is a good candidate electrode material for high capacity energy storage applications, such as lithium ion batteries and supercapacitors. In this work, we investigate lithium intercalation and diffusion kinetics in MoS2 by using first-principles density-functional theory (DFT) calculations. Two different lithium intercalation sites (1-H and 2-T) in MoS2 are found to be stable for lithium intercalation at different van der Waals' (vdW) gap distances. It is found that both thermodynamic and kinetic properties are highly related to the interlayer vdW gap distance, and that the optimal gap distance leads to effective solid-state diffusion in MoS2. Additionally, through the use of compressive sensing, we build accurate cluster expansion models to study the thermodynamic properties of MoS2 at high lithium content by truncating the higher order effective clusters with significant contributions. The results show that compressive sensing cluster expansion is a rigorous and powerful tool for model construction for advanced electrochemical applications in the future.

Accurate van der Waals force field for gas adsorption in porous materials.

PubMed

Sun, Lei; Yang, Li; Zhang, Ya-Dong; Shi, Qi; Lu, Rui-Feng; Deng, Wei-Qiao

2017-09-05

An accurate van der Waals force field (VDW FF) was derived from highly precise quantum mechanical (QM) calculations. Small molecular clusters were used to explore van der Waals interactions between gas molecules and porous materials. The parameters of the accurate van der Waals force field were determined by QM calculations. To validate the force field, the prediction results from the VDW FF were compared with standard FFs, such as UFF, Dreiding, Pcff, and Compass. The results from the VDW FF were in excellent agreement with the experimental measurements. This force field can be applied to the prediction of the gas density (H 2 , CO 2 , C 2 H 4 , CH 4 , N 2 , O 2 ) and adsorption performance inside porous materials, such as covalent organic frameworks (COFs), zeolites and metal organic frameworks (MOFs), consisting of H, B, N, C, O, S, Si, Al, Zn, Mg, Ni, and Co. This work provides a solid basis for studying gas adsorption in porous materials. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Bonding between graphene and MoS 2 monolayers without and with Li intercalation

DOE PAGES

Ahmed, Towfiq; Modine, N. A.; Zhu, Jian-Xin

2015-07-27

We performed density functional theory (DFT) calculations for a bi-layered heterostructure combining a graphene layer with a MoS 2 layer with and without intercalated Li atoms. Our calculations demonstrate the importance of the van der Waals (vdW) interaction, which is crucial for forming stable bonding between the layers. Our DFT calculation correctly reproduces the linear dispersion, or Dirac cone, feature at the Fermi energy for the isolated graphene monolayer and the band gap for the MoS 2 monolayer. For the combined graphene/MoS 2 bi-layer, we observe interesting electronic structure and density of states (DOS) characteristics near the Fermi energy, showingmore » both the gap like features of the MoS 2 layer and in-gap states with linear dispersion contributed mostly by the graphene layer. Our calculated total DOS in this vdW heterostructure reveals that the graphene layer significantly contributes to pinning the Fermi energy at the center of the band gap of MoS 2. We also find that intercalating Li ions in between the layers of the graphene/MoS2 heterostructure enhances the binding energy through orbital hybridizations between cations (Li adatoms) and anions (graphene and MoS 2 monolayers). Moreover, we calculate the dielectric function of the Li intercalated graphene/MoS 2 heterostructure, the imaginary component of which can be directly compared with experimental measurements of optical conductivity in order to validate our theoretical prediction. We observe sharp features in the imaginary component of the dielectric function, which shows the presence of a Drude peak in the optical conductivity, and therefore metallicity in the lithiated graphene/MoS 2 heterostructure.« less

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ambrosio, Francesco, E-mail: Francesco.Ambrosio@epfl.ch; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-28

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subjectmore » to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H{sup +}/H{sub 2} level defining the standard hydrogen electrode, the OH{sup −}/OH{sup ∗} level corresponding to the oxidation of the hydroxyl ion, and the H{sub 2}O/OH{sup ∗} level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.« less

Quantum dynamics of the vibrations of helium bound to the nanosurface of a large planar organic molecule: phthalocyanine . He van der Waals complex.

PubMed

Gibbons, Brittney R; Xu, Minzhong; Bacić, Zlatko

2009-04-23

We report rigorous quantum three-dimensional calculations of highly excited intermolecular vibrational states of the van der Waals (vdW) complex phthalocyanine.He (Pc.He). The Pc molecule was treated as rigid and the intermolecular potential energy surface (IPES) was represented as a sum of atom-atom Lennard-Jones pair potentials. The IPES has four equivalent global minima on the diagonals of the square-shaped Pc, inside its five-membered rings, and four slightly shallower local minima between them, creating a distinctive corrugation pattern of the molecular nanosurface. The vdW vibrational states analyzed in this work extend to about two-thirds of the well depth of the IPES. For the assignment of the in-plane (xy) vdW vibrational excitations it was necessary to resort to two sets of quantum numbers, the Cartesian quantum numbers [nu(x), nu(y)] and the quantum numbers (v, l) of the 2D isotropic oscillator, depending on the nodal structure and the symmetry of the wave functions. The delocalization of the He atom parallel to the molecular surface is large already in the ground vdW state. It increases rapidly with the number of quanta in the in-plane vdW vibrations, with the maximum root-mean-square amplitudes Deltax and Deltay of about 7 au at the excitation energies around 40 cm(-1). The wave functions of the highly excited states tend to be delocalized over the entire nanosurface and often have a square shape, reflecting that of the substrate.

Room Temperature Intrinsic Ferromagnetism in Epitaxial Manganese Selenide Films in the Monolayer Limit

NASA Astrophysics Data System (ADS)

O'Hara, Dante J.; Zhu, Tiancong; Trout, Amanda H.; Ahmed, Adam S.; Luo, Yunqiu Kelly; Lee, Choong Hee; Brenner, Mark R.; Rajan, Siddharth; Gupta, Jay A.; McComb, David W.; Kawakami, Roland K.

2018-05-01

Monolayer van der Waals (vdW) magnets provide an exciting opportunity for exploring two-dimensional (2D) magnetism for scientific and technological advances, but the intrinsic ferromagnetism has only been observed at low temperatures. Here, we report the observation of room temperature ferromagnetism in manganese selenide (MnSe$_x$) films grown by molecular beam epitaxy (MBE). Magnetic and structural characterization provides strong evidence that in the monolayer limit, the ferromagnetism originates from a vdW manganese diselenide (MnSe$_2$) monolayer, while for thicker films it could originate from a combination of vdW MnSe$_2$ and/or interfacial magnetism of $\\alpha$-MnSe(111). Magnetization measurements of monolayer MnSe$_x$ films on GaSe and SnSe$_2$ epilayers show ferromagnetic ordering with large saturation magnetization of ~ 4 Bohr magnetons per Mn, which is consistent with density functional theory calculations predicting ferromagnetism in monolayer 1T-MnSe$_2$. Growing MnSe$_x$ films on GaSe up to high thickness (~ 40 nm) produces $\\alpha$-MnSe(111), and an enhanced magnetic moment (~ 2x) compared to the monolayer MnSe$_x$ samples. Detailed structural characterization by scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), and reflection high energy electron diffraction (RHEED) reveal an abrupt and clean interface between GaSe(0001) and $\\alpha$-MnSe(111). In particular, the structure measured by STEM is consistent with the presence of a MnSe$_2$ monolayer at the interface. These results hold promise for potential applications in energy efficient information storage and processing.

Protein-protein interfaces are vdW dominant with selective H-bonds and (or) electrostatics towards broad functional specificity.

PubMed

Nilofer, Christina; Sukhwal, Anshul; Mohanapriya, Arumugam; Kangueane, Pandjassarame

2017-01-01

Several catalysis, cellular regulation, immune function, cell wall assembly, transport, signaling and inhibition occur through Protein- Protein Interactions (PPI). This is possible with the formation of specific yet stable protein-protein interfaces. Therefore, it is of interest to understand its molecular principles using structural data in relation to known function. Several interface features have been documented using known X-ray structures of protein complexes since 1975. This has improved our understanding of the interface using structural features such as interface area, binding energy, hydrophobicity, relative hydrophobicity, salt bridges and hydrogen bonds. The strength of binding between two proteins is dependent on interface size (number of residues at the interface) and thus its corresponding interface area. It is known that large interfaces have high binding energy (sum of (van der Waals) vdW, H-bonds, electrostatics). However, the selective role played by each of these energy components and more especially that of vdW is not explicitly known. Therefore, it is important to document their individual role in known protein-protein structural complexes. It is of interest to relate interface size with vdW, H-bonds and electrostatic interactions at the interfaces of protein structural complexes with known function using statistical and multiple linear regression analysis methods to identify the prominent force. We used the manually curated non-redundant dataset of 278 hetero-dimeric protein structural complexes grouped using known functions by Sowmya et al. (2015) to gain additional insight to this phenomenon using a robust inter-atomic non-covalent interaction analyzing tool PPCheck (Anshul and Sowdhamini, 2015). This dataset consists of obligatory (enzymes, regulator, biological assembly), immune and nonobligatory (enzyme and regulator inhibitors) complexes. Results show that the total binding energy is more for large interfaces. However, this is not true for its individual energy factors. Analysis shows that vdW energies contribute to about 75% ± 11% on average among all complexes and it also increases with interface size (r2 ranging from 0.67 to 0.89 with p<0.01) at 95% confidence limit irrespective of molecular function. Thus, vdW is both dominant and proportional at the interface independent of molecular function. Nevertheless, H bond energy contributes to 15% ± 6.5% on average in these complexes. It also moderately increases with interface size (r2 ranging from 0.43 to 0.61 with p<0.01) only among obligatory and immune complexes. Moreover, there is about 11.3% ± 8.7% contribution by electrostatic energy. It increases with interface size specifically among non-obligatory regulator-inhibitors (r2 = 0.44). It is implied that both H-bonds and electrostatics are neither dominant nor proportional at the interface. Nonetheless, their presence cannot be ignored in binding. Therefore, H-bonds and (or) electrostatic energy having specific role for improved stability in complexes is implied. Thus, vdW is common at the interface stabilized further with selective H-bonds and (or) electrostatic interactions at an atomic level in almost all complexes. Comparison of this observation with residue level analysis of the interface is compelling. The role by H-bonds (14.83% ± 6.5% and r2 = 0.61 with p<0.01) among obligatory and electrostatic energy (8.8% ± 4.77% and r2 = 0.63 with p <0.01) among non-obligatory complexes within interfaces (class A) having more non-polar residues than surface is influencing our inference. However, interfaces (class B) having less non-polar residues than surface show 1.5 fold more electrostatic energy on average. The interpretation of the interface using inter-atomic (vdW, H-bonds, electrostatic) interactions combined with inter-residue predominance (class A and class B) in relation to known function is the key to reveal its molecular principles with new challenges.

First-Principles Thermodynamics of Energetic Materials

DTIC Science & Technology

2012-01-01

thermal and zero-point energy ( ZPE ) effects on the crystalline environment [8]. By including vdW, thermal, and ZPE effects into DFT (DFT+vdW+T...by their relation to experiment (triangles) pure DFT over-predicts, while DFT+vdW under-predicts the EOSs. Only when temperature and ZPE effects...crystals with ZPE effects still included. To get a sense of how the vdW damping function might affect the calculation of the dynamical matrix, the

Multibody correlations in the hydrophobic solvation of glycine peptides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harris, Robert C.; Drake, Justin A.; Pettitt, B. Montgomery, E-mail: mpettitt@utmb.edu

2014-12-14

Protein collapse during folding is often assumed to be driven by a hydrophobic solvation energy (ΔG{sub vdw}) that scales linearly with solvent-accessible surface area (A). In a previous study, we argued that ΔG{sub vdw}, as well as its attractive (ΔG{sub att}) and repulsive (ΔG{sub rep}) components, was not simply a linear function of A. We found that the surface tensions, γ{sub rep}, γ{sub att}, and γ{sub vdw}, gotten from ΔG{sub rep}, ΔG{sub att}, and ΔG{sub vdw} against A for four configurations of deca-alanine differed from those obtained for a set of alkanes. In the present study, we extend our analysismore » to fifty decaglycine structures and atomic decompositions. We find that different configurations of decaglycine generate different estimates of γ{sub rep}. Additionally, we considered the reconstruction of the solvation free energy from scaling the free energy of solvation of each atom type, free in solution. The free energy of the isolated atoms, scaled by the inverse surface area the atom would expose in the molecule does not reproduce the γ{sub rep} for the intact decaglycines. Finally, γ{sub att} for the decaglycine conformations is much larger in magnitude than those for deca-alanine or the alkanes, leading to large negative values of γ{sub vdw} (−74 and −56 cal/mol/Å{sup 2} for CHARMM27 and AMBER ff12sb force fields, respectively). These findings imply that ΔG{sub vdw} favors extended rather than compact structures for decaglycine. We find that ΔG{sub rep} and ΔG{sub vdw} have complicated dependencies on multibody correlations between solute atoms, on the geometry of the molecular surface, and on the chemical identities of the atoms.« less

Persistent photoconductivity in two-dimensional Mo 1-xW xSe 2–MoSe 2 van der Waals heterojunctions

DOE PAGES

Puretzky, Alexander A.; Basile, Leonardo; Idrobo, Juan Carlos; ...

2016-02-16

Van der Waals (vdW) heterojunctions consisting of vertically-stacked individual or multiple layers of two-dimensional (2D) layered semiconductors, especially the transition metal dichalcogenides (TMDs), are fascinating new artificial solids just nanometers-thin that promise novel optoelectronic functionalities due to the sensitivity of their electronic and optical properties to strong quantum confinement and interfacial interactions. Here, monolayers of n-type MoSe 2 and p-type Mo 1-xW xSe 2–MoSe 2 are grown by vapor transport methods, then transferred and stamped to form artificial vdW heterostructures with different interlayer orientations. Atomic-resolution Z-contrast electron microscopy and electron diffraction are used to characterize both the individual monolayers andmore » the atomic registry between layers in the bilayer vdW heterostructures. These measurements are compared with photoluminescence and low-frequency Raman spectroscopy, which indicates strong interlayer coupling in heterostructures. Remarkably, the heterojunctions exhibit an unprecedented photoconductivity effect that persists at room temperature for several days. This persistent photoconductivity is shown to be tunable by applying a gate bias that equilibrates the charge distribution. Furthermore, these measurements indicate that such ultrathin vdW heterojunctions can function as rewritable optoelectronic switches or memory elements under time-dependent photo-illumination, an effect which appears promising for new monolayer TMDs-based optoelectronic devices applications.« less

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit.

PubMed

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-08

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ∼3  nm. Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

The Nature of Bonding in Bulk Tellurium Composed of One-Dimensional Helical Chains.

PubMed

Yi, Seho; Zhu, Zhili; Cai, Xiaolin; Jia, Yu; Cho, Jun-Hyung

2018-05-07

Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.

Probing Carrier Transport and Structure-Property Relationship of Highly Ordered Organic Semiconductors at the Two-Dimensional Limit

NASA Astrophysics Data System (ADS)

Zhang, Yuhan; Qiao, Jingsi; Gao, Si; Hu, Fengrui; He, Daowei; Wu, Bing; Yang, Ziyi; Xu, Bingchen; Li, Yun; Shi, Yi; Ji, Wei; Wang, Peng; Wang, Xiaoyong; Xiao, Min; Xu, Hangxun; Xu, Jian-Bin; Wang, Xinran

2016-01-01

One of the basic assumptions in organic field-effect transistors, the most fundamental device unit in organic electronics, is that charge transport occurs two dimensionally in the first few molecular layers near the dielectric interface. Although the mobility of bulk organic semiconductors has increased dramatically, direct probing of intrinsic charge transport in the two-dimensional limit has not been possible due to excessive disorders and traps in ultrathin organic thin films. Here, highly ordered single-crystalline mono- to tetralayer pentacene crystals are realized by van der Waals (vdW) epitaxy on hexagonal BN. We find that the charge transport is dominated by hopping in the first conductive layer, but transforms to bandlike in subsequent layers. Such an abrupt phase transition is attributed to strong modulation of the molecular packing by interfacial vdW interactions, as corroborated by quantitative structural characterization and density functional theory calculations. The structural modulation becomes negligible beyond the second conductive layer, leading to a mobility saturation thickness of only ˜3 nm . Highly ordered organic ultrathin films provide a platform for new physics and device structures (such as heterostructures and quantum wells) that are not possible in conventional bulk crystals.

Density, structure, and dynamics of water: The effect of van der Waals interactions

NASA Astrophysics Data System (ADS)

Wang, Jue; Román-Pérez, G.; Soler, Jose M.; Artacho, Emilio; Fernández-Serra, M.-V.

2011-01-01

It is known that ab initio molecular dynamics (AIMD) simulations of liquid water at ambient conditions, based on the generalized gradient approximation (GGA) to density functional theory (DFT), with commonly used functionals fail to produce structural and diffusive properties in reasonable agreement with experiment. This is true for canonical, constant temperature simulations where the density of the liquid is fixed to the experimental density. The equilibrium density, at ambient conditions, of DFT water has recently been shown by Schmidt et al. [J. Phys. Chem. B, 113, 11959 (2009)] to be underestimated by different GGA functionals for exchange and correlation, and corrected by the addition of interatomic pair potentials to describe van der Waals (vdW) interactions. In this contribution we present a DFT-AIMD study of liquid water using several GGA functionals as well as the van der Waals density functional (vdW-DF) of Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. As expected, we find that the density of water is grossly underestimated by GGA functionals. When a vdW-DF is used, the density improves drastically and the experimental diffusivity is reproduced without the need of thermal corrections. We analyze the origin of the density differences between all the functionals. We show that the vdW-DF increases the population of non-H-bonded interstitial sites, at distances between the first and second coordination shells. However, it excessively weakens the H-bond network, collapsing the second coordination shell. This structural problem is partially associated to the choice of GGA exchange in the vdW-DF. We show that a different choice for the exchange functional is enough to achieve an overall improvement both in structure and diffusivity.

PS1-20: VDW Operational Committee: Current Activities and Future Directions

PubMed Central

Brown, Jeffrey; McDonald, Sarah; Moore, Kristen; Saylor, Gwyn; Hart, Gene; Hornbrook, Mark; Magid, David; Go, Alan

2010-01-01

Background/Aims: The Virtual Data Warehouse (VDW) is the HMO Research Network (HMORN) approach for facilitating multisite research while protecting the privacy of members and proprietary corporate information. A valid and sustainable VDW is critical to the success of the HMORN, and is needed for HMORN’s inclusion in many of the most important public health initiatives planned for the next few years. Methods: In November 2007 the HMORN Governing Board approved the VDW 5-Year Strategic Plan, including creation of a VDW Operational Committee (VOC), reporting to the Assets Stewardship Committee (ASC) and providing coordinated oversight of the development, maintenance, and enhancement of the VDW. The seven members of the VOC are investigators and analysts representing HMORN’s major consortia projects: CERT, CVRN and CRN. Results: In 2008, the VOC accomplished two major short term goals: Creation of a comprehensive data quality checking system, implemented by seven content area expert Working Groups (WGs) consisting of 23 investigators and 23 programmer\\analysts. The content areas of the WGs are enrollment and demographics, pharmacy, utilization, tumor, vital signs, laboratory, and census. The WGs assessed data availability and completeness for their content area and reported findings to the VOC and ASC, including recommendations for changes and enhancements. WG reports will form the basis for ongoing VDW documentation that will be used to standardize HMORN VDW descriptions for grants and proposals; Development of a budget, staffing plan and priorities for 2009. The 2009 priorities include development of VOC standard operating procedures for creating new data content areas and changing current data areas/definitions, documenting policies for use of the VDW, promoting use of the VDW, and creation of additional WGs for death (new VDW content area), informatics, implementation, and data documentation. The documentation WG will oversee issues such as data dictionaries, data checking documentation, programming resources, a clinical concepts library, user guides, and incorporating updated VDW information in the HMORN Collaboration Toolkit. Looking forward, the VDW 5-year Strategic Plan includes streamlining IRB approval for multisite research and enhancing HMORN informatics capabilities. Conclusions: The newly created VOC has made substantial progress in helping make the HMORN VDW an even more valuable and useful resource for the network.

PS3-21: Extracting Utilization Data from Clarity into VDW Using Oracle and SAS

PubMed Central

Chimmula, Srivardhan

2013-01-01

Background/Aims The purpose of the presentation is to demonstrate how we use SAS and Oracle to load VDW_Utilization, VDW_DX, and VDW_PX tables from Clarity at the Kaiser Permanente Northern California (KPNC) Division of Research (DOR) site. Methods DOR uses the best of Oracle PL/ SQL and SAS capabilities in building Extract Transform and Load (ETL) processes. These processes extract patient encounter, diagnosis, and procedure data from Teradata-based Clarity. The data is then transformed to fit HMORN’s VDW definitions of the table. This data is then loaded into the Oracle-based VDW table on DOR’s research database and then finally a copy of the table is also created as a SAS dataset. Results DOR builds robust and efficient ETL processes that refresh VDW Utilization table on a monthly basis processing millions of records/observations. The ETL processes have the capability to identify daily changes in Clarity and update the VDW tables on a daily basis. Conclusions KPNC DOR combines the best of both Oracle and SAS worlds to build ETL processes that load the data into VDW Utilization tables efficiently.

Including screening in van der Waals corrected density functional theory calculations: the case of atoms and small molecules physisorbed on graphene.

PubMed

Silvestrelli, Pier Luigi; Ambrosetti, Alberto

2014-03-28

The Density Functional Theory (DFT)/van der Waals-Quantum Harmonic Oscillator-Wannier function (vdW-QHO-WF) method, recently developed to include the vdW interactions in approximated DFT by combining the quantum harmonic oscillator model with the maximally localized Wannier function technique, is applied to the cases of atoms and small molecules (X=Ar, CO, H2, H2O) weakly interacting with benzene and with the ideal planar graphene surface. Comparison is also presented with the results obtained by other DFT vdW-corrected schemes, including PBE+D, vdW-DF, vdW-DF2, rVV10, and by the simpler Local Density Approximation (LDA) and semilocal generalized gradient approximation approaches. While for the X-benzene systems all the considered vdW-corrected schemes perform reasonably well, it turns out that an accurate description of the X-graphene interaction requires a proper treatment of many-body contributions and of short-range screening effects, as demonstrated by adopting an improved version of the DFT/vdW-QHO-WF method. We also comment on the widespread attitude of relying on LDA to get a rough description of weakly interacting systems.

Two-dimensional GaSe/MoSe 2 misfit bilayer heterojunctions by van der Waals epitaxy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xufan; Lin, Ming-Wei; Lin, Junhao

Two-dimensional (2D) heterostructures hold the promise for future atomically-thin electronics and optoelectronics due to their diverse functionalities. While heterostructures consisting of different transition metal dichacolgenide monolayers with well-matched lattices and novel physical properties have been successfully fabricated via van der Waals (vdW) or edge epitaxy, constructing heterostructures from monolayers of layered semiconductors with large lattice misfits still remains challenging. Here, we report the growth of monolayer GaSe/MoSe 2 heterostructures with large lattice misfit by two-step chemical vapor deposition (CVD). Both vertically stacked and lateral heterostructures are demonstrated. The vertically stacked GaSe/MoSe 2 heterostructures exhibit vdW epitaxy with well-aligned lattice orientationmore » between the two layers, forming an incommensurate vdW heterostructure. However, the lateral heterostructures exhibit no lateral epitaxial alignment at the interface between GaSe and MoSe 2 crystalline domains. Instead of a direct lateral connection at the boundary region where the same lattice orientation is observed between GaSe and MoSe 2 monolayer domains in lateral GaSe/MoSe 2 heterostructures, GaSe monolayers are found to overgrow MoSe 2 during CVD, forming a stripe of vertically stacked vdW heterostructure at the crystal interface. Such vertically-stacked vdW GaSe/MoSe 2 heterostructures are shown to form p-n junctions with effective transport and separation of photo-generated charge carriers between layers, resulting in a gate-tunable photovoltaic response. In conclusion, these GaSe/MoSe 2 vdW heterostructures should have applications as gate-tunable field-effect transistors, photodetectors, and solar cells.« less

Two-dimensional GaSe/MoSe 2 misfit bilayer heterojunctions by van der Waals epitaxy

DOE PAGES

Li, Xufan; Lin, Ming-Wei; Lin, Junhao; ...

2016-04-01

Two-dimensional (2D) heterostructures hold the promise for future atomically-thin electronics and optoelectronics due to their diverse functionalities. While heterostructures consisting of different transition metal dichacolgenide monolayers with well-matched lattices and novel physical properties have been successfully fabricated via van der Waals (vdW) or edge epitaxy, constructing heterostructures from monolayers of layered semiconductors with large lattice misfits still remains challenging. Here, we report the growth of monolayer GaSe/MoSe 2 heterostructures with large lattice misfit by two-step chemical vapor deposition (CVD). Both vertically stacked and lateral heterostructures are demonstrated. The vertically stacked GaSe/MoSe 2 heterostructures exhibit vdW epitaxy with well-aligned lattice orientationmore » between the two layers, forming an incommensurate vdW heterostructure. However, the lateral heterostructures exhibit no lateral epitaxial alignment at the interface between GaSe and MoSe 2 crystalline domains. Instead of a direct lateral connection at the boundary region where the same lattice orientation is observed between GaSe and MoSe 2 monolayer domains in lateral GaSe/MoSe 2 heterostructures, GaSe monolayers are found to overgrow MoSe 2 during CVD, forming a stripe of vertically stacked vdW heterostructure at the crystal interface. Such vertically-stacked vdW GaSe/MoSe 2 heterostructures are shown to form p-n junctions with effective transport and separation of photo-generated charge carriers between layers, resulting in a gate-tunable photovoltaic response. In conclusion, these GaSe/MoSe 2 vdW heterostructures should have applications as gate-tunable field-effect transistors, photodetectors, and solar cells.« less

Polytypism and unexpected strong interlayer coupling in two-dimensional layered ReS2

NASA Astrophysics Data System (ADS)

Qiao, Xiao-Fen; Wu, Jiang-Bin; Zhou, Linwei; Qiao, Jingsi; Shi, Wei; Chen, Tao; Zhang, Xin; Zhang, Jun; Ji, Wei; Tan, Ping-Heng

2016-04-01

Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and anisotropic-like (AI) N layer (NL, N > 1) ReS2 are revealed by ultralow- and high-frequency Raman spectroscopy, photoluminescence and first-principles density functional theory calculation. Two interlayer shear modes are observed in AI-NL-ReS2 while only one shear mode appears in IS-NL-ReS2, suggesting anisotropic- and isotropic-like stacking orders in IS- and AI-NL-ReS2, respectively. This explicit difference in the observed frequencies identifies an unexpected strong interlayer coupling in IS- and AI-NL-ReS2. Quantitatively, the force constants of them are found to be around 55-90% of those of multilayer MoS2. The revealed strong interlayer coupling and polytypism in multi-layer ReS2 may stimulate future studies on engineering physical properties of other anisotropic 2D materials by stacking orders.Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and anisotropic-like (AI) N layer (NL, N > 1) ReS2 are revealed by ultralow- and high-frequency Raman spectroscopy, photoluminescence and first-principles density functional theory calculation. Two interlayer shear modes are observed in AI-NL-ReS2 while only one shear mode appears in IS-NL-ReS2, suggesting anisotropic- and isotropic-like stacking orders in IS- and AI-NL-ReS2, respectively. This explicit difference in the observed frequencies identifies an unexpected strong interlayer coupling in IS- and AI-NL-ReS2. Quantitatively, the force constants of them are found to be around 55-90% of those of multilayer MoS2. The revealed strong interlayer coupling and polytypism in multi-layer ReS2 may stimulate future studies on engineering physical properties of other anisotropic 2D materials by stacking orders. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01569g

Changes in the reflectivity of a lithium niobate crystal decorated with a graphene layer

NASA Astrophysics Data System (ADS)

Salas, O.; Garcés, E.; Castillo, F. L.; Magaña, L. F.

2017-01-01

Density functional theory and molecular dynamics were used to study the interaction of a graphene layer with the surface of lithium niobate. The simulations were performed at atmospheric pressure and 300K. We found that the graphene layer is physisorbed with an adsorption energy of -0.8205 eV/C-atom. Subsequently, the optical absorption of the graphene-(lithium niobate) system was calculated and compared with that of graphene solo and lithium niobate alone, respectively. The calculations were performed using the Quantum Espresso code with the GGA approximation and Vdw-DF2 (which includes long-range correlation effects as Van der Waals interactions).

C-A1-03: Considerations in the Design and Use of an Oracle-based Virtual Data Warehouse

PubMed Central

Bredfeldt, Christine; McFarland, Lela

2011-01-01

Background/Aims The amount of clinical data available for research is growing exponentially. As it grows, increasing the efficiency of both data storage and data access becomes critical. Relational database management systems (rDBMS) such as Oracle are ideal solutions for managing longitudinal clinical data because they support large-scale data storage and highly efficient data retrieval. In addition, they can greatly simplify the management of large data warehouses, including security management and regular data refreshes. However, the HMORN Virtual Data Warehouse (VDW) was originally designed based on SAS datasets, and this design choice has a number of implications for both the design and use of an Oracle-based VDW. From a design standpoint, VDW tables are designed as flat SAS datasets, which do not take full advantage of Oracle indexing capabilities. From a data retrieval standpoint, standard VDW SAS scripts do not take advantage of SAS pass-through SQL capabilities to enable Oracle to perform the processing required to narrow datasets to the population of interest. Methods Beginning in 2009, the research department at Kaiser Permanente in the Mid-Atlantic States (KPMA) has developed an Oracle-based VDW according to the HMORN v3 specifications. In order to take advantage of the strengths of relational databases, KPMA introduced an interface layer to the VDW data, using views to provide access to standardized VDW variables. In addition, KPMA has developed SAS programs that provide access to SQL pass-through processing for first-pass data extraction into SAS VDW datasets for processing by standard VDW scripts. Results We discuss both the design and performance considerations specific to the KPMA Oracle-based VDW. We benchmarked performance of the Oracle-based VDW using both standard VDW scripts and an initial pre-processing layer to evaluate speed and accuracy of data return. Conclusions Adapting the VDW for deployment in an Oracle environment required minor changes to the underlying structure of the data. Further modifications of the underlying data structure would lead to performance enhancements. Maximally efficient data access for standard VDW scripts requires an extra step that involves restricting the data to the population of interest at the data server level prior to standard processing.

Effects of partial La filling and Sb vacancy defects on CoS b 3 skutterudites

DOE PAGES

Hu, Chongze; Zeng, Xiaoyu; Liu, Yufei; ...

2017-04-25

Over the past decade, the open frame ("cagey") structure of CoSb 3 skutterudite has invited intensive filling studies with various rare-earth elements for delivering state-of-the-art mid-temperature thermoelectric performance. In order to rationalize previously reported experimental results and provide new insight into the underexplored roles of La fillers and Sb vacancies, ab initio density functional theory studies, along with semi-classical Boltzmann transport theory calculations, are performed for pristine CoSb 3 of different lattice settings and La-filled CoSb 3 with and without Sb s mono- and di-vacancy defects. We examine the effects of van der Waals (vdW) interactions, spin-orbit coupling (SOC), spinmore » polarization, partial La-filling, and Sb vacancy defects on the structural, electronic, and thermoelectric properties. The vdW interactions profoundly affect the lattice constant, which in turn affects the band gap. The SOC shows minor effects on the electronic and thermoelectric properties. The peculiar quasi-Dirac band in the pristine CoSb 3 largely survives La filling but not Sb vacancies, which instead introduce dispersive bands in the band gap region. Importantly, the band structure, density of states, and Fermi surface of La-filled CoSb 3 are significantly spin polarized, giving rise to spin-dependent thermoelectric properties. Seebeck coefficients directly calculated as a function of chemical potential are interpreted in connection with the electronic structures. Temperature-dependent Seebeck coefficients derived for the experimentally studied materials agree well with available experimental data. Seebeck coefficients obtained as a function of charge carrier concentration corroborate a thermoelectrically favorable role at high filling fractions played by the electron/hole pockets on the Fermi surface associated with the degenerate valleys/hills in the conduction/valence bands, respectively. Our results serve to advance the understanding of CoSb 3 skutterudite, a class of materials with important fundamental and application implications for thermoelectrics and spintronics.« less

Effects of partial La filling and Sb vacancy defects on CoS b 3 skutterudites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Chongze; Zeng, Xiaoyu; Liu, Yufei

Over the past decade, the open frame ("cagey") structure of CoSb 3 skutterudite has invited intensive filling studies with various rare-earth elements for delivering state-of-the-art mid-temperature thermoelectric performance. In order to rationalize previously reported experimental results and provide new insight into the underexplored roles of La fillers and Sb vacancies, ab initio density functional theory studies, along with semi-classical Boltzmann transport theory calculations, are performed for pristine CoSb 3 of different lattice settings and La-filled CoSb 3 with and without Sb s mono- and di-vacancy defects. We examine the effects of van der Waals (vdW) interactions, spin-orbit coupling (SOC), spinmore » polarization, partial La-filling, and Sb vacancy defects on the structural, electronic, and thermoelectric properties. The vdW interactions profoundly affect the lattice constant, which in turn affects the band gap. The SOC shows minor effects on the electronic and thermoelectric properties. The peculiar quasi-Dirac band in the pristine CoSb 3 largely survives La filling but not Sb vacancies, which instead introduce dispersive bands in the band gap region. Importantly, the band structure, density of states, and Fermi surface of La-filled CoSb 3 are significantly spin polarized, giving rise to spin-dependent thermoelectric properties. Seebeck coefficients directly calculated as a function of chemical potential are interpreted in connection with the electronic structures. Temperature-dependent Seebeck coefficients derived for the experimentally studied materials agree well with available experimental data. Seebeck coefficients obtained as a function of charge carrier concentration corroborate a thermoelectrically favorable role at high filling fractions played by the electron/hole pockets on the Fermi surface associated with the degenerate valleys/hills in the conduction/valence bands, respectively. Our results serve to advance the understanding of CoSb 3 skutterudite, a class of materials with important fundamental and application implications for thermoelectrics and spintronics.« less

Coarse-Grained Model for Water Involving a Virtual Site.

PubMed

Deng, Mingsen; Shen, Hujun

2016-02-04

In this work, we propose a new coarse-grained (CG) model for water by combining the features of two popular CG water models (BMW and MARTINI models) as well as by adopting a topology similar to that of the TIP4P water model. In this CG model, a CG unit, representing four real water molecules, consists of a virtual site, two positively charged particles, and a van der Waals (vdW) interaction center. Distance constraint is applied to the bonds formed between the vdW interaction center and the positively charged particles. The virtual site, which carries a negative charge, is determined by the locations of the two positively charged particles and the vdW interaction center. For the new CG model of water, we coined the name "CAVS" (charge is attached to a virtual site) due to the involvment of the virtual site. After being tested in molecular dynamic (MD) simulations of bulk water at various time steps, under different temperatures and in different salt (NaCl) concentrations, the CAVS model offers encouraging predictions for some bulk properties of water (such as density, dielectric constant, etc.) when compared to experimental ones.

Wave function delocalization and large-amplitude vibrations of helium on corrugated aromatic microsurfaces: tetracene.He and pentacene.He van der Waals complexes.

PubMed

Xu, Minzhong; Bacić, Zlatko

2007-08-09

We report accurate quantum three-dimensional calculations of highly excited intermolecular vibrational states of the van der Waals (vdW) complexes tetracene.He and pentacene.He in the S1 excited electronic state. The aromatic molecules were taken to be rigid and the intermolecular potential energy surfaces (IPESs) were modeled as a sum of atom-atom Lennard-Jones pair potentials. The IPESs are corrugated in the direction of the long (x) axis of the aromatic molecules, due to the presence of the symmetrically equivalent global double minimum for tetracene.He, and a triple minimum (central global minimum and two equivalent local minima) for pentacene.He, on each side of the aromatic plane. Both IPESs have two additional minor equivalent local minima further away from the center of the molecule. The vdW vibrational states analyzed in this work cover about 80% of the well depths of the IPESs. The mode coupling is generally weak for those states whose out-of-plane (z) mode is unexcited. However, the z-mode fundamental is strongly coupled to the short-axis (y) in-plane mode, so that the pure z-mode excitation could not be identified. The He atom exhibits large in-plane spatial delocalizaton already in the ground vdW vibrational state, which increases rapidly upon the excitation of the in-plane x and y modes, with little hindrance by the corrugation of the aromatic microsurfaces. For the vdW vibrational energies considered, the He atom spatial delocalization reaches Deltax and Deltay values of approximately 5 and 4 A, respectively, and is limited only by the finite size of the aromatic substrates. Side-crossing delocalization of the wave functions on both sides of the molecular plane is found at excitation energies >30 cm(-1), giving rise to the energy splittings of the pairs of states symmetric/antisymmetric with respect to the aromatic plane; the splittings show strong vdW vibrational mode specificity.

Equations of state for real gases on the nuclear scale

NASA Astrophysics Data System (ADS)

Vovchenko, Volodymyr

2017-07-01

The formalism to augment the classical models of the equation of state for real gases with quantum statistical effects is presented. It allows an arbitrary excluded volume procedure to model repulsive interactions, and an arbitrary density-dependent mean field to model attractive interactions. Variations on the excluded volume mechanism include van der Waals (VDW) and Carnahan-Starling models, while the mean fields are based on VDW, Redlich-Kwong-Soave, Peng-Robinson, and Clausius equations of state. The VDW parameters of the nucleon-nucleon interaction are fitted in each model to the properties of the ground state of nuclear matter, and the following range of values is obtained: a =330 -430 MeV fm3 and b =2.5 -4.4 fm3 . In the context of the excluded volume approach, the fits to the nuclear ground state disfavor the values of the effective hard-core radius of a nucleon significantly smaller than 0.5 fm , at least for the nuclear matter region of the phase diagram. Modifications to the standard VDW repulsion and attraction terms allow one to improve significantly the value of the nuclear incompressibility factor K0, bringing it closer to empirical estimates. The generalization to include the baryon-baryon interactions into the hadron resonance gas model is performed. The behavior of the baryon-related lattice QCD observables at zero chemical potential is shown to be strongly correlated to the nuclear matter properties: an improved description of the nuclear incompressibility also yields an improved description of the lattice data at μ =0 .

Van der Waals Epitaxy of GaSe/Graphene Heterostructure: Electronic and Interfacial Properties.

PubMed

Ben Aziza, Zeineb; Henck, Hugo; Pierucci, Debora; Silly, Mathieu G; Lhuillier, Emmanuel; Patriarche, Gilles; Sirotti, Fausto; Eddrief, Mahmoud; Ouerghi, Abdelkarim

2016-10-07

Stacking two-dimensional materials in so-called van der Waals (vdW) heterostructures, like the combination of GaSe and graphene, provides the ability to obtain hybrid systems which are suitable to design optoelectronic devices. Here, we report the structural and electronic properties of the direct growth of multilayered GaSe by Molecular beam Epitaxy (MBE) on graphene. Reflection high-energy electron diffraction (RHEED) images exhibited sharp streaky features indicative of high quality GaSe layer produced via a vdW epitaxy. Micro-Raman spectroscopy showed that, after the vdW hetero-interface formation, the Raman signature of pristine graphene is preserved. However, the GaSe film tuned the charge density of graphene layer by shifting the Dirac point by about 80 meV toward lower binding energies, attesting an electron transfer from graphene to GaSe. Angle-resolved photoemission spectroscopy (ARPES) measurements showed that the maximum of the valence band of few layers of GaSe are located at the Γ point at a binding energy of about -0.73 eV relatively to the Fermi level (p-type doping). From the ARPES measurements, a hole effective mass defined along the ΓM direction and equal to about m*/m0 = -1.1 was determined. By coupling the ARPES data with high resolution X-ray photoemission spectroscopy (HR-XPS) measurements, the Schottky interface barrier height was estimated to be 1.2 eV. These findings allow deeper understanding of the interlayer interactions and the electronic structure of GaSe/graphene vdW heterostructure.

Adsorption of benzene on low index surfaces of platinum in the presence of van der Waals interactions

NASA Astrophysics Data System (ADS)

K, Ayishabi P.; Chatanathodi, Raghu

2017-10-01

We have studied the adsorption of benzene on three low index surfaces of platinum using plane-wave Density Functional Theory (DFT) calculations, taking into consideration van der Waals (vdW) interaction. Experimentally, it is known that benzene adsorbs at the bridge site on the (111) surface, but in case of (110) and (100), this is not known yet. Our calculations show that benzene preferably adsorbs on bridge position on Pt(111) surface, whereas on Pt(110) and Pt(100) surfaces, the hollow position is energetically more favoured. The structural and electronic modifications of molecule and the surfaces are also examined. In all cases, adsorption-induced distortions of adsorbate-substrate complex are found to be modest in character, but relatively maximum in case of the (110) facet. The molecule is bound most strongly to the (110) surface. Importantly, we find that adsorption at bridge and atop positions are energetically feasible on the (110) surface, with the canting of benzene ring at a small angle from the metal plane. We study changes in electronic structure and the net charge transfer upon adsorption of benzene on all three low index planes. Inclusion of vdW interactions is important for obtaining realistic adsorption strengths for benzene on various Pt facets.

Two-dimensional GaSe/MoSe2 misfit bilayer heterojunctions by van der Waals epitaxy.

PubMed

Li, Xufan; Lin, Ming-Wei; Lin, Junhao; Huang, Bing; Puretzky, Alexander A; Ma, Cheng; Wang, Kai; Zhou, Wu; Pantelides, Sokrates T; Chi, Miaofang; Kravchenko, Ivan; Fowlkes, Jason; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

2016-04-01

Two-dimensional (2D) heterostructures hold the promise for future atomically thin electronics and optoelectronics because of their diverse functionalities. Although heterostructures consisting of different 2D materials with well-matched lattices and novel physical properties have been successfully fabricated via van der Waals (vdW) epitaxy, constructing heterostructures from layered semiconductors with large lattice misfits remains challenging. We report the growth of 2D GaSe/MoSe2 heterostructures with a large lattice misfit using two-step chemical vapor deposition (CVD). Both vertically stacked and lateral heterostructures are demonstrated. The vertically stacked GaSe/MoSe2 heterostructures exhibit vdW epitaxy with well-aligned lattice orientation between the two layers, forming a periodic superlattice. However, the lateral heterostructures exhibit no lateral epitaxial alignment at the interface between GaSe and MoSe2 crystalline domains. Instead of a direct lateral connection at the boundary region where the same lattice orientation is observed between GaSe and MoSe2 monolayer domains in lateral GaSe/MoSe2 heterostructures, GaSe monolayers are found to overgrow MoSe2 during CVD, forming a stripe of vertically stacked vdW heterostructures at the crystal interface. Such vertically stacked vdW GaSe/MoSe2 heterostructures are shown to form p-n junctions with effective transport and separation of photogenerated charge carriers between layers, resulting in a gate-tunable photovoltaic response. These GaSe/MoSe2 vdW heterostructures should have applications as gate-tunable field-effect transistors, photodetectors, and solar cells.

Two-dimensional GaSe/MoSe2 misfit bilayer heterojunctions by van der Waals epitaxy

PubMed Central

Li, Xufan; Lin, Ming-Wei; Lin, Junhao; Huang, Bing; Puretzky, Alexander A.; Ma, Cheng; Wang, Kai; Zhou, Wu; Pantelides, Sokrates T.; Chi, Miaofang; Kravchenko, Ivan; Fowlkes, Jason; Rouleau, Christopher M.; Geohegan, David B.; Xiao, Kai

2016-01-01

Two-dimensional (2D) heterostructures hold the promise for future atomically thin electronics and optoelectronics because of their diverse functionalities. Although heterostructures consisting of different 2D materials with well-matched lattices and novel physical properties have been successfully fabricated via van der Waals (vdW) epitaxy, constructing heterostructures from layered semiconductors with large lattice misfits remains challenging. We report the growth of 2D GaSe/MoSe2 heterostructures with a large lattice misfit using two-step chemical vapor deposition (CVD). Both vertically stacked and lateral heterostructures are demonstrated. The vertically stacked GaSe/MoSe2 heterostructures exhibit vdW epitaxy with well-aligned lattice orientation between the two layers, forming a periodic superlattice. However, the lateral heterostructures exhibit no lateral epitaxial alignment at the interface between GaSe and MoSe2 crystalline domains. Instead of a direct lateral connection at the boundary region where the same lattice orientation is observed between GaSe and MoSe2 monolayer domains in lateral GaSe/MoSe2 heterostructures, GaSe monolayers are found to overgrow MoSe2 during CVD, forming a stripe of vertically stacked vdW heterostructures at the crystal interface. Such vertically stacked vdW GaSe/MoSe2 heterostructures are shown to form p-n junctions with effective transport and separation of photogenerated charge carriers between layers, resulting in a gate-tunable photovoltaic response. These GaSe/MoSe2 vdW heterostructures should have applications as gate-tunable field-effect transistors, photodetectors, and solar cells. PMID:27152356

Physical adsorption at the nanoscale: Towards controllable scaling of the substrate-adsorbate van der Waals interaction

NASA Astrophysics Data System (ADS)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi; Tkatchenko, Alexandre

2017-06-01

The Lifshitz-Zaremba-Kohn (LZK) theory is commonly considered as the correct large-distance limit for the van der Waals (vdW) interaction of adsorbates (atoms, molecules, or nanoparticles) with solid substrates. In the standard approximate form, implicitly based on local dielectric functions, the LZK approach predicts universal power laws for vdW interactions depending only on the dimensionality of the interacting objects. However, recent experimental findings are challenging the universality of this theoretical approach at finite distances of relevance for nanoscale assembly. Here, we present a combined analytical and numerical many-body study demonstrating that physical adsorption can be significantly enhanced at the nanoscale. Regardless of the band gap or the nature of the adsorbate specie, we find deviations from conventional LZK power laws that extend to separation distances of up to 10-20 nm. Comparison with recent experimental observations of ultra-long-ranged vdW interactions in the delamination of graphene from a silicon substrate reveals qualitative agreement with the present theory. The sensitivity of vdW interactions to the substrate response and to the adsorbate characteristic excitation frequency also suggests that adsorption strength can be effectively tuned in experiments, paving the way to an improved control of physical adsorption at the nanoscale.

Non-additivity of molecule-surface van der Waals potentials from force measurements.

PubMed

Wagner, Christian; Fournier, Norman; Ruiz, Victor G; Li, Chen; Müllen, Klaus; Rohlfing, Michael; Tkatchenko, Alexandre; Temirov, Ruslan; Tautz, F Stefan

2014-11-26

Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction.

Application of vdW-DF Methods to Hydrogen Adsorptions and an Organic Ferroelectric

NASA Astrophysics Data System (ADS)

Lee, Kyuho

2012-02-01

In recent years, several schemes have been proposed to include van der Waals (vdW) interactions into the framework of density functional theory (DFT). These offer the potential to extend the scope and usefulness of DFT, allowing applications to an entire new class of sparse materials. For finite systems, we validated our non-empirical van der Waals density functionals (vdW-DFs) with respect to very accurate quantum chemical calculations of the potential energy curves (PECs) for small molecular duplexes [1]. For extended systems, however, typical tests focus on comparisons with a few accessible observations, such as binding energy and bond length [1]. In this talk, we present a third approach in which full PECs from accurate experiments are used for the assessment of vdW methods for extended systems [2]. We calculate the PECs of the H2 molecule and light atoms on the (100), (110), and (111) surfaces of Cu. The gas-surface-scattering experiments provide the rich data bank that covers results for the whole shape of the physisorption potentials. We also present an application of vdW-DF2 to an organic ferroelectric, phenazine-chloranilic acid [3]. In spite of extensive experimental efforts to characterize this rare organic material, the origin of the long-range order is unclear and even the ground state structure is not completely determined yet. We study its structure, energetics, ferroelectric properties, structural instability, and the proton-transfer process in it in comparison with PBE results and experiments wherever possible. [4pt]% [1] K. Lee, E. Murray, L. Kong, B. I. Lundqvist, and D. C. Langreth, Phys. Rev. B 82, 081101 (2010). [1pt]% [2] K. Lee, A. K. Kelkkanen, K. Berland, S. Andersson, D. C. Langreth, E. Schr"oder, B. I. Lundqvist, and P. Hyldgaard, Phys. Rev. B 84, 193408 (2011). [1pt]% [3] K. Lee, B. Kolb, T. Thonhauser, D. C. Langreth, and D. Vanderbilt, in preparation.

Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes.

PubMed

Dishon, Matan; Zohar, Ohad; Sivan, Uri

2011-11-01

Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.

Tuning electronic transport in epitaxial graphene-based van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Lin, Yu-Chuan; Li, Jun; de La Barrera, Sergio C.; Eichfeld, Sarah M.; Nie, Yifan; Addou, Rafik; Mende, Patrick C.; Wallace, Robert M.; Cho, Kyeongjae; Feenstra, Randall M.; Robinson, Joshua A.

2016-04-01

Two-dimensional tungsten diselenide (WSe2) has been used as a component in atomically thin photovoltaic devices, field effect transistors, and tunneling diodes in tandem with graphene. In some applications it is necessary to achieve efficient charge transport across the interface of layered WSe2-graphene, a semiconductor to semimetal junction with a van der Waals (vdW) gap. In such cases, band alignment engineering is required to ensure a low-resistance, ohmic contact. In this work, we investigate the impact of graphene electronic properties on the transport at the WSe2-graphene interface. Electrical transport measurements reveal a lower resistance between WSe2 and fully hydrogenated epitaxial graphene (EGFH) compared to WSe2 grown on partially hydrogenated epitaxial graphene (EGPH). Using low-energy electron microscopy and reflectivity on these samples, we extract the work function difference between the WSe2 and graphene and employ a charge transfer model to determine the WSe2 carrier density in both cases. The results indicate that WSe2-EGFH displays ohmic behavior at small biases due to a large hole density in the WSe2, whereas WSe2-EGPH forms a Schottky barrier junction.Two-dimensional tungsten diselenide (WSe2) has been used as a component in atomically thin photovoltaic devices, field effect transistors, and tunneling diodes in tandem with graphene. In some applications it is necessary to achieve efficient charge transport across the interface of layered WSe2-graphene, a semiconductor to semimetal junction with a van der Waals (vdW) gap. In such cases, band alignment engineering is required to ensure a low-resistance, ohmic contact. In this work, we investigate the impact of graphene electronic properties on the transport at the WSe2-graphene interface. Electrical transport measurements reveal a lower resistance between WSe2 and fully hydrogenated epitaxial graphene (EGFH) compared to WSe2 grown on partially hydrogenated epitaxial graphene (EGPH). Using low-energy electron microscopy and reflectivity on these samples, we extract the work function difference between the WSe2 and graphene and employ a charge transfer model to determine the WSe2 carrier density in both cases. The results indicate that WSe2-EGFH displays ohmic behavior at small biases due to a large hole density in the WSe2, whereas WSe2-EGPH forms a Schottky barrier junction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01902a

Interface characteristics at an organic/metal junction: pentacene on Cu stepped surfaces.

PubMed

Matos, Jeronimo; Kara, Abdelkader

2016-11-09

The adsorption of pentacene on Cu (2 2 1), Cu (5 1 1) and Cu (9 1 1) is investigated using density functional theory (DFT) with the self-consistent inclusion of van der Waals (vdW) interactions. Cu (2 1 1) is a vicinal of Cu (1 1 1) while Cu (5 1 1) and (9 1 1) are vicinals of Cu (1 0 0). For all the three surfaces, we found pentacene to prefer to adsorb parallel to the surface and near the steps. The addition of vdW interactions resulted in an enhancement in adsorption energies, with reference to the PBE functional, of around 2 eV. With vdWs inclusion, the adsorption energies were found to be 2.98 eV, 3.20 eV and 3.49 eV for Cu (2 2 1), Cu (5 1 1) and Cu (9 1 1) respectively. These values reflect that pentacene adsorbs stronger on (1 0 0) terraces with a preference for larger terraces. The molecule tilts upon adsorption with a small tilt angle on the (1 0 0) vicinals (about a few degrees) as compared to a large one on Cu (2 2 1) where the tilt angle is found to be about 20°. We find that the adsorption results in a net charge transfer to the molecule of ~1 electron, for all surfaces.

mBEEF-vdW: Robust fitting of error estimation density functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lundgaard, Keld T.; Wellendorff, Jess; Voss, Johannes

Here, we propose a general-purpose semilocal/nonlocal exchange-correlation functional approximation, named mBEEF-vdW. The exchange is a meta generalized gradient approximation, and the correlation is a semilocal and nonlocal mixture, with the Rutgers-Chalmers approximation for van der Waals (vdW) forces. The functional is fitted within the Bayesian error estimation functional (BEEF) framework. We improve the previously used fitting procedures by introducing a robust MM-estimator based loss function, reducing the sensitivity to outliers in the datasets. To more reliably determine the optimal model complexity, we furthermore introduce a generalization of the bootstrap 0.632 estimator with hierarchical bootstrap sampling and geometric mean estimator overmore » the training datasets. Using this estimator, we show that the robust loss function leads to a 10% improvement in the estimated prediction error over the previously used least-squares loss function. The mBEEF-vdW functional is benchmarked against popular density functional approximations over a wide range of datasets relevant for heterogeneous catalysis, including datasets that were not used for its training. Overall, we find that mBEEF-vdW has a higher general accuracy than competing popular functionals, and it is one of the best performing functionals on chemisorption systems, surface energies, lattice constants, and dispersion. We also show the potential-energy curve of graphene on the nickel(111) surface, where mBEEF-vdW matches the experimental binding length. mBEEF-vdW is currently available in gpaw and other density functional theory codes through Libxc, version 3.0.0.« less

mBEEF-vdW: Robust fitting of error estimation density functionals

DOE PAGES

Lundgaard, Keld T.; Wellendorff, Jess; Voss, Johannes; ...

2016-06-15

Here, we propose a general-purpose semilocal/nonlocal exchange-correlation functional approximation, named mBEEF-vdW. The exchange is a meta generalized gradient approximation, and the correlation is a semilocal and nonlocal mixture, with the Rutgers-Chalmers approximation for van der Waals (vdW) forces. The functional is fitted within the Bayesian error estimation functional (BEEF) framework. We improve the previously used fitting procedures by introducing a robust MM-estimator based loss function, reducing the sensitivity to outliers in the datasets. To more reliably determine the optimal model complexity, we furthermore introduce a generalization of the bootstrap 0.632 estimator with hierarchical bootstrap sampling and geometric mean estimator overmore » the training datasets. Using this estimator, we show that the robust loss function leads to a 10% improvement in the estimated prediction error over the previously used least-squares loss function. The mBEEF-vdW functional is benchmarked against popular density functional approximations over a wide range of datasets relevant for heterogeneous catalysis, including datasets that were not used for its training. Overall, we find that mBEEF-vdW has a higher general accuracy than competing popular functionals, and it is one of the best performing functionals on chemisorption systems, surface energies, lattice constants, and dispersion. We also show the potential-energy curve of graphene on the nickel(111) surface, where mBEEF-vdW matches the experimental binding length. mBEEF-vdW is currently available in gpaw and other density functional theory codes through Libxc, version 3.0.0.« less

Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

PubMed

Huang, Yu Li; Wruss, Elisabeth; Egger, David A; Kera, Satoshi; Ueno, Nobuo; Saidi, Wissam A; Bucko, Tomas; Wee, Andrew T S; Zojer, Egbert

2014-03-07

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

Magnetic engineering in InSe/black-phosphorus heterostructure by transition-metal-atom Sc-Zn doping in the van der Waals gap

NASA Astrophysics Data System (ADS)

Ding, Yi-min; Shi, Jun-jie; Zhang, Min; Zhu, Yao-hui; Wu, Meng; Wang, Hui; Cen, Yu-lang; Guo, Wen-hui; Pan, Shu-hang

2018-07-01

Within the framework of the spin-polarized density-functional theory, we have studied the electronic and magnetic properties of InSe/black-phosphorus (BP) heterostructure doped with 3d transition-metal (TM) atoms from Sc to Zn. The calculated binding energies show that TM-atom doping in the van der Waals (vdW) gap of InSe/BP heterostructure is energetically favorable. Our results indicate that magnetic moments are induced in the Sc-, Ti-, V-, Cr-, Mn- and Co-doped InSe/BP heterostructures due to the existence of non-bonding 3d electrons. The Ni-, Cu- and Zn-doped InSe/BP heterostructures still show nonmagnetic semiconductor characteristics. Furthermore, in the Fe-doped InSe/BP heterostructure, the half-metal property is found and a high spin polarization of 100% at the Fermi level is achieved. The Cr-doped InSe/BP has the largest magnetic moment of 4.9 μB. The Sc-, Ti-, V-, Cr- and Mn-doped InSe/BP heterostructures exhibit antiferromagnetic ground state. Moreover, the Fe- and Co-doped systems display a weak ferromagnetic and paramagnetic coupling, respectively. Our studies demonstrate that the TM doping in the vdW gap of InSe/BP heterostructure is an effective way to modify its electronic and magnetic properties.

Carbon Nanotube Oscillator Surface Profiling Device and Method of Use

DTIC Science & Technology

2011-11-15

distance p. The constants A and B are the Hamaker constants, which depend on the materials of the two interacting bodies. The total vdW inter...wall CNT 45 with 2L1 =2L2 =150 A and a sample of specific material char- acterized with atomic density a, Hamaker constants A and B, and a friction

Functional Independent Scaling Relation for ORR/OER Catalysts

DOE PAGES

Christensen, Rune; Hansen, Heine A.; Dickens, Colin F.; ...

2016-10-11

A widely used adsorption energy scaling relation between OH* and OOH* intermediates in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), has previously been determined using density functional theory and shown to dictate a minimum thermodynamic overpotential for both reactions. Here, we show that the oxygen–oxygen bond in the OOH* intermediate is, however, not well described with the previously used class of exchange-correlation functionals. By quantifying and correcting the systematic error, an improved description of gaseous peroxide species versus experimental data and a reduction in calculational uncertainty is obtained. For adsorbates, we find that the systematic error largelymore » cancels the vdW interaction missing in the original determination of the scaling relation. An improved scaling relation, which is fully independent of the applied exchange–correlation functional, is obtained and found to differ by 0.1 eV from the original. Lastly, this largely confirms that, although obtained with a method suffering from systematic errors, the previously obtained scaling relation is applicable for predictions of catalytic activity.« less

Structure and properties of fullerene molecular crystals with linear-scaling van der Waals density functional theory

NASA Astrophysics Data System (ADS)

Mostofi, Arash; Andrinopoulos, Lampros; Hine, Nicholas

2014-03-01

Fullerene molecular crystals are of technological promise for their use in heterojunction photovoltaic cells. An improved theoretical understanding of their structure and properties would be a step towards the rational design of new devices. Simulations based on density-functional theory (DFT) are invaluable for developing such insight, but standard semi-local functionals do not capture the important inter-molecular van der Waals (vdW) interactions in fullerene crystals. Furthermore the computational cost associated with the large unit cells needed are at the limit or beyond the capabilities of traditional DFT methods. In this work we overcome these limitations by using our implementation of a number of vdW-DFs in the ONETEP linear-scaling DFT code to study the structural properties of C60 molecular crystals. Powder neutron diffraction shows that the low-temperature Pa-3 phase is orientationally ordered with individual C60 units rotated around the [111] direction. We fully explore the energy landscape associated with the rotation angle and find two stable structures that are energetically very close, one of which corresponds to the experimentally observed structure. We further consider the effect of orientational disorder in very large supercells of thousands of atoms.

Reprint of "Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)"

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2017-02-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2016-12-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Combination Rules for Morse-Based van der Waals Force Fields.

PubMed

Yang, Li; Sun, Lei; Deng, Wei-Qiao

2018-02-15

In traditional force fields (FFs), van der Waals interactions have been usually described by the Lennard-Jones potentials. Conventional combination rules for the parameters of van der Waals (VDW) cross-termed interactions were developed for the Lennard-Jones based FFs. Here, we report that the Morse potentials were a better function to describe VDW interactions calculated by highly precise quantum mechanics methods. A new set of combination rules was developed for Morse-based FFs, in which VDW interactions were described by Morse potentials. The new set of combination rules has been verified by comparing the second virial coefficients of 11 noble gas mixtures. For all of the mixed binaries considered in this work, the combination rules work very well and are superior to all three other existing sets of combination rules reported in the literature. We further used the Morse-based FF by using the combination rules to simulate the adsorption isotherms of CH 4 at 298 K in four covalent-organic frameworks (COFs). The overall agreement is great, which supports the further applications of this new set of combination rules in more realistic simulation systems.

Constructing high-accuracy intermolecular potential energy surface with multi-dimension Morse/Long-Range model

NASA Astrophysics Data System (ADS)

Zhai, Yu; Li, Hui; Le Roy, Robert J.

2018-04-01

Spectroscopically accurate Potential Energy Surfaces (PESs) are fundamental for explaining and making predictions of the infrared and microwave spectra of van der Waals (vdW) complexes, and the model used for the potential energy function is critically important for providing accurate, robust and portable analytical PESs. The Morse/Long-Range (MLR) model has proved to be one of the most general, flexible and accurate one-dimensional (1D) model potentials, as it has physically meaningful parameters, is flexible, smooth and differentiable everywhere, to all orders and extrapolates sensibly at both long and short ranges. The Multi-Dimensional Morse/Long-Range (mdMLR) potential energy model described herein is based on that 1D MLR model, and has proved to be effective and accurate in the potentiology of various types of vdW complexes. In this paper, we review the current status of development of the mdMLR model and its application to vdW complexes. The future of the mdMLR model is also discussed. This review can serve as a tutorial for the construction of an mdMLR PES.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE PAGES

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching; ...

2017-11-14

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

mBEEF-vdW: Robust fitting of error estimation density functionals

NASA Astrophysics Data System (ADS)

Lundgaard, Keld T.; Wellendorff, Jess; Voss, Johannes; Jacobsen, Karsten W.; Bligaard, Thomas

2016-06-01

We propose a general-purpose semilocal/nonlocal exchange-correlation functional approximation, named mBEEF-vdW. The exchange is a meta generalized gradient approximation, and the correlation is a semilocal and nonlocal mixture, with the Rutgers-Chalmers approximation for van der Waals (vdW) forces. The functional is fitted within the Bayesian error estimation functional (BEEF) framework [J. Wellendorff et al., Phys. Rev. B 85, 235149 (2012), 10.1103/PhysRevB.85.235149; J. Wellendorff et al., J. Chem. Phys. 140, 144107 (2014), 10.1063/1.4870397]. We improve the previously used fitting procedures by introducing a robust MM-estimator based loss function, reducing the sensitivity to outliers in the datasets. To more reliably determine the optimal model complexity, we furthermore introduce a generalization of the bootstrap 0.632 estimator with hierarchical bootstrap sampling and geometric mean estimator over the training datasets. Using this estimator, we show that the robust loss function leads to a 10 % improvement in the estimated prediction error over the previously used least-squares loss function. The mBEEF-vdW functional is benchmarked against popular density functional approximations over a wide range of datasets relevant for heterogeneous catalysis, including datasets that were not used for its training. Overall, we find that mBEEF-vdW has a higher general accuracy than competing popular functionals, and it is one of the best performing functionals on chemisorption systems, surface energies, lattice constants, and dispersion. We also show the potential-energy curve of graphene on the nickel(111) surface, where mBEEF-vdW matches the experimental binding length. mBEEF-vdW is currently available in gpaw and other density functional theory codes through Libxc, version 3.0.0.

Dynamics of vortex domain walls in ferromagnetic nanowires - A possible method for chirality manipulation

NASA Astrophysics Data System (ADS)

Li, Y.; Lu, Z.; Chen, C.; Cheng, M.; Yin, H.; Wang, W.; Li, C.; Liu, Y.; Xiong, R.; Shi, J.

2018-06-01

The dynamic behaviors of vortex domain walls (VDWs) in ferromagnetic nanowires driven by a magnetic field above Walker breakdown field (Hw) were investigated using micromagnetic simulation. It was found when nanowire has proper geometrical dimensions, the VDW may oscillate in a chirality invariant mode or a chirality switching mode depending on applied field and damping constant. At fixed damping constant, the oscillation mode can be controlled by applied field - with the increase of applied field, the oscillation of VDW change from a chirality invariant mode to a variant one. As the oscillation of VDW changes from chirality invariant regime to chirality switching regime, the oscillation frequency and amplification will undergo an abnormal change, which may offer a fingerprint for the switch of oscillation mode. Our finding proposes a simple way to control the chirality of a VDW by properly manipulating nanowire geometry and applied field, which may have important applications in VDW-based devices.

Hybrid density functional study on the mechanism for the enhanced photocatalytic properties of the ultrathin hybrid layered nanocomposite g-C3N4/BiOCl

NASA Astrophysics Data System (ADS)

Yao, Wenzhi; Zhang, Jihua; Wang, Yuanxu; Ren, Fengzhu

2018-03-01

To investigate the origin of the high photocatalytic performance of experimentally synthesized g-C3N4/ BiOCl, we studied its geometry structure, electronic structure, and photocatalytic properties by means of hybrid density-functional theory (DFT). The calculated band alignment of g-C3N4 and few-layer BiOCl sheets clearly shows that g-C3N4/ BiOCl is a standard type-II nanocomposite. The density of states, Bader charge, partial charge density, charge density difference, and the effective masses show that electron-hole pair can be effectively separated in the g-C3N4/BiOCl interface. The calculated absorption coefficients indicate an obvious redshift of the absorption edge. The band gap of g-C3N4/BiOCl can be modulated by external electric field, and a semiconductor-semimetal transition is observed. The type-II vdW heterostructure is still maintained during the changes of external electric field. Especially, when the electric field reaches to +0.7 V/Å, the impurity states have been eliminated with the band gap of 2.3 eV. An analysis of optical properties shows that the absorption coefficient in the visible-light region is enhanced considerably as the electric-field strength increases. Our calculation results suggest that the ultrathin hybrid layered g-C3N4/BiOCl nanocomposite may have significant advantages for visible-light photocatalysis.

Near-zero hysteresis and near-ideal subthreshold swing in h-BN encapsulated single-layer MoS2 field-effect transistors

NASA Astrophysics Data System (ADS)

Vu, Quoc An; Fan, Sidi; Hyup Lee, Sang; Joo, Min-Kyu; Jong Yu, Woo; Lee, Young Hee

2018-07-01

While two-dimensional (2D) van der Waals (vdW) layered materials are promising channel materials for wearable electronics and energy-efficient field-effect transistors (FETs), large hysteresis and large subthreshold swing induced by either dangling bonds at gate oxide dielectrics and/or trap molecules in bubbles at vdW interface are a serious drawback, hampering implementation of the 2D-material based FETs in real electronics. Here, we report a monolayer MoS2 FET with near-zero hysteresis reaching 0.15% of the sweeping range of the gate bias, a record-value observed so far in 2D FETs. This was realized by squeezing the MoS2 channel between top h-BN layer and bottom h-BN gate dielectrics and further removing the trap molecules in bubbles at the vdW interfaces via post-annealing. By segregating the bubbles out to the edge of the channel, we also obtain excellent switching characteristics with a minimum subthreshold swing of 63 mV/dec, an average subthreshold slope of 69 mV/dec for a current range of four orders of magnitude at room temperature, and a high on/off current ratio of 108 at a small operating voltage (<1 V). Such a near-zero hysteresis and a near-ideal subthreshold limit originate from the reduced trap density of ~5.2  ×  109 cm‑2 eV‑1, a thousand times smaller than previously reported values.

Assessing Ion-Water Interactions in the AMOEBA Force Field Using Energy Decomposition Analysis of Electronic Structure Calculations.

PubMed

Mao, Yuezhi; Demerdash, Omar; Head-Gordon, Martin; Head-Gordon, Teresa

2016-11-08

AMOEBA is a molecular mechanics force field that addresses some of the shortcomings of a fixed partial charge model, by including permanent atomic point multipoles through quadrupoles, as well as many-body polarization through the use of point inducible dipoles. In this work, we investigate how well AMOEBA formulates its non-bonded interactions, and how it implicitly incorporates quantum mechanical effects such as charge penetration (CP) and charge transfer (CT), for water-water and water-ion interactions. We find that AMOEBA's total interaction energies, as a function of distance and over angular scans for the water dimer and for a range of water-monovalent cations, agree well with an advanced density functional theory (DFT) model, whereas the water-halides and water-divalent cations show significant disagreement with the DFT result, especially in the compressed region when the two fragments overlap. We use a second-generation energy decomposition analysis (EDA) scheme based on absolutely localized molecular orbitals (ALMOs) to show that in the best cases AMOEBA relies on cancellation of errors by softening of the van der Waals (vdW) wall to balance permanent electrostatics that are too unfavorable, thereby compensating for the missing CP effect. CT, as another important stabilizing effect not explicitly taken into account in AMOEBA, is also found to be incorporated by the softened vdW interaction. For the water-halides and water-divalent cations, this compensatory approach is not as well executed by AMOEBA over all distances and angles, wherein permanent electrostatics remains too unfavorable and polarization is overdamped in the former while overestimated in the latter. We conclude that the DFT-based EDA approach can help refine a next-generation AMOEBA model that either realizes a better cancellation of errors for problematic cases like those illustrated here, or serves to guide the parametrization of explicit functional forms for short-range contributions from CP and/or CT.

Reversible Tailoring of Mechanical Properties of Carbon Nanotube Forests by Immersing in Solvents

DTIC Science & Technology

2014-12-07

quantify the strength of vdW interactions between CNTs, Hamaker constant of CNTs in vacuum, Av ¼ V 12pD 2 G , was evaluated where ‘V’ is the vdW...effectively do not interact with each other. Therefore, we assumed curved surface–surface vdW interaction between two CNTs to evaluate the Hamaker ...of the vdW forces are directly proportional to Hamaker constant, which depends on the macroscopic properties of the interacting objects and the

Measuring and predicting Delta(vap)H298 values of ionic liquids.

PubMed

Deyko, Alexey; Lovelock, Kevin R J; Corfield, Jo-Anne; Taylor, Alasdair W; Gooden, Peter N; Villar-Garcia, Ignacio J; Licence, Peter; Jones, Robert G; Krasovskiy, Vladimir G; Chernikova, Elena A; Kustov, Leonid M

2009-10-14

We report the enthalpies of vaporisation (measured using temperature programmed desorption by mass spectrometry) of twelve ionic liquids (ILs), covering four imidazolium, [C(m)C(n)Im]+, five pyrrolidinium, [C(n)C(m)Pyrr]+, two pyridinium, [C(n)Py]+, and a dication, [C3(C1Im)2]2+ based IL. These cations were paired with a range of anions: [BF4]-, [FeCl4]-, [N(CN)2]-, [PF3(C2F5)3]- ([FAP]-), [(CF3SO2)2N]- ([Tf2N]-) and [SCN]-. Using these results, plus those for a further eight imidazolium based ILs published earlier (which include the anions [CF3SO3]- ([TfO]-), [PF6]- and [EtSO4]-), we show that the enthalpies of vaporisation can be decomposed into three components. The first component is the Coulombic interaction between the ions, DeltaU(Cou,R), which is a function of the IL molar volume, V(m), and a parameter R(r) which quantifies the relative change in anion-cation distance on evaporation from the liquid phase to the ion pair in the gas phase. The second and third components are the van der Waals contributions from the anion, DeltaH(vdw,A), and the cation, DeltaH(vdw,C). We derive a universal value for R(r), and individual values of DeltaH(vdw,A) and DeltaH(vdw,C) for each of the anions and cations considered in this study. Given the molar volume, it is possible to estimate the enthalpies of vaporisation of ILs composed of any combination of the ions considered here; values for fourteen ILs which have not yet been studied experimentally are given.

Evaluation of Two New Electronic Apex-Locator-Controlled Handpieces Using a NiTi Rotary File: An In Vitro Study.

PubMed

Nazarimoghadam, Kiumarz; Labaf, Hossein

2013-11-01

The aim of this in-vitro study was to compare the accuracy of two new electronic apex-locator controlled handpieces (EALHs) using the first rotary Mtwo file while rotating in the canal. A total of 36 extracted mandibular molar teeth were selected. The lengths of the mesio-buccal canals to the major foramina were measured directly using a size 10 K-file introduced in the canal until the tip was visible under a loupe and then 0.5 mm was subtracted from the recorded lengths as the actual working lengths (AWLs). Subsequently, the teeth were randomly assigned to two groups and embedded in an alginate model. Auto-stop function of the EALHs was preset at "0.5" mark and then electrical working lengths (EWLs) in groups 1 and 2 were recorded by VDW GOLD and Dentaport ZX, respectively. Analysis of variance (ANOVA, 1-way) and Tukey pairwise multiple comparison intervals (0.05) were used to compare the accuracy of the two electronic devices. For VDW GOLD, 61.1% of the measurements were within ±0.5 mm and 88.9% were within ±1 mm of the AWL. For Dentaport ZX, 88.9% of the measurements were within ±0.5 mm and 94.4% were within ±1mm of the AWL. There was no significant difference between AWLs and EWLs (p=0.466 for Dentaport ZX and p=0.283 for VDW Gold) and between the accuracy of the two devices in determining the EWL (p=0.8). Both Dentaport ZX and VDW Gold were suitable for determining working length using a rotary file. To avoid over instrumenting the canal, we recommend setting the devices to automatically stop or reverse the rotary file at 1 mm level.

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

Van der Waals Interactions of Organic Molecules on Semiconductor and Metal Surfaces: a Comparative Study

NASA Astrophysics Data System (ADS)

Li, Guo; Cooper, Valentino; Cho, Jun-Hyung; Tamblyn, Isaac; Du, Shixuan; Neaton, Jeffrey; Gao, Hong-Jun; Zhang, Zhenyu

2012-02-01

We present a comparative investigation of vdW interactions of the organic molecules on semiconductor and metal surfaces using the DFT method implemented with vdW-DF. For styrene/H-Si(100), the vdW interactions reverse the effective intermolecular interaction from repulsive to attractive, ensuring preferred growth of long wires as observed experimentally. We further propose that an external E field and the selective creation of Si dangling bonds can drastically improve the ordered arrangement of the molecular nanowires [1]. For BDA/Au(111), the vdW interactions not only dramatically enhances the adsorption energies, but also significantly changes the molecular configurations. In the azobenzene/Ag(111) system, vdW-DF produces superior predictions for the adsorption energy than those obtained with other vdW corrected DFT approaches, providing evidence for the applicability of the vdW-DF method [2].

Strong magnetization and Chern insulators in compressed graphene/CrI 3 van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Zhang, Jiayong; Zhao, Bao; Zhou, Tong; Xue, Yang; Ma, Chunlan; Yang, Zhongqin

2018-02-01

Graphene-based heterostructures are a promising material system for designing the topologically nontrivial Chern insulating devices. Recently, a two-dimensional monolayer ferromagnetic insulator CrI3 was successfully synthesized in experiments [B. Huang et al., Nature (London) 546, 270 (2017), 10.1038/nature22391]. Here, these two interesting materials are proposed to build a heterostructure (Gr /CrI3). Our first-principles calculations show that the system forms a van der Waals (vdW) heterostructure, which is relatively facilely fabricated in experiments. A Chern insulating state is acquired in the Gr /CrI3 heterostructure if the vdW gap is compressed to a distance between about 3.3 and 2.4 Å, corresponding to a required external pressure between about 1.4 and 18.3 GPa. Amazingly, very strong magnetization (about 150 meV) is found in graphene, induced by the substrate CrI3, despite the vdW interactions between them. A low-energy effective model is employed to understand the mechanism. The work functions, contact types, and band alignments of the Gr /CrI3 heterostructure system are also studied. Our work demonstrates that the Gr /CrI3 heterostructure is a promising system to observe the quantum anomalous Hall effect at high temperatures (up to 45 K) in experiments.

Solvation Free Energies of Alanine Peptides: The Effect of Flexibility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kokubo, Hironori; Harris, Robert C.; Asthagiri, Dilip

The electrostatic (?Gel), cavity-formation (?Gvdw), and total (?G) solvation free energies for 10 alanine peptides ranging in length (n) from 1 to 10 monomers were calculated. The free energies were computed both with xed, extended conformations of the peptides and again for some of the peptides without constraints. The solvation free energies, ?Gel, ?Gvdw, and ?G, were found to be linear in n, with the slopes of the best-fit lines being gamma_el, gamma_vdw, and gamma, respectively. Both gamma_el and gamma were negative for fixed and flexible peptides, and gamma_vdw was negative for fixed peptides. That gamma_vdw was negative was surprising,more » as experimental data on alkanes, theoretical models, and MD computations on small molecules and model systems generally suggest that gamma_vdw should be positive. A negative gamma_vdw seemingly contradicts the notion that ?Gvdw drives the initial collapse of the protein when it folds by favoring conformations with small surface areas, but when we computed ?Gvdw for the flexible peptides, thereby allowing the peptides to assume natural ensembles of more compact conformations, gamma-vdw was positive. Because most proteins do not assume extended conformations, a ?Gvdw that increases with increasing surface area may be typical for globular proteins. An alternative hypothesis is that the collapse is driven by intramolecular interactions. We show that the intramolecular van der Waal's interaction energy is more favorable for the flexible than for the extended peptides, seemingly favoring this hypothesis, but the large fluctuations in this energy may make attributing the collapse of the peptide to this intramolecular energy difficult.« less

Evolution of Moiré Profiles from van der Waals Superstructures of Boron Nitride Nanosheets

PubMed Central

Liao, Yunlong; Cao, Wei; Connell, John W.; Chen, Zhongfang; Lin, Yi

2016-01-01

Two-dimensional (2D) van der Waals (vdW) superstructures, or vdW solids, are formed by the precise restacking of 2D nanosheet lattices, which can lead to unique physical and electronic properties that are not available in the parent nanosheets. Moiré patterns formed by the crystalline mismatch between adjacent nanosheets are the most direct features for vdW superstructures under microscopic imaging. In this article, transmission electron microscopy (TEM) observation of hexagonal Moiré patterns with unusually large micrometer-sized lateral areas (up to ~1 μm2) and periodicities (up to ~50 nm) from restacking of liquid exfoliated hexagonal boron nitride nanosheets (BNNSs) is reported. This observation was attributed to the long range crystallinity and the contaminant-free surfaces of these chemically inert nanosheets. Parallel-line-like Moiré fringes with similarly large periodicities were also observed. The simulations and experiments unambiguously revealed that the hexagonal patterns and the parallel fringes originated from the same rotationally mismatched vdW stacking of BNNSs and can be inter-converted by simply tilting the TEM specimen following designated directions. This finding may pave the way for further structural decoding of other 2D vdW superstructure systems with more complex Moiré images. PMID:27188697

Ab initio study of structural and mechanical property of solid molecular hydrogens

NASA Astrophysics Data System (ADS)

Ye, Yingting; Yang, Li; Yang, Tianle; Nie, Jinlan; Peng, Shuming; Long, Xinggui; Zu, Xiaotao; Du, Jincheng

2015-06-01

Ab initio calculations based on density functional theory (DFT) were performed to investigate the structural and the elastic properties of solid molecular hydrogens (H2). The influence of molecular axes of H2 on structural relative stabilities of hexagonal close-packed (hcp) and face-centered cubic (fcc) structured hydrogen molecular crystals were systematically investigated. Our results indicate that for hcp structures, disordered hydrogen molecule structure is more stable, while for fcc structures, Pa3 hydrogen molecular crystal is most stable. The cohesive energy of fcc H2 crystal was found to be lower than hcp. The mechanical properties of fcc and hcp hydrogen molecular crystals were obtained, with results consistent with previous theoretical calculations. In addition, the effects of zero point energy (ZPE) and van der Waals (vdW) correction on the cohesive energy and the stability of hydrogen molecular crystals were systematically studied and discussed.

Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions.

PubMed

Blood-Forsythe, Martin A; Markovich, Thomas; DiStasio, Robert A; Car, Roberto; Aspuru-Guzik, Alán

2016-03-01

An accurate treatment of the long-range electron correlation energy, including van der Waals (vdW) or dispersion interactions, is essential for describing the structure, dynamics, and function of a wide variety of systems. Among the most accurate models for including dispersion into density functional theory (DFT) is the range-separated many-body dispersion (MBD) method [A. Ambrosetti et al. , J. Chem. Phys. , 2014, 140 , 18A508], in which the correlation energy is modeled at short-range by a semi-local density functional and at long-range by a model system of coupled quantum harmonic oscillators. In this work, we develop analytical gradients of the MBD energy with respect to nuclear coordinates, including all implicit coordinate dependencies arising from the partitioning of the charge density into Hirshfeld effective volumes. To demonstrate the efficiency and accuracy of these MBD gradients for geometry optimizations of systems with intermolecular and intramolecular interactions, we optimized conformers of the benzene dimer and isolated small peptides with aromatic side-chains. We find excellent agreement with the wavefunction theory reference geometries of these systems (at a fraction of the computational cost) and find that MBD consistently outperforms the popular TS and D3(BJ) dispersion corrections. To demonstrate the performance of the MBD model on a larger system with supramolecular interactions, we optimized the C 60 @C 60 H 28 buckyball catcher host-guest complex. In our analysis, we also find that neglecting the implicit nuclear coordinate dependence arising from the charge density partitioning, as has been done in prior numerical treatments, leads to an unacceptable error in the MBD forces, with relative errors of ∼20% (on average) that can extend well beyond 100%.

The potential for fast van der Waals computations for layered materials using a Lifshitz model

NASA Astrophysics Data System (ADS)

Zhou, Yao; Pellouchoud, Lenson A.; Reed, Evan J.

2017-06-01

Computation of the van der Waals (vdW) interactions plays a crucial role in the study of layered materials. The adiabatic-connection fluctuation-dissipation theorem within random phase approximation (ACFDT-RPA) has been empirically reported to be the most accurate of commonly used methods, but it is limited to small systems due to its computational complexity. Without a computationally tractable vdW correction, fictitious strains are often introduced in the study of multilayer heterostructures, which, we find, can change the vdW binding energy by as much as 15%. In this work, we employed for the first time a defined Lifshitz model to provide the vdW potentials for a spectrum of layered materials orders of magnitude faster than the ACFDT-RPA for representative layered material structures. We find that a suitably defined Lifshitz model gives the correlation component of the binding energy to within 8-20% of the ACFDT-RPA calculations for a variety of layered heterostructures. Using this fast Lifshitz model, we studied the vdW binding properties of 210 three-layered heterostructures. Our results demonstrate that the three-body vdW effects are generally small (10% of the binding energy) in layered materials for most cases, and that non-negligible second-nearest neighbor layer interaction and three-body effects are observed for only those cases in which the middle layer is atomically thin (e.g. BN or graphene). We find that there is potential for particular combinations of stacked layers to exhibit repulsive three-body van der Waals effects, although these effects are likely to be much smaller than two-body effects.

Gate-tunable diode-like current rectification and ambipolar transport in multilayer van der Waals ReSe2/WS2 p-n heterojunctions.

PubMed

Wang, Cong; Yang, Shengxue; Xiong, Wenqi; Xia, Congxin; Cai, Hui; Chen, Bin; Wang, Xiaoting; Zhang, Xinzheng; Wei, Zhongming; Tongay, Sefaattin; Li, Jingbo; Liu, Qian

2016-10-12

Vertically stacked van der Waals (vdW) heterojunctions of two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted a great deal of attention due to their fascinating properties. In this work, we report two important gate-tunable phenomena in new artificial vdW p-n heterojunctions created by vertically stacking p-type multilayer ReSe 2 and n-type multilayer WS 2 : (1) well-defined strong gate-tunable diode-like current rectification across the p-n interface is observed, and the tunability of the electronic processes is attributed to the tunneling-assisted interlayer recombination induced by majority carriers across the vdW interface; (2) the distinct ambipolar behavior under gate voltage modulation both at forward and reverse bias voltages is found in the vdW ReSe 2 /WS 2 heterojunction transistors and a corresponding transport model is proposed for the tunable polarity behaviors. The findings may provide some new opportunities for building nanoscale electronic and optoelectronic devices.

Tunable Schottky barrier and electronic properties in borophene/g-C2N van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Jiang, J. W.; Wang, X. C.; Song, Y.; Mi, W. B.

2018-05-01

By stacking different layers of two dimensional (2D) monolayer materials, the electronic properties of the 2D van der Waals (vdW) heterostructures can be tailored. However, the Schottky barrier formed between 2D semiconductor and metallic electrode has greatly limited the application of 2D semiconductor in nanoelectronic and optoelectronic devices. Herewith, we investigate the electronic properties of borophene/g-C2N vdW heterostructures by first-principles calculations. The results indicate that electronic structures of borophene and g-C2N are preserved in borophene/g-C2N vdW heterostructures. Meanwhile, upon the external electric field, a transition from the n-type Schottky contact to Ohmic contact is induced, and the carrier concentration between the borophene and g-C2N interfaces can be tuned. These results are expected to provide useful insight in the nanoelectronic and optoelectronic devices based on the borophene/g-C2N vdW heterostructures.

Predicting the influence of long-range molecular interactions on macroscopic-scale diffusion by homogenization of the Smoluchowski equation

NASA Astrophysics Data System (ADS)

Kekenes-Huskey, P. M.; Gillette, A. K.; McCammon, J. A.

2014-05-01

The macroscopic diffusion constant for a charged diffuser is in part dependent on (1) the volume excluded by solute "obstacles" and (2) long-range interactions between those obstacles and the diffuser. Increasing excluded volume reduces transport of the diffuser, while long-range interactions can either increase or decrease diffusivity, depending on the nature of the potential. We previously demonstrated [P. M. Kekenes-Huskey et al., Biophys. J. 105, 2130 (2013)] using homogenization theory that the configuration of molecular-scale obstacles can both hinder diffusion and induce diffusional anisotropy for small ions. As the density of molecular obstacles increases, van der Waals (vdW) and electrostatic interactions between obstacle and a diffuser become significant and can strongly influence the latter's diffusivity, which was neglected in our original model. Here, we extend this methodology to include a fixed (time-independent) potential of mean force, through homogenization of the Smoluchowski equation. We consider the diffusion of ions in crowded, hydrophilic environments at physiological ionic strengths and find that electrostatic and vdW interactions can enhance or depress effective diffusion rates for attractive or repulsive forces, respectively. Additionally, we show that the observed diffusion rate may be reduced independent of non-specific electrostatic and vdW interactions by treating obstacles that exhibit specific binding interactions as "buffers" that absorb free diffusers. Finally, we demonstrate that effective diffusion rates are sensitive to distribution of surface charge on a globular protein, Troponin C, suggesting that the use of molecular structures with atomistic-scale resolution can account for electrostatic influences on substrate transport. This approach offers new insight into the influence of molecular-scale, long-range interactions on transport of charged species, particularly for diffusion-influenced signaling events occurring in crowded cellular environments.

Size of graphene sheets determines the structural and mechanical properties of 3D graphene foams

NASA Astrophysics Data System (ADS)

Shen, Zhiqiang; Ye, Huilin; Zhou, Chi; Kröger, Martin; Li, Ying

2018-03-01

Graphene is recognized as an emerging 2D nanomaterial for many applications. Assembly of graphene sheets into 3D structures is an attractive way to enable their macroscopic applications and to preserve the exceptional mechanical and physical properties of their constituents. In this study, we develop a coarse-grained (CG) model for 3D graphene foams (GFs) based on the CG model for a 2D graphene sheet by Ruiz et al (2015 Carbon 82 103-15). We find that the size of graphene sheets plays an important role in both the structural and mechanical properties of 3D GFs. When their size is smaller than 10 nm, the graphene sheets can easily stack together under the influence of van der Waals interactions (vdW). These stacks behave like building blocks and are tightly packed together within 3D GFs, leading to high density, small pore radii, and a large Young’s modulus. However, if the sheet sizes exceed 10 nm, they are staggered together with a significant amount of deformation (bending). Therefore, the density of 3D GFs has been dramatically reduced due to the loosely packed graphene sheets, accompanied by large pore radii and a small Young’s modulus. Under uniaxial compression, rubber-like stress-strain curves are observed for all 3D GFs. This material characteristic is dominated by the vdW interactions between different graphene layers and slightly affected by the out-of-plane deformation of the graphene sheets. We find a simple scaling law E˜ {ρ }4.2 between the density ρ and Young’s modulus E for a model of 3D GFs. The simulation results reveal structure-property relations of 3D GFs, which can be applied to guide the design of 3D graphene assemblies with exceptional properties.

Interlayer coupling effects on Schottky barrier in the arsenene-graphene van der Waals heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Congxin, E-mail: xiacongxin@htu.edu.cn; Xue, Bin; Wang, Tianxing

The electronic characteristics of arsenene-graphene van der Waals (vdW) heterostructures are studied by using first-principles methods. The results show that a linear Dirac-like dispersion relation around the Fermi level can be quite well preserved in the vdW heterostructures. Moreover, the p-type Schottky barrier (0.18 eV) to n-type Schottky barrier (0.31 eV) transition occurs when the interlayer distance increases from 2.8 to 4.5 Å, which indicates that the Schottky barrier can be tuned effectively by the interlayer distance in the vdW heterostructures.

Centimeter Scale Patterned Growth of Vertically Stacked Few Layer Only 2D MoS2/WS2 van der Waals Heterostructure.

PubMed

Choudhary, Nitin; Park, Juhong; Hwang, Jun Yeon; Chung, Hee-Suk; Dumas, Kenneth H; Khondaker, Saiful I; Choi, Wonbong; Jung, Yeonwoong

2016-05-05

Two-dimensional (2D) van der Waal (vdW) heterostructures composed of vertically-stacked multiple transition metal dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) are envisioned to present unprecedented materials properties unobtainable from any other material systems. Conventional fabrications of these hybrid materials have relied on the low-yield manual exfoliation and stacking of individual 2D TMD layers, which remain impractical for scaled-up applications. Attempts to chemically synthesize these materials have been recently pursued, which are presently limited to randomly and scarcely grown 2D layers with uncontrolled layer numbers on very small areas. Here, we report the chemical vapor deposition (CVD) growth of large-area (>2 cm(2)) patterned 2D vdW heterostructures composed of few layer, vertically-stacked MoS2 and WS2. Detailed structural characterizations by Raman spectroscopy and high-resolution/scanning transmission electron microscopy (HRTEM/STEM) directly evidence the structural integrity of two distinct 2D TMD layers with atomically sharp vdW heterointerfaces. Electrical transport measurements of these materials reveal diode-like behavior with clear current rectification, further confirming the formation of high-quality heterointerfaces. The intrinsic scalability and controllability of the CVD method presented in this study opens up a wide range of opportunities for emerging applications based on the unconventional functionalities of these uniquely structured materials.

A partition function-based weighting scheme in force field parameter development using ab initio calculation results in global configurational space.

PubMed

Wu, Yao; Dai, Xiaodong; Huang, Niu; Zhao, Lifeng

2013-06-05

In force field parameter development using ab initio potential energy surfaces (PES) as target data, an important but often neglected matter is the lack of a weighting scheme with optimal discrimination power to fit the target data. Here, we developed a novel partition function-based weighting scheme, which not only fits the target potential energies exponentially like the general Boltzmann weighting method, but also reduces the effect of fitting errors leading to overfitting. The van der Waals (vdW) parameters of benzene and propane were reparameterized by using the new weighting scheme to fit the high-level ab initio PESs probed by a water molecule in global configurational space. The molecular simulation results indicate that the newly derived parameters are capable of reproducing experimental properties in a broader range of temperatures, which supports the partition function-based weighting scheme. Our simulation results also suggest that structural properties are more sensitive to vdW parameters than partial atomic charge parameters in these systems although the electrostatic interactions are still important in energetic properties. As no prerequisite conditions are required, the partition function-based weighting method may be applied in developing any types of force field parameters. Copyright © 2013 Wiley Periodicals, Inc.

Intermolecular orbital interaction in π systems

NASA Astrophysics Data System (ADS)

Zhao, Rundong; Zhang, Rui-Qin

2018-04-01

Intermolecular interactions, in regard to which people tend to emphasise the noncovalent van der Waals (vdW) forces when conducting investigations throughout chemistry, can influence the structure, stability and function of molecules and materials. Despite the ubiquitous nature of vdW interactions, a simplified electrostatic model has been popularly adopted to explain common intermolecular interactions, especially those existing in π-involved systems. However, this classical model has come under fire in revealing specific issues such as substituent effects, due to its roughness; and it has been followed in past decades by sundry explanations which sometimes bring in nebulous descriptions. In this account, we try to summarise and present a unified model for describing and analysing the binding mechanism of such systems from the viewpoint of energy decomposition. We also emphasise a commonly ignored factor - orbital interaction, pointing out that the noncovalent intermolecular orbital interactions actually exhibit similar bonding and antibonding phenomena as those in covalent bonds.

Adhesion of Particulate Materials to Mesostructured Polypyrrole

NASA Astrophysics Data System (ADS)

Hoss, Darby; Knepper, Robert; Hotchkiss, Peter; Tappan, Alexander; Boudouris, Bryan; Beaudoin, Stephen

Interactions based on van der Waals (vdW) forces will influence the performance and reliability of mesostructured polypyrrole swabs used for the collection and detection of trace particles. The vdW adhesion force between materials is described by the Hamaker constant, and these constants are measured via optical and dielectric properties (i.e., according to Lifshitz theory), inverse gas chromatography (IGC), and contact angle measurements. Here, contact angle measurements were performed on films of several common materials and used to estimate Hamaker constants. This, in turn, will allow for the tuning of the design properties associated with the polypyrrole swabs. A comparison of these results to Hamaker constants estimated using Lifshitz Theory and IGC reveals the fundamental behavior of the materials. The Hamaker constants were then used in a new computational vdW adhesion model. The idealized model describes particle adhesion to an array of mesostrucures. This model elucidates the importance of where the particle makes contact with the mesostructure and the independence of vdW forces generated by each mesostructure. These results will facilitate the rational design of polypyrrole swabs optimized for harvesting microscale particles of trace materials.

Error estimates for (semi-)empirical dispersion terms and large biomacromolecules.

PubMed

Korth, Martin

2013-10-14

The first-principles modeling of biomaterials has made tremendous advances over the last few years with the ongoing growth of computing power and impressive developments in the application of density functional theory (DFT) codes to large systems. One important step forward was the development of dispersion corrections for DFT methods, which account for the otherwise neglected dispersive van der Waals (vdW) interactions. Approaches at different levels of theory exist, with the most often used (semi-)empirical ones based on pair-wise interatomic C6R(-6) terms. Similar terms are now also used in connection with semiempirical QM (SQM) methods and density functional tight binding methods (SCC-DFTB). Their basic structure equals the attractive term in Lennard-Jones potentials, common to most force field approaches, but they usually use some type of cutoff function to make the mixing of the (long-range) dispersion term with the already existing (short-range) dispersion and exchange-repulsion effects from the electronic structure theory methods possible. All these dispersion approximations were found to perform accurately for smaller systems, but error estimates for larger systems are very rare and completely missing for really large biomolecules. We derive such estimates for the dispersion terms of DFT, SQM and MM methods using error statistics for smaller systems and dispersion contribution estimates for the PDBbind database of protein-ligand interactions. We find that dispersion terms will usually not be a limiting factor for reaching chemical accuracy, though some force fields and large ligand sizes are problematic.

A Study of Vertical Transport through Graphene toward Control of Quantum Tunneling.

PubMed

Zhu, Xiaodan; Lei, Sidong; Tsai, Shin-Hung; Zhang, Xiang; Liu, Jun; Yin, Gen; Tang, Min; Torres, Carlos M; Navabi, Aryan; Jin, Zehua; Tsai, Shiao-Po; Qasem, Hussam; Wang, Yong; Vajtai, Robert; Lake, Roger K; Ajayan, Pulickel M; Wang, Kang L

2018-02-14

Vertical integration of van der Waals (vdW) materials with atomic precision is an intriguing possibility brought forward by these two-dimensional (2D) materials. Essential to the design and analysis of these structures is a fundamental understanding of the vertical transport of charge carriers into and across vdW materials, yet little has been done in this area. In this report, we explore the important roles of single layer graphene in the vertical tunneling process as a tunneling barrier. Although a semimetal in the lateral lattice plane, graphene together with the vdW gap act as a tunneling barrier that is nearly transparent to the vertically tunneling electrons due to its atomic thickness and the transverse momenta mismatch between the injected electrons and the graphene band structure. This is accentuated using electron tunneling spectroscopy (ETS) showing a lack of features corresponding to the Dirac cone band structure. Meanwhile, the graphene acts as a lateral conductor through which the potential and charge distribution across the tunneling barrier can be tuned. These unique properties make graphene an excellent 2D atomic grid, transparent to charge carriers, and yet can control the carrier flux via the electrical potential. A new model on the quantum capacitance's effect on vertical tunneling is developed to further elucidate the role of graphene in modulating the tunneling process. This work may serve as a general guideline for the design and analysis of vdW vertical tunneling devices and heterostructures, as well as the study of electron/spin injection through and into vdW materials.

Mechanistic Origin of the Ultrastrong Adhesion between Graphene and a-SiO2: Beyond van der Waals.

PubMed

Kumar, Sandeep; Parks, David; Kamrin, Ken

2016-07-26

The origin of the ultrastrong adhesion between graphene and a-SiO2 has remained a mystery. This adhesion is believed to be predominantly van der Waals (vdW) in nature. By rigorously analyzing recently reported blistering and nanoindentation experiments, we show that the ultrastrong adhesion between graphene and a-SiO2 cannot be attributed to vdW forces alone. Our analyses show that the fracture toughness of the graphene/a-SiO2 interface, when the interfacial adhesion is modeled with vdW forces alone, is anomalously weak compared to the measured values. The anomaly is related to an ultrasmall fracture process zone (FPZ): owing to the lack of a third dimension in graphene, the FPZ for the graphene/a-SiO2 interface is extremely small, and the combination of predominantly tensile vdW forces, distributed over such a small area, is bound to result in a correspondingly small interfacial fracture toughness. Through multiscale modeling, combining the results of finite element analysis and molecular dynamics simulations, we show that the adhesion between graphene and a-SiO2 involves two different kinds of interactions: one, a weak, long-range interaction arising from vdW adhesion and, second, discrete, short-range interactions originating from graphene clinging to the undercoordinated Si (≡Si·) and the nonbridging O (≡Si-O·) defects on a-SiO2. A strong resistance to relative opening and sliding provided by the latter mechanism is identified as the operative mechanism responsible for the ultrastrong adhesion between graphene and a-SiO2.

Modeling the interaction of seven bisphosphonates with the hydroxyapatite(100) face.

PubMed

Chen, Chunyu; Xia, Mingzhu; Wu, Lei; Zhou, Chao; Wang, Fengyun

2012-09-01

The interaction of seven pamidronate bisphosphonate (Pami-BPs) and its analogs with the hydroxyapatite (HAP) (100) surface was studied using density functional theory (DFT) and molecular dynamic (MD) methods. Partial Mulliken oxygen atomic charges in protonated structures were calculated at the level of B3LYP/6-31G*. The MD simulation was performed using the Discover module of Material Studio by compass force field. The results indicate the abilities of donating electrons of the oxygen atoms of the phosphate groups that are closely associated with the antiresorptive potency. The binding energies, including vdw and electrostatic, are used to discuss the mechanism of antiresorption. The results of calculations show that the strength of interaction of the HAP (100) face with the bisphosphonates is N(4) > N(6) > N(7) > N(5) > N(3) > N(2) > N(1) according to their experimental pIC(50) values.

Sub-Doppler Electronic Spectrum of the BENZENE-D2 Complex

NASA Astrophysics Data System (ADS)

Hayashi, Masato; Ohshima, Yasuhiro

2014-06-01

Excitation spectrum of the benzene-D2 van der Waals (vdW) complex in the vicinity of the S1 ← S0 601 vibronic transition of the monomer was recorded by utilizing mass-selective two-color resonance-enhanced two-photon ionization. Extensive adiabatic cooling with the rotational temperature of ěrb|<| 0.5 K was conducted by the high-pressure pulsed expansion, and sub-Doppler resolution yielding the line width of 250 MHz was realized in a collimated molecular beam by employing Fourier-transform-limited ultraviolet pulses for the excitation. In contrast to our previous study on the benzene-H2 complex, weaker binding ortho nuclear-spin isomer, correlating to the j = 0 state of a freely rotating D2, was observed in addition to the stronger binding para isomer (with j = 1), by using a gas sample of normal D2. Three and two vibronic bands involving vdW-mode excitation were observed for the para and ortho isomers, respectively. By comparing the present results with those of the benzene-H2 complex, we made unambiguous assignments on the vdW modes involved in each observed band, and obtained complete sets of vibrational frequencies of all the three vdW modes for the both H2 and D2 isotopomers in the S1 61 manifold. One of the vdW frequency correlates to the splitting between the m = 0 and ± 1 sublevels in the j = 1 state of a freely rotating H2/D2 molecule, and the potential barrier for the hindered internal rotation has been evaluated to be ca. 60 cm-1 from the values. Ratio of the vdW frequencies between the H2 and D2 species deviate significantly from the value for the harmonic vibration (i.e., √{2} ≈ 1.4), indicating substantial anharmonic character of the vdW modes in the complex. M. Hayashi and Y. Ohshima, Chem. Phys. 419, 131-137 (2013). M. Hayashi and Y. Ohshima, J. Phys. Chem. A 117, 9819-9830 (2013).

Band engineering in twisted molybdenum disulfide bilayers

NASA Astrophysics Data System (ADS)

Zhao, Yipeng; Liao, Chengwei; Ouyang, Gang

2018-05-01

In order to explore the theoretical relationship between interlayer spacing, interaction and band offset at the atomic level in vertically stacked two-dimensional (2D) van der Waals (vdW) structures, we propose an analytical model to address the evolution of interlayer vdW coupling with random stacking configurations in MoS2 bilayers based on the atomic-bond-relaxation correlation mechanism. We found that interlayer spacing changes substantially with respect to the orientations, and the bandgap increases from 1.53 eV (AB stacking) to 1.68 eV (AA stacking). Our results reveal that the evolution of interlayer vdW coupling originates from the interlayer interaction, leading to interlayer separations and electronic properties changing with stacking configurations. Our predictions constitute a demonstration of twist engineering the band shift in the emergent class of 2D crystals, transition-metal dichalcogenides.

A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides.

PubMed

Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M; Cho, Kyeongjae

2017-06-07

Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

Topological mosaics in moiré superlattices of van der Waals heterobilayers

NASA Astrophysics Data System (ADS)

Tong, Qingjun; Yu, Hongyi; Zhu, Qizhong; Wang, Yong; Xu, Xiaodong; Yao, Wang

2017-04-01

Van der Waals (vdW) heterostructures formed by two-dimensional atomic crystals provide a powerful approach towards designer condensed matter systems. Incommensurate heterobilayers with small twisting and/or lattice mismatch lead to the interesting concept of moiré superlattices, where the atomic registry is locally indistinguishable from commensurate bilayers but has local-to-local variation over long range. Here we show that such moiré superlattices can lead to periodic modulation of local topological order in vdW heterobilayers formed by two massive Dirac materials. By tuning the vdW heterojunction from normal to the inverted type-II regime via an interlayer bias, the commensurate heterobilayer can become a topological insulator (TI), depending on the interlayer hybridization controlled by the atomic registry between the vdW layers. This results in a mosaic pattern of TI regions and normal insulator (NI) regions in moiré superlattices, where topologically protected helical modes exist at the TI/NI phase boundaries. By using symmetry-based k .p and tight-binding models, we predict that this topological phenomenon can be present in inverted transition metal dichalcogenides heterobilayers. Our work points to a new means of realizing programmable and electrically switchable topological superstructures from two-dimensional arrays of TI nano-dots to one-dimensional arrays of TI nano-stripes.

Towards understanding the effects of van der Waals strengths on the electric double-layer structures and capacitive behaviors

NASA Astrophysics Data System (ADS)

Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa

2017-10-01

Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.

The formation of organic (propolis films)/inorganic (layered crystals) interfaces for optoelectronic applications

NASA Astrophysics Data System (ADS)

Drapak, S. I.; Bakhtinov, A. P.; Gavrylyuk, S. V.; Kovalyuk, Z. D.; Lytvyn, O. S.

2008-10-01

Propolis (honeybee glue) organic films were prepared from an alcoholic solution on the surfaces of inorganic layered semiconductors (indium, gallium and bismuth selenides). Atomic force microscopy (AFM) and X-ray diffraction (XRD) are used to characterize structural properties of an organic/inorganic interfaces. It is shown that nanodimensional linear defects and nanodimensional cavities of various shapes are formed on the van der Waals (VDW) surfaces of layered crystals as a result of chemical interaction between the components of propolis (flavonoids, aminoacids and phenolic acids) and the VDW surfaces as well as deformation interaction between the VDW surfaces and propolis films during their polymerization. The nanocavities are formed as a result of the rupture of strong covalent bonds in the upper layers of layered crystals and have the shape of hexagons or triangles in the (0001) plane. The shape, lateral size and distribution of nanodimensional defects on the VDW surfaces depends on the type of crystals, the magnitude and distribution of surface stresses. We have obtained self-organized nanofold structures of propolis/InSe interface. It is established that such heterostructures have photosensitivity in the infrared range hν<1.2 eV (the values of energy gap are 1.2 eV for InSe and 3.07 eV for propolis films at room temperature).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Vibrational Properties of Anhydrous and Partially Hydrated Uranyl Fluoride

DOE PAGES

Anderson, Brian B.; Kirkegaard, Marie C.; Miskowiec, Andrew J.; ...

2017-01-01

Uranyl fluoride (UO 2F 2) is a hygroscopic powder with two main structural phases: an anhydrous crystal and a partially hydrated crystal of the same R¯3m symmetry. The formally closed-shell electron structure of anhydrous UO 2F 2 is amenable to density functional theory calculations. We use density functional perturbation theory (DFPT) to calculate the vibrational frequencies of the anhydrous crystal structure and employ complementary inelastic neutron scattering and temperature-dependent Raman scattering to validate those frequencies. As a model closed-shell actinide, we investigated the effect of LDA, GGA, and non-local vdW functionals as well as the spherically-averaged Hubbard +U correction onmore » vibrational frequencies, electronic structure, and geometry of anhydrous UO 2F 2. A particular choice of U eff = 5.5 eV yields the correct U Oyl bond distance and vibrational frequencies for the characteristic Eg and A1g modes that are within the resolution of experiment. Inelastic neutron scattering and Raman scattering suggest a degree of water coupling to the lattice vibrations in the more experimentally accessible partially hydrated UO 2F 2 system, with the symmetric O-U-O stretching vibration shifted approximately 47 cm -1 lower in energy compared to the anhydrous structure. Evidence of water interaction with the uranyl ion is present from a two-peak decomposition of the uranyl stretching vibration in the Raman spectra and anion hydrogen stretching vibrations in the inelastic neutron scattering spectra. A first-order dehydration phase transition temperature is definitively identified to be 125 °C using temperature-dependent Raman scattering.« less

Two-Dimensional Semiconductor Optoelectronics Based on van der Waals Heterostructures.

PubMed

Lee, Jae Yoon; Shin, Jun-Hwan; Lee, Gwan-Hyoung; Lee, Chul-Ho

2016-10-27

Two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDCs) and black phosphorous have drawn tremendous attention as an emerging optical material due to their unique and remarkable optical properties. In addition, the ability to create the atomically-controlled van der Waals (vdW) heterostructures enables realizing novel optoelectronic devices that are distinct from conventional bulk counterparts. In this short review, we first present the atomic and electronic structures of 2D semiconducting TMDCs and their exceptional optical properties, and further discuss the fabrication and distinctive features of vdW heterostructures assembled from different kinds of 2D materials with various physical properties. We then focus on reviewing the recent progress on the fabrication of 2D semiconductor optoelectronic devices based on vdW heterostructures including photodetectors, solar cells, and light-emitting devices. Finally, we highlight the perspectives and challenges of optoelectronics based on 2D semiconductor heterostructures.

Mechanics of rolling of nanoribbon on tube and sphere.

PubMed

Yin, Qifang; Shi, Xinghua

2013-06-21

The configuration of graphene nano-ribbon (GNR) assembly on carbon nanotube (CNT) and sphere is studied through theoretical modeling and molecular simulation. The GNR can spontaneously wind onto the CNT due to van der Waals (vdW) interaction and form two basic configurations: helix and scroll. The final configuration arises from the competition among three energy terms: the bending energy of the GNR, the vdW interaction between GNR and CNT, the vdW between the GNR itself. We derive analytical solutions by accounting for the three energy parts, with which we draw phase diagrams and predict the final configuration (helix or scroll) based on the selected parameters. The molecular simulations are conducted to verify the model with the results agree well with the model predicted. Our work can be used to actively control and transfer the tube-like nanoparticles and viruses as well as to assemble ribbon-like nanomaterials.

Two-Dimensional Semiconductor Optoelectronics Based on van der Waals Heterostructures

PubMed Central

Lee, Jae Yoon; Shin, Jun-Hwan; Lee, Gwan-Hyoung; Lee, Chul-Ho

2016-01-01

Two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDCs) and black phosphorous have drawn tremendous attention as an emerging optical material due to their unique and remarkable optical properties. In addition, the ability to create the atomically-controlled van der Waals (vdW) heterostructures enables realizing novel optoelectronic devices that are distinct from conventional bulk counterparts. In this short review, we first present the atomic and electronic structures of 2D semiconducting TMDCs and their exceptional optical properties, and further discuss the fabrication and distinctive features of vdW heterostructures assembled from different kinds of 2D materials with various physical properties. We then focus on reviewing the recent progress on the fabrication of 2D semiconductor optoelectronic devices based on vdW heterostructures including photodetectors, solar cells, and light-emitting devices. Finally, we highlight the perspectives and challenges of optoelectronics based on 2D semiconductor heterostructures. PMID:28335321

Self-Assembly of Nanoclusters into Mono-, Few-, and Multilayered Sheets via Dipole-Induced Asymmetric van der Waals Attraction.

PubMed

Wu, Zhennan; Liu, Jiale; Li, Yanchun; Cheng, Ziyi; Li, Tingting; Zhang, Hao; Lu, Zhongyuan; Yang, Bai

2015-06-23

Two-dimensional (2D) nanomaterials possessing regular layered structures and versatile chemical composition are highly expected in many applications. Despite the importance of van der Waals (vdW) attraction in constructing and maintaining layered structures, the origin of 2D anisotropy is not fully understood, yet. Here, we report the 2D self-assembly of ligand-capped Au15 nanoclusters into mono-, few-, and multilayered sheets in colloidal solution. Both the experimental results and computer simulation reveal that the 2D self-assembly is initiated by 1D dipolar attraction common in nanometer-sized objects. The dense 1D attachment of Au15 leads to a redistribution of the surface ligands, thus generating asymmetric vdW attraction. The deliberate control of the coordination of dipolar and vdW attraction further allows to manipulate the thickness and morphologies of 2D self-assembly architectures.

Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

PubMed Central

Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

Molecular Beam Epitaxial Growth and Characterization of Graphene and Hexagonal Boron Nitride Two-Dimensional Layers

NASA Astrophysics Data System (ADS)

Zheng, Renjing

Van der Waals (vdW) materials (also called as two-dimensional (2D) material in some literature) systems have received extensive attention recently due to their potential applications in next-generation electronics platform. Exciting properties have been discovered in this field, however, the performance and properties of the systems rely on the materials' quality and interface significantly, leading to the urgent need for scalable synthesis of high-quality vdW crystals and heterostructures. Toward this direction, this dissertation is devoted on the study of Molecular Beam Epitaxy (MBE) growth and various characterization of vdW materials and heterostructures, especially graphene and hexagonal boron nitride (h-BN). The goal is to achieve high-quality vdW materials and related heterostructures. There are mainly four projects discussed in this dissertation. The first project (Chapter 2) is about MBE growth of large-area h-BN on copper foil. After the growth, the film was transferred onto SiO2 substrate for characterization. It is observed that as-grown film gives evident h-BN Raman spectrum; what's more, h-BN peak intensity and position is dependent on film thickness. N-1s and B-1s XPS peaks further suggest the formation of h-BN. AFM and SEM images show the film is flat and continuous over large area. Our synthesis method shows it's possible to use MBE to achieve h-BN growth and could also pave a way for some unique structure, such as h-BN/graphene heterostructures and doped h-BN films by MBE. The second project (Chapter 3) is focused on establishment of grapehene/h-BN heterostructure on cobalt (Co) film. In-situ epitaxial growth of graphene/h-BN heterostructures on Co film substrate was achieved by using plasma-assisted MBE. The direct graphene/h-BN vertical stacking structures were demonstrated and further confirmed by various characterizations, such as Raman spectroscopy, SEM, XPS and TEM. Large area heterostructures consisting of single- /bilayer graphene and multilayer h-BN were achieved. The mismatch angle between graphene and h-BN is below 1º. The third project (Chapter 4) is about graphene growth on Fe by MBE at low temperature. Temperature-dependent growth of graphene on Fe using MBE is studied. Two-dimensional (2D), large-area graphene samples were grown on Fe thin films, and characterized by Raman, X-ray photoelectron spectroscopy, X-ray diffraction, optical microscopy, transmission electron microscopy and atomic force microscopy. Graphene is achieved on Fe at a wide growth temperature range and as low as 400 °C. The growth mechanism is studied and shows graphene growth is associated with formation and decomposition of iron carbide. The forth part is about a convenient way to produce vdW heterostructures: graphene growth of exfoliated h-BN on Co. We demonstrated graphene/h-BN heterostructures by growing graphene onto the substrates which consist of exfoliated h-BN on Co thin film using MBE. The heterostructure samples grown at different temperatures and growth durations were characterized by Raman, optical microscopy, atomic force microscopy, microwave impedance microscopy and scanning tunneling microscopy. It is found that the graphene/h-BN heterostructures were formed by the formation of graphene underneath rather than on top of the h-BN flakes. The growth mechanism is discussed. In summary, we develop and optimize growth of vdW materials (h-BN and graphene), and vdW heterostructures by MBE. Various characterization has been carried out to evaluate properties of the films in structural, optical and electrical aspects. Our results reveal that MBE can provide an excellent alternative way for reliable growth of high-quality and large-size vdW materials and related heterostructures, which will attract more attention for the utilization of MBE in vdW materials research.

Esaki Diodes in van der Waals Heterojunctions with Broken-Gap Energy Band Alignment.

PubMed

Yan, Rusen; Fathipour, Sara; Han, Yimo; Song, Bo; Xiao, Shudong; Li, Mingda; Ma, Nan; Protasenko, Vladimir; Muller, David A; Jena, Debdeep; Xing, Huili Grace

2015-09-09

van der Waals (vdW) heterojunctions composed of two-dimensional (2D) layered materials are emerging as a solid-state materials family that exhibits novel physics phenomena that can power a range of electronic and photonic applications. Here, we present the first demonstration of an important building block in vdW solids: room temperature Esaki tunnel diodes. The Esaki diodes were realized in vdW heterostructures made of black phosphorus (BP) and tin diselenide (SnSe2), two layered semiconductors that possess a broken-gap energy band offset. The presence of a thin insulating barrier between BP and SnSe2 enabled the observation of a prominent negative differential resistance (NDR) region in the forward-bias current-voltage characteristics, with a peak to valley ratio of 1.8 at 300 K and 2.8 at 80 K. A weak temperature dependence of the NDR indicates electron tunneling being the dominant transport mechanism, and a theoretical model shows excellent agreement with the experimental results. Furthermore, the broken-gap band alignment is confirmed by the junction photoresponse, and the phosphorus double planes in a single layer of BP are resolved in transmission electron microscopy (TEM) for the first time. Our results represent a significant advance in the fundamental understanding of vdW heterojunctions and broaden the potential applications of 2D layered materials.

Thermionic Energy Conversion Based on Graphene van der Waals Heterostructures

PubMed Central

Liang, Shi-Jun; Liu, Bo; Hu, Wei; Zhou, Kun; Ang, L. K.

2017-01-01

Seeking for thermoelectric (TE) materials with high figure of merit (or ZT), which can directly converts low-grade wasted heat (400 to 500 K) into electricity, has been a big challenge. Inspired by the concept of multilayer thermionic devices, we propose and design a solid-state thermionic devices (as a power generator or a refrigerator) in using van der Waals (vdW) heterostructure sandwiched between two graphene electrodes, to achieve high energy conversion efficiency in the temperature range of 400 to 500 K. The vdW heterostructure is composed of suitable multiple layers of transition metal dichalcogenides (TMDs), such as MoS2, MoSe2, WS2 and WSe2. From our calculations, WSe2 and MoSe2 are identified as two ideal TMDs (using the reported experimental material’s properties), which can harvest waste heat at 400 K with efficiencies about 7% to 8%. To our best knowledge, this design is the first in combining the advantages of graphene electrodes and TMDs to function as a thermionic-based device. PMID:28387363

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirkov, Leonid; Makarewicz, Jan, E-mail: jama@amu.edu.pl

An ab initio intermolecular potential energy surface (PES) has been constructed for the benzene-krypton (BKr) van der Waals (vdW) complex. The interaction energy has been calculated at the coupled cluster level of theory with single, double, and perturbatively included triple excitations using different basis sets. As a result, a few analytical PESs of the complex have been determined. They allowed a prediction of the complex structure and its vibrational vdW states. The vibrational energy level pattern exhibits a distinct polyad structure. Comparison of the equilibrium structure, the dipole moment, and vibrational levels of BKr with their experimental counterparts has allowedmore » us to design an optimal basis set composed of a small Dunning’s basis set for the benzene monomer, a larger effective core potential adapted basis set for Kr and additional midbond functions. Such a basis set yields vibrational energy levels that agree very well with the experimental ones as well as with those calculated from the available empirical PES derived from the microwave spectra of the BKr complex. The basis proposed can be applied to larger complexes including Kr because of a reasonable computational cost and accurate results.« less

Charge Separation at Mixed-Dimensional Single and Multilayer MoS2/Silicon Nanowire Heterojunctions.

PubMed

Henning, Alex; Sangwan, Vinod K; Bergeron, Hadallia; Balla, Itamar; Sun, Zhiyuan; Hersam, Mark C; Lauhon, Lincoln J

2018-05-16

Layered two-dimensional (2-D) semiconductors can be combined with other low-dimensional semiconductors to form nonplanar mixed-dimensional van der Waals (vdW) heterojunctions whose charge transport behavior is influenced by the heterojunction geometry, providing a new degree of freedom to engineer device functions. Toward that end, we investigated the photoresponse of Si nanowire/MoS 2 heterojunction diodes with scanning photocurrent microscopy and time-resolved photocurrent measurements. Comparison of n-Si/MoS 2 isotype heterojunctions with p-Si/MoS 2 heterojunction diodes under varying biases shows that the depletion region in the p-n heterojunction promotes exciton dissociation and carrier collection. We measure an instrument-limited response time of 1 μs, which is 10 times faster than the previously reported response times for planar Si/MoS 2 devices, highlighting the advantages of the 1-D/2-D heterojunction. Finite element simulations of device models provide a detailed understanding of how the electrostatics affect charge transport in nanowire/vdW heterojunctions and inform the design of future vdW heterojunction photodetectors and transistors.

Trends on band alignments: Validity of Anderson's rule in SnS2- and SnSe2-based van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Koda, Daniel S.; Bechstedt, Friedhelm; Marques, Marcelo; Teles, Lara K.

2018-04-01

Van der Waals (vdW) heterostructures are promising candidates for building blocks in novel electronic and optoelectronic devices with tailored properties, since their electronic action is dominated by the band alignments upon their contact. In this work, we analyze 10 vdW heterobilayers based on tin dichalcogenides by first-principles calculations. Structural studies show that all systems are stable, and that commensurability leads to smaller interlayer distances. Using hybrid functional calculations, we derive electronic properties and band alignments for all the heterosystems and isolated two-dimensional (2D) crystals. Natural band offsets are derived from calculated electron affinities and ionization energies of 11 freestanding 2D crystals. They are compared with band alignments in true heterojunctions, using a quantum mechanical criterion, and available experimental data. For the hBN/SnSe 2 system, we show that hBN suffers an increase in band gap, while leaving almost unchanged the electronic properties of SnSe2. Similarly, MX2 (M = Mo, W; X = S, Se) over SnX2 preserve the natural discontinuities from each side of the heterobilayer. Significant charge transfer occurs in junctions with graphene, which becomes p-doped and forms an Ohmic contact with SnX2. Zirconium and hafnium dichalcogenides display stronger interlayer interactions, leading to larger shifts in band alignments with tin dichalcogenides. Significant orbital overlap is found, which creates zero conduction band offset systems. The validity of the Anderson electron affinity rule is discussed. Failures of this model are traced back to interlayer interaction, band hybridization, and quantum dipoles. The systematic work sheds light on interfacial engineering for future vdW electronic and optoelectronic devices.

Irreversible evolution of angular-dependent coercivity in Fe80Ni20 nanowire arrays: Detection of a single vortex state

NASA Astrophysics Data System (ADS)

Alikhani, M.; Ramazani, A.; Almasi Kashi, M.; Samanifar, S.; Montazer, A. H.

2016-09-01

The irreversible evolution of magnetic coercivity in arrays of 75 nm diameter Fe80Ni20 nanowires (NWs) has been explored by means of first-order reversal curve (FORC) analysis as a function of the angle between the magnetic field and the NW axis (0°≤θ≤90°). The Fe80Ni20 NWs with lengths up to 60 μm were fabricated using a pulsed electrodeposition method into hard-anodic aluminum oxide templates with an interpore distance of 275 nm. Investigating the interwire and intrawire magnetostatic interactions, the angular FORC (AFORC) diagrams indicated enhanced intrawire interactions with increasing length and θ (<90°), induced by a magnetization reversal through vortex domain wall (VDW) propagation. Intriguingly, in addition to the VDW mode, a single vortex state with broad irreversible switching of nucleation and annihilation fields was detected at θ=83° for 60 μm long NWs. At θ=90°, the NWs reversed magnetization through transverse domain wall, involving a reversible component by a fraction of 95%. Furthermore, the transition angle between the reversal modes was found to decrease with increasing aspect ratio from 200 to 800. The irreversible angular-dependent coercivity (HcIrrev(θ)) of Fe80Ni20 NWs was extracted from the AFORC measurements and compared with the major angular dependence of coercivity (HcMajor(θ)) obtained from the conventional hysteresis loop measurements. While HcMajor(θ) showed a non-monotonic behavior, HcIrrev(θ) constantly increased with increasing θ (<90°). On the other hand, using analytical models, a 93% agreement was obtained between the theoretical angular-dependent nucleation field and experimental HcIrrev(θ) for irreversible switching of VDW when 0°≤θ≤86°.

Comparison of capnovolumetry-derived dead space parameters with pulmonary function test in normal adults using histamine provocation.

PubMed

Sun, Xiaoli; Zhang, Yan; Yang, Wenlan; Liu, Jinming

2015-04-01

This study in healthy adults was conducted to explore the clinical application of capnovolumetric indices as compared to lung function parameters using histamine provocation. Forty healthy subjects received aerosol histamine or salbutamol in an automatic stimulation system with escalating doses of histamine. Dead space volumes of capnovolumetry and lung function parameters were examined with increased concentrations of histamine at a fixed time interval. The doses of histamine were selected from 0.0562 mg-2.2 mg and 0.1 mg salbutamol was inhaled when a maximal dose of histamine was reached. Baseline values in each group were calculated prior to histamine inhalation. Fowler dead space (VDF), Wolff dead space (VDW), threshold dead space (VDT), Bohr dead space (VDB), forced expiratory volume in 1 s (FEV1 ) and peak expiratory flow (PEF) showed a dose-dependent reduction following histamine provocation, but there were no statistical differences in the measurements at baseline and post S6 provocation. The value of dC3/DV at the maximal dose was significantly increased over its baseline value (P < 0.05). VDF, VDT and VDW were significantly increased after bronchodilator use (P < 0.05 or <0.01). The changes in capnovolumetry did not correspond with the results of lung function test. The dC3/DV and airway dead spaces of capnovolumetry in healthy adults are significantly increased compared to lung function parameters before or after bronchodilator use, suggesting that capnovolumetry is feasible in diagnostic evaluation of airway reactivity, especially for persons who are unable to undertake lung function test. © 2014 John Wiley & Sons Ltd.

Temperature Dependence of Densities and Excess Molar Volumes of the Ternary Mixture (1-Butanol + Chloroform + Benzene) and its Binary Constituents (1-Butanol + Chloroform and 1-Butanol + Benzene)

NASA Astrophysics Data System (ADS)

Smiljanić, Jelena D.; Kijevčanin, Mirjana Lj.; Djordjević, Bojan D.; Grozdanić, Dušan K.; Šerbanović, Slobodan P.

2008-04-01

Densities ρ of the 1-butanol + chloroform + benzene ternary mixture and the 1-butanol + chloroform and 1-butanol + benzene binaries have been measured at six temperatures (288.15, 293.15, 298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure, using an oscillating U-tube densimeter. From these densities, excess molar volumes ( V E) were calculated and fitted to the Redlich Kister equation for all binary mixtures and to the Nagata and Tamura equation for the ternary system. The Radojković et al. equation has been used to predict excess molar volumes of the ternary mixtures. Also, V E data of the binary systems were correlated by the van der Waals (vdW1) and Twu Coon Bluck Tilton (TCBT) mixing rules coupled with the Peng Robinson Stryjek Vera (PRSV) equation of state. The prediction and correlation of V E data for the ternary system were performed by the same models.

The 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)-imide ionic liquid nanodroplets on solid surfaces and in electric field: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Dong, Dengpan; Vatamanu, Jenel P.; Wei, Xiaoyu; Bedrov, Dmitry

2018-05-01

Atomistic molecular dynamics simulations were conducted to study the wetting states of 1-ethyl-3-methylimidazolium bis(trifluoro-methylsulfonyl)-imide ionic liquid (IL) nanodroplets on surfaces with different strengths of van der Waals (VDW) interactions and in the presence of an electric field. By adjusting the depth of Lennard-Jones potential, the van der Waals interaction between the solid surface and ionic liquid was systematically varied. The shape of the droplets was analyzed to extract the corresponding contact angle utilized to characterize wetting states of the nanodroplets. The explored range of surface-IL interactions allowed contact angles ranging from complete IL spreading on the surface to poor wettability. The effect of the external electrical field was explored by adding point charges to the surface atoms. Systems with two charge densities (±0.002 e/atom and ±0.004 e/atom) that correspond to 1.36 V/nm and 2.72 V/nm electric fields were investigated. Asymmetrical wetting states were observed for both cases. At 1.36 V/nm electric field, contributions of IL-surface VDW interactions and Coulombic interactions to the wetting state were competitive. At 2.72 V/nm field, electrostatic interactions dominate the interaction between the nanodroplet and surface, leading to enhanced wettability on all surfaces.

Reconstruction of low-index graphite surfaces

NASA Astrophysics Data System (ADS)

Thinius, Sascha; Islam, Mazharul M.; Bredow, Thomas

2016-07-01

The low-index graphite surfaces (10 1 -0), (10 1 -1), (11 2 -0) and (11 2 - 1) have been studied by density functional theory (DFT) including van-der-Waals (vdW) corrections. Different from the (0001) surface which has been extensively investigated both experimentally and theoretically, there is no comprehensive study on the (10 1 -0)- (10 1 -1)-, (11 2 -0)- and (11 2 - 1)-surfaces available, although they are of relevance for Li insertion processes, e.g. in Li-ion batteries. In this study the structure and stability of all non-(0001) low-index surfaces were calculated with RPBE-D3 and converged slab models. In all cases reconstruction involving bond formation between unsaturated carbon atoms of two neighboring graphene sheets reduces the surface energy dramatically. Two possible reconstruction patterns have been considered. The first possibility leads to formation of oblong nanotubes. Alternatively, the graphene sheets form bonds to different neighboring sheets at the upper and lower sides and sinusoidal structures are formed. Both structure types have similar stabilities. Based on the calculated surface energies the Gibbs-Wulff theorem was applied to construct the macroscopic shape of graphite single crystals.

Imaging exciton–polariton transport in MoSe2 waveguides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, F.; Luan, Y.; Scott, M. E.

The exciton polariton (EP), a half-light and half-matter quasiparticle, is potentially an important element for future photonic and quantum technologies1-4. It provides both strong light-matter interactions and long-distance propagation that is necessary for applications associated with energy or information transfer. Recently, strongly-coupled cavity EPs at room temperature have been demonstrated in van der Waals (vdW) materials due to their strongly-bound excitons5-9. Here we report a nano-optical imaging study of waveguide EPs in MoSe2, a prototypical vdW semiconductor. The measured propagation length of the EPs is sensitive to the excitation photon energy and reaches over 12 μm. The polariton wavelength canmore » be conveniently altered from 600 nm down to 300 nm by controlling the waveguide thickness. Furthermore, we found an intriguing back-bending polariton dispersion close to the exciton resonance. The observed EPs in vdW semiconductors could be useful in future nanophotonic circuits operating in the near-infrared to visible spectral regions.« less

Imaging exciton–polariton transport in MoSe2 waveguides

DOE PAGES

Hu, F.; Luan, Y.; Scott, M. E.; ...

2017-05-08

The exciton polariton (EP), a half-light and half-matter quasiparticle, is potentially an important element for future photonic and quantum technologies1-4. It provides both strong light-matter interactions and long-distance propagation that is necessary for applications associated with energy or information transfer. Recently, strongly-coupled cavity EPs at room temperature have been demonstrated in van der Waals (vdW) materials due to their strongly-bound excitons5-9. Here we report a nano-optical imaging study of waveguide EPs in MoSe2, a prototypical vdW semiconductor. The measured propagation length of the EPs is sensitive to the excitation photon energy and reaches over 12 μm. The polariton wavelength canmore » be conveniently altered from 600 nm down to 300 nm by controlling the waveguide thickness. Furthermore, we found an intriguing back-bending polariton dispersion close to the exciton resonance. The observed EPs in vdW semiconductors could be useful in future nanophotonic circuits operating in the near-infrared to visible spectral regions.« less

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

PubMed

Zheng, Qijing; Saidi, Wissam A; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V; Petek, Hrvoje; Zhao, Jin

2017-10-11

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Can nonadditive dispersion forces explain chain formation of nanoparticles?

NASA Astrophysics Data System (ADS)

Kwaadgras, Bas W.; Verdult, Maarten W. J.; Dijkstra, Marjolein; van Roij, René

2013-03-01

We study to what extent dielectric nanoparticles prefer to self-assemble into linear chains or into more compact structures. To calculate the Van der Waals (VdW) attraction between the clusters we use the Coupled Dipole Method (CDM), which treats each atom in the nanoparticle as an inducible oscillating point dipole. The VdW attraction then results from the full many-body interactions between the dipoles. For non-capped nanoparticles, we calculate in which configuration the VdW attraction is maximal. We find that in virtually all cases we studied, many-body effects only result in local potential minima at the linear configuration, as opposed to global ones, and that these metastable minima are in most cases rather shallow compared to the thermal energy. In this work, we also compare the CDM results with those from Hamaker-de Boer and Axilrod-Teller theory to investigate the influence of the many-body effects and the accuracy of these two approximate methods.

Asymmetric van der Waals Forces Drive Orientation of Compositionally Anisotropic Nanocylinders within Smectic Arrays: Experiment and Simulation

PubMed Central

Smith, Benjamin D.; Fichthorn, Kristen A.; Kirby, David J.; Quimby, Lisa M.; Triplett, Derek A.; González, Pedro; Hernández, Darimar; Keating, Christine D.

2014-01-01

Understanding how micro- and nanoparticles interact is important for achieving bottom-up assembly of desired structures. Here, we examine the self-assembly of two-component, compositionally asymmetric nanocylinders that sediment from solution onto a solid surface. These particles spontaneously formed smectic arrays. Within the rows of an array, nanocylinders tended to assemble such that neighboring particles had the same orientation of their segments. As a probe of interparticle interactions, we classified nanocylinder alignments by measuring the segment orientations of many sets of neighboring particles. Monte Carlo simulations incorporating an exact expression for the van der Waals (vdW) energy indicate that differences in the vdW interactions, even when small, are the key factor in producing observed segment alignment. These results point to asymmetrical vdW interactions as a potentially powerful means of controlling orientation in multicomponent cylinder arrays, and suggest that designing for these interactions could yield new ways to control self-assembly. PMID:24308771

Relativistic coupled-cluster and density-functional studies of argon at high pressure

NASA Astrophysics Data System (ADS)

Schwerdtfeger, Peter; Steenbergen, Krista G.; Pahl, Elke

2017-06-01

The equation of state P (V ,T ) for solid argon is determined by the calculation of accurate static and vibrational terms in the free energy. The static component comes from a quantum theoretical many-body expansion summing over all energetic contributions from two-, three-, and four-body fragments treated with relativistic coupled cluster theory, while the lattice vibrations are described at an anharmonic level including two- and three-body forces as well as temperature effects. The dynamic part is calculated within the Debye and Einstein approximation, as well as by a more accurate phonon treatment where the vibrational motions in the lattice are coupled. Our results are in good agreement with room-temperature high-pressure experimental data up to ˜20 GPa. In the 20-100 GPa pressure range, however, we see considerable deviations between experiment and theory, perhaps indicating missing four-body contributions (beyond the quadruple dipole terms included here), missing five and higher-body effects, and the need to go beyond the coupled cluster singles-doubles with perturbative triples treatment in such higher-body forces. This contrasts with the results for solid neon, where excellent agreement has been achieved taking only two- and three-body forces into account [P. Schwerdtfeger and A. Hermann, Phys. Rev. B 80, 064106 (2009), 10.1103/PhysRevB.80.064106]. We demonstrate that the phase transition from fcc to hcp cannot account for the large discrepancies observed. Density functional calculations give very mixed results in the high-pressure region, but some functionals such as optB88-vdW (proposed by Lundqvist and co-workers) describe the many-body forces in argon reasonably well over the range of pressures investigated. Theoretical investigations of the heavier rare gas solids reaching experimental accuracy in the high-pressure regime therefore remain a significant challenge.

Molecular dynamics simulation and TDDFT study of the structures and UV-vis absorption spectra of MCT-β-CD and its inclusion complexes.

PubMed

Lu, Huijuan; Wang, Yujiao; Xie, Xiaomei; Chen, Feifei; Li, Wei

2015-01-01

In this research, the inclusion ratios and inclusion constants of MCT-β-CD/PERM and MCT-β-CD/CYPERM inclusion complexes were measured by UV-vis and fluorescence spectroscopy. The inclusion ratios are both 1:1, and the inclusion constants are 60 and 342.5 for MCT-β-CD/PERM and MCT-β-CD/CYPERM, respectively. The stabilities of inclusion complexes were investigated by MD simulation. MD shows that VDW energy plays a vital role in the stability of inclusion complex, and the destruction of inclusion complex is due to the increasing temperature. The UV-vis absorption spectra of MCT-β-CD and its inclusion complexes were studied by time-dependent density functional theory (TDDFT) method employing BLYP-D3, B3LYP-D3 and M06-2X-D3 functionals. BLYP-D3 well reproduces the UV-vis absorption spectrum and reveals that the absorption bands of MCT-β-CD mainly arise from n→π(∗) and n→σ(∗) transition, and those of inclusion complexes mainly arise from intramolecular charge transfer (ICT). ICT results in the shift of main absorption bands of MCT-β-CD. Copyright © 2015 Elsevier B.V. All rights reserved.

Physisorption of three amine terminated molecules (TMBDA, BDA, TFBDA) on the Au(111) Surface: The Role of van der Waals Interaction

NASA Astrophysics Data System (ADS)

Aminpour, Maral; Le, Duy; Rahman, Talat S.

2012-02-01

Recently, the electronic properties and alignment of tetramethyl-1,4-benzenediamine (TMBDA), 1,4-benzenediamine (BDA) and tetrafluro-1,4-benzenediamine (TFBDA) molecules were studied experimentally. Discrepancies were found for both the binding energy and the molecule tilt angle with respect to the surface, when results were compared with density functional theory calculations [1]. We have included the effect of vdW interactions both between the molecules and the Au(111) surface and find binding energies which are in very good agreement with experiments. We also find that at low coverages each of these molecules would adsorb almost parallel to the surface. N-Au bond lengths and charge redistribution on adsorption of the molecules are also analyzed. Our calculations are based on DFT using vdW-DF exchange correlation functionals. For BDA (since we are aware of experimental data), we show that for higher coverage, inclusion of intermolecular van der Waals interaction leads to tilting of the molecules with respect to the surface and formation of line structures. Our results demonstrate the central role played by intermolecular interaction in pattern formation on this surface.[4pt] [1] M. Dell'Angela et al, Nano Lett. 2010, 10, 2470; M. Kamenetska et al, J. Phys. Chem. C, 2011, 115, 12625

Calculation of Beach Change Under Interacting Cross-Shore and Longshore Processes

DTIC Science & Technology

2010-01-01

the dune toe , berm width, and shoreline position are calculated, while maintaining longshore transport rates representative of the regional long-term...during growth together with the dune shape, the seaward movement of the dune toe ΔyDw for a given increase in dune volume ΔVDw is: ΔyDw = ΔVDw DD ð2Þ...Expressing Eq. (1) in terms of dune toe advance yields: dyDw dt = qw DD ð3Þ It is assumed that sand transport to the dune is related to thewidth of the

Dynamic surface electronic reconstruction as symmetry-protected topological orders in topological insulator Bi2Se3

NASA Astrophysics Data System (ADS)

Shu, G. J.; Liou, S. C.; Karna, S. K.; Sankar, R.; Hayashi, M.; Chou, F. C.

2018-04-01

The layered narrow-band-gap semiconductor Bi2Se3 is composed of heavy elements with strong spin-orbital coupling, which has been identified both as a good candidate for a thermoelectric material with high thermoelectric figure of merit (Z T ) and as a topological insulator of the Z2 type with a gapless surface band in a Dirac-cone shape. The existence of a conjugated π -bond system on the surface of each Bi2Se3 quintuple layer is proposed based on an extended valence bond model with valence electrons distributed in the hybridized orbitals. Supporting experimental evidence of a two-dimensional (2D) conjugated π -bond system on each quintuple layer of Bi2Se3 is provided using electron energy-loss spectroscopy and electron density mapping through inverse Fourier transform of x-ray diffraction data. Quantum chemistry calculations support the π -bond existence between partially filled 4 pz orbitals of Se via side-to-side orbital overlap positively. The conjugated π -bond system on the surface of each quintuple Bi2Se3 layer is proposed to be similar to that found in graphite (graphene) and responsible for the unique 2D conduction mechanism. The van der Waals (vdW) attractive force between quintuple layers is interpreted to be coming from the antiferroelectrically ordered effective electric dipoles, which are constructed with π -bond trimer pairs on Se layers across the vdW gap of minimized Coulomb repulsion.

Three-particle annihilation in a 2D heterostructure revealed through data-hypercubic photoresponse microscopy (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gabor, Nathaniel M.

2017-05-01

Van de Waals (vdW) heterostructures - which consist of precisely assembled atomically thin electronic materials - exhibit unusual quantum behavior. These quantum materials-by-design are of fundamental interest in basic scientific research and hold tremendous potential in advanced technological applications. Problematically, the fundamental optoelectronic response in these heterostructures is difficult to access using the standard techniques within the traditions of materials science and condensed matter physics. In the standard approach, characterization is based on the measurement of a small amount of one-dimensional data, which is used to gain a precise picture of the material properties of the sample. However, these techniques are fundamentally lacking in describing the complex interdependency of experimental degrees of freedom in vdW heterostructures. In this talk, I will present our recent experiments that utilize a highly data-intensive approach to gain deep understanding of the infrared photoresponse in vdW heterostructure photodetectors. These measurements, which combine state-of-the-art data analytics and measurement design with fundamentally new device structures and experimental parameters, give a clear picture of electron-hole pair interactions at ultrafast time scales.

Controllable Schottky barrier in GaSe/graphene heterostructure: the role of interface dipole

NASA Astrophysics Data System (ADS)

Si, Chen; Lin, Zuzhang; Zhou, Jian; Sun, Zhimei

2017-03-01

The discoveries of graphene and other related two-dimensional crystals have recently led to a new technology: van der Waals (vdW) heterostructures based on these atomically thin materials. Such a paradigm has been proved promising for a wide range of applications from nanoelectronics to optoelectronics and spintronics. Here, using first-principles calculations, we investigate the electronic structure and interface characteristics of a newly synthesized GaSe/graphene (GaSe/g) vdW heterostructure. We show that the intrinsic electronic properties of GaSe and graphene are both well preserved in the heterostructure, with a Schottky barrier formed at the GaSe/g interface. More interestingly, the band alignment between graphene and GaSe can be effectively modulated by tuning the interfacial distance or applying an external electric filed. This makes the Schottky barrier height (SBH) controllable, which is highly desirable in the electronic and optoelectronic devices based on vdW heterostructures. In particular, the tunability of the interface dipole and potential step is further uncovered to be the underlying mechanism that ensures this controllable tuning of SBH.

Tunable Schottky barrier in van der Waals heterostructures of graphene and g-GaN

NASA Astrophysics Data System (ADS)

Sun, Minglei; Chou, Jyh-Pin; Ren, Qingqiang; Zhao, Yiming; Yu, Jin; Tang, Wencheng

2017-04-01

Using first-principles calculations, we systematically investigated the electronic properties of graphene/g-GaN van der Waals (vdW) heterostructures. We discovered that the Dirac cone of graphene could be quite well preserved in the vdW heterostructures. Moreover, a transition from an n-type to p-type Schottky contact at the graphene/g-GaN interface was induced with a decreased interlayer distance from 4.5 to 2.5 Å. This relationship is expected to enable effective control of the Schottky barrier, which is an important development in the design of Schottky devices.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makarewicz, Jan, E-mail: jama@amu.edu.pl; Shirkov, Leonid

The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center ofmore » mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy D{sub e} of 392 cm{sup −1} is close to that of 387 cm{sup −1} calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, D{sub e} for PAr becomes slightly lower than D{sub e} for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.« less

Character of intermolecular interaction in pyridine-argon complex: Ab initio potential energy surface, internal dynamics, and interrelations between SAPT energy components.

PubMed

Makarewicz, Jan; Shirkov, Leonid

2016-05-28

The pyridine-Ar (PAr) van der Waals (vdW) complex is studied using a high level ab initio method. Its structure, binding energy, and intermolecular vibrational states are determined from the analytical potential energy surface constructed from interaction energy (IE) values computed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations with the augmented correlation consistent polarized valence double-ζ (aug-cc-pVDZ) basis set complemented by midbond functions. The structure of the complex at its global minimum with Ar at a distance of 3.509 Å from the pyridine plane and shifted by 0.218 Å from the center of mass towards nitrogen agrees well with the corresponding equilibrium structure derived previously from the rotational spectrum of PAr. The PAr binding energy De of 392 cm(-1) is close to that of 387 cm(-1) calculated earlier at the same ab initio level for the prototypical benzene-Ar (BAr) complex. However, under an extension of the basis set, De for PAr becomes slightly lower than De for BAr. The ab initio vdW vibrational energy levels allow us to estimate the reliability of the methods for the determination of the vdW fundamentals from the rotational spectra. To disclose the character of the intermolecular interaction in PAr, the symmetry-adapted perturbation theory (SAPT) is employed for the analysis of different physical contributions to IE. It is found that SAPT components of IE can be approximately expressed in the binding region by only two of them: the exchange repulsion and dispersion energy. The total induction effect is negligible. The interrelations between various SAPT components found for PAr are fulfilled for a few other complexes involving aromatic molecules and Ar or Ne, which indicates that they are valid for all rare gas (Rg) atoms and aromatics.

Free vibration of multiwall carbon nanotubes

NASA Astrophysics Data System (ADS)

Wang, C. Y.; Ru, C. Q.; Mioduchowski, A.

2005-06-01

A multiple-elastic shell model is applied to systematically study free vibration of multiwall carbon nanotubes (MWNTs). Using Flugge [Stresses in Shells (Springer, Berlin, 1960)] equations of elastic shells, vibrational frequencies and associated modes are calculated for MWNTs of innermost radii 5 and 0.65 nm, respectively. The emphasis is placed on the effect of interlayer van der Waals (vdW) interaction on free vibration of MWNTs. Our results show that the interlayer vdW interaction has a crucial effect on radial (R) modes of large-radius MWNTs (e.g., of the innermost radius 5 nm), but is less pronounced for R modes of small-radius MWNTs (e.g., of the innermost radius 0.65 nm), and usually negligible for torsional (T) and longitudinal (L) modes of MWNTs. This is attributed to the fact that the interlayer vdW interaction, characterized by a radius-independent vdW interaction coefficient, depends on radial deflections only, and is dominant only for large-radius MWNTs of lower radial rigidity but less pronounced for small-radius MWNTs of much higher radial rigidity. As a result, the R modes of large-radius MWNTs are typically collective motions of almost all nested tubes, and the R modes of small-radius MWNTs, as well as the T and L modes of MWNTs, are basically vibrations of individual tubes. In particular, an approximate single-shell model is suggested to replace the multiple-shell model in calculating the lowest frequency of R mode of thin MWNTs (defined by the innermost radius-to-thickness ratio not less than 4) with relative errors less than 10%. In addition, the simplified Flugge single equation is adopted to substitute the exact Flugge equations in determining the R-mode frequencies of MWNTs with relative errors less than 10%.

Computations of Lifshitz-van der Waals interaction energies between irregular particles and surfaces at all separations for resuspension modelling

NASA Astrophysics Data System (ADS)

Priye, Aashish; Marlow, William H.

2013-10-01

The phenomenon of particle resuspension plays a vital role in numerous fields. Among many aspects of particle resuspension dynamics, a dominant concern is the accurate description and formulation of the van der Waals (vdW) interactions between the particle and substrate. Current models treat adhesion by incorporating a material-dependent Hamaker's constant which relies on the heuristic Hamaker's two-body interactions. However, this assumption of pairwise summation of interaction energies can lead to significant errors in condensed matter as it does not take into account the many-body interaction and retardation effects. To address these issues, an approach based on Lifshitz continuum theory of vdW interactions has been developed to calculate the principal many-body interactions between arbitrary geometries at all separation distances to a high degree of accuracy through Lifshitz's theory. We have applied this numerical implementation to calculate the many-body vdW interactions between spherical particles and surfaces with sinusoidally varying roughness profile and also to non-spherical particles (cubes, cylinders, tetrahedron etc) orientated differently with respect to the surface. Our calculations revealed that increasing the surface roughness amplitude decreases the adhesion force and non-spherical particles adhere to the surfaces more strongly when their flatter sides are oriented towards the surface. Such practical shapes and structures of particle-surface systems have not been previously considered in resuspension models and this rigorous treatment of vdW interactions provides more realistic adhesion forces between the particle and the surface which can then be coupled with computational fluid dynamics models to improve the predictive capabilities of particle resuspension dynamics.

Effect of dispersion correction on the Au(1 1 1)-H2O interface: A first-principles study

NASA Astrophysics Data System (ADS)

Nadler, Roger; Sanz, Javier Fdez.

2012-09-01

A theoretical study of the H2O-Au(1 1 1) interface based on first principles density functional theory (DFT) calculations with and without inclusion of dispersion correction is reported. Three different computational approaches are considered. First, the standard generalized gradient approximation (GGA) functional PBE is employed. Second, an additional energy term is further included that adds a semi-empirically derived dispersion correction (PBE-D2), and, finally, a recently proposed functional that includes van der Waals (vdW) interactions directly in its functional form (optB86b-vdW) was used to represent the state-of-the art of DFT functionals. The monomeric water adsorption was first considered in order to explore the dependency of geometry on the details of the model slab used to represent it (size, thickness, coverage). When the dispersion corrections are included the Au-H2O interaction is stronger, as manifested by the smaller dAu-O and stronger adsorption energies. Additionally, the interfacial region between Au(1 1 1) slab surfaces and a liquid water layer was investigated with Born-Oppenheimer molecular dynamics (BOMD) using the same functionals. Two or three interfacial orientations can be determined, depending on the theoretical methodology applied. Closest to the surface, H2O is adsorbed O-down, whereas further away it is oriented with one OH bond pointing to the surface and the molecular plane parallel to the normal direction. For the optB86b-vdW functional a third orientation is found where one H atom points into the bulk water layer and the second OH bond is oriented parallel to the metal surface. As for the water density in the first adsorption layer we find a very small increase of roughly 8%. From the analysis of vibrational spectra a weakening of the H-bond network is observed upon the inclusion of the Au(1 1 1) slab, however, no disruption of H-bonds is observed. While the PBE and PBE-D2 spectra are very similar, the optB86b-vdW spectrum shows that the H-bonds are even more weakened.

Dispersion corrected hartree-fock and density functional theory for organic crystal structure prediction.

PubMed

Brandenburg, Jan Gerit; Grimme, Stefan

2014-01-01

We present and evaluate dispersion corrected Hartree-Fock (HF) and Density Functional Theory (DFT) based quantum chemical methods for organic crystal structure prediction. The necessity of correcting for missing long-range electron correlation, also known as van der Waals (vdW) interaction, is pointed out and some methodological issues such as inclusion of three-body dispersion terms are discussed. One of the most efficient and widely used methods is the semi-classical dispersion correction D3. Its applicability for the calculation of sublimation energies is investigated for the benchmark set X23 consisting of 23 small organic crystals. For PBE-D3 the mean absolute deviation (MAD) is below the estimated experimental uncertainty of 1.3 kcal/mol. For two larger π-systems, the equilibrium crystal geometry is investigated and very good agreement with experimental data is found. Since these calculations are carried out with huge plane-wave basis sets they are rather time consuming and routinely applicable only to systems with less than about 200 atoms in the unit cell. Aiming at crystal structure prediction, which involves screening of many structures, a pre-sorting with faster methods is mandatory. Small, atom-centered basis sets can speed up the computation significantly but they suffer greatly from basis set errors. We present the recently developed geometrical counterpoise correction gCP. It is a fast semi-empirical method which corrects for most of the inter- and intramolecular basis set superposition error. For HF calculations with nearly minimal basis sets, we additionally correct for short-range basis incompleteness. We combine all three terms in the HF-3c denoted scheme which performs very well for the X23 sublimation energies with an MAD of only 1.5 kcal/mol, which is close to the huge basis set DFT-D3 result.

A density functional theory computational study of adsorption of Di-Meta-Cyano Azobenzene molecules on Si (111) surfaces

NASA Astrophysics Data System (ADS)

Motevalli, Benyamin; Taherifar, Neda; Wu, Bisheng; Tang, Wenxin; Liu, Jefferson Zhe

2017-11-01

The adsorption of di-meta-cyano azobenzene (DMC) cis and trans isomers on non-passivated and passivated Si (111) (7 × 7) surfaces is studied using density functional theory (DFT) calculations. Our results reveal that on the non-passivated surface the 12 Si adatoms are accessible to form chemical bonds with DMC molecules. Interestingly, the trans isomer forms two chemical bonds near the corner hole atom in Si (111) (7 × 7) surface, which is not observed in the widely studied metallic surfaces. The DMC isomers show significant structural distortion in the chemisorption case. The strong chemical bonds (and high bonding energy) could be detrimental to conformation switching between these two isomers under external stimuli. The physisorption case is also examined. Monte Carlo (MC) simulations with empirical force fields were employed to search about 106 different adsorption positions and DMC molecule orientations to identify the stable adsorption sites (up to six). The DFT-PBE and DFT-D2 calculations were then carried out to obtain the relaxed atomistic structures and accurate adsorption energy. We find that it is imperative to take van der Waals (vdW) interaction into account in DFT calculations. Our results show that the adsorption sites generally are encompassed by either the Si adatoms or the passivated H atoms, which could enhance the long-range dispersion interaction between DMC molecules and Si surfaces. The molecular structures of both isomers remain unchanged compared with gas phase. The obtained adsorption energy results ΔEads are moderate (0.2-0.8 eV). At some adsorption sites on the passivated surface, both isomers have similar moderate ΔEads (0.4-0.6 eV), implying promises of molecular switching that should be examined in experiments.

Nonadditivity of van der Waals forces on liquid surfaces

NASA Astrophysics Data System (ADS)

Venkataram, Prashanth S.; Whitton, Jeremy D.; Rodriguez, Alejandro W.

2016-09-01

We present an approach for modeling nanoscale wetting and dewetting of textured solid surfaces that exploits recently developed, sophisticated techniques for computing exact long-range dispersive van der Waals (vdW) or (more generally) Casimir forces in arbitrary geometries. We apply these techniques to solve the variational formulation of the Young-Laplace equation and predict the equilibrium shapes of liquid-vacuum interfaces near solid gratings. We show that commonly employed methods of computing vdW interactions based on additive Hamaker or Derjaguin approximations, which neglect important electromagnetic boundary effects, can result in large discrepancies in the shapes and behaviors of liquid surfaces compared to exact methods.

Communication: Many-body stabilization of non-covalent interactions: Structure, stability, and mechanics of Ag3Co(CN)6 framework.

PubMed

Liu, Xiaofei; Hermann, Jan; Tkatchenko, Alexandre

2016-12-28

Stimuli-responsive metal-organic frameworks (MOFs) and other framework materials exhibit a broad variety of useful properties, which mainly stem from an interplay of strong covalent bonds within the organic linkers with presumably weak van der Waals (vdW) interactions which determine the overall packing of the framework constituents. Using Ag 3 Co(CN) 6 as a fundamental test case-a system with a colossal positive and negative thermal expansion [A. L. Goodwin et al., Science 319, 794 (2008)]-we demonstrate that its structure, stability, dielectric, vibrational, and mechanical properties are critically influenced by many-body electronic correlation contributions to non-covalent vdW interactions. The Ag 3 Co(CN) 6 framework is a remarkable molecular crystal, being visibly stabilized, rather than destabilized, by many-body vdW correlations. A detailed comparison with H 3 Co(CN) 6 highlights the crucial role of strongly polarized metallophilic interactions in dictating the exceptional properties of denser MOFs. Beyond MOFs, our findings indicate that many-body electronic correlations can substantially stabilize polarizable materials, providing a novel mechanism for tuning the properties of nanomaterials with intricate structural motifs.

Molecular Self-Assembly Driven by London Dispersion Forces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guo; Cooper, Valentino R; Cho, Jun-Hyung

2011-01-01

The nature and strength of intermolecular interactions are crucial to a variety of kinetic and dynamic processes at surfaces. Whereas strong chemisorption bonds are known to facilitate molecular binding, the importance of the weaker yet ubiquitous van der Waals (vdW) interactions remains elusive in most cases. Here we use first-principles calculations combined with kinetic Monte Carlo simulations to unambiguously demonstrate the vital role that vdW interactions play in molecular self-assembly, using styrene nanowire growth on silicon as a prototypical example. We find that, only when the London dispersion forces are included, accounting for the attractive parts of vdW interactions, canmore » the effective intermolecular interaction be reversed from being repulsive to attractive. Such attractive interactions, in turn, ensure the preferred growth of long wires under physically realistic conditions as observed experimentally. We further propose a cooperative scheme, invoking the application of an electric field and the selective creation of Si dangling bonds, to drastically improve the ordered arrangement of the molecular structures. The present study represents a significant step forward in the fundamental understanding and precise control of molecular self-assembly guided by London dispersion forces.« less

Tunneling Diode Based on WSe2 /SnS2 Heterostructure Incorporating High Detectivity and Responsivity.

PubMed

Zhou, Xing; Hu, Xiaozong; Zhou, Shasha; Song, Hongyue; Zhang, Qi; Pi, Lejing; Li, Liang; Li, Huiqiao; Lü, Jingtao; Zhai, Tianyou

2018-02-01

van der Waals (vdW) heterostructures based on atomically thin 2D materials have led to a new era in next-generation optoelectronics due to their tailored energy band alignments and ultrathin morphological features, especially in photodetectors. However, these photodetectors often show an inevitable compromise between photodetectivity and photoresponsivity with one high and the other low. Herein, a highly sensitive WSe 2 /SnS 2 photodiode is constructed on BN thin film by exfoliating each material and manually stacking them. The WSe 2 /SnS 2 vdW heterostructure shows ultralow dark currents resulting from the depletion region at the junction and high direct tunneling current when illuminated, which is confirmed by the energy band structures and electrical characteristics fitted with direct tunneling. Thus, the distinctive WSe 2 /SnS 2 vdW heterostructure exhibits both ultrahigh photodetectivity of 1.29 × 10 13 Jones (I ph /I dark ratio of ≈10 6 ) and photoresponsivity of 244 A W -1 at a reverse bias under the illumination of 550 nm light (3.77 mW cm -2 ). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theory of coherent van der Waals matter.

PubMed

Kulić, Igor M; Kulić, Miodrag L

2014-12-01

We explain in depth the previously proposed theory of the coherent van der Waals (cvdW) interaction, the counterpart of van der Waals (vdW) force, emerging in spatially coherently fluctuating electromagnetic fields. We show that cvdW driven matter is dominated by many-body interactions, which are significantly stronger than those found in standard van der Waals (vdW) systems. Remarkably, the leading two- and three-body interactions are of the same order with respect to the distance (∝R(-6)), in contrast to the usually weak vdW three-body effects (∝R(-9)). From a microscopic theory we show that the anisotropic cvdW many-body interactions drive the formation of low-dimensional structures such as chains, membranes, and vesicles with very unusual, nonlocal properties. In particular, cvdW chains display a logarithmically growing stiffness with the chain length, while cvdW membranes have a bending modulus growing linearly with their size. We argue that the cvdW anisotropic many-body forces cause local cohesion but also a negative effective "surface tension." We conclude by deriving the equation of state for cvdW materials and propose experiments to test the theory, in particular the unusual three-body nature of cvdW.

Theory of coherent van der Waals matter

NASA Astrophysics Data System (ADS)

Kulić, Igor M.; Kulić, Miodrag L.

2014-12-01

We explain in depth the previously proposed theory of the coherent van der Waals (cvdW) interaction, the counterpart of van der Waals (vdW) force, emerging in spatially coherently fluctuating electromagnetic fields. We show that cvdW driven matter is dominated by many-body interactions, which are significantly stronger than those found in standard van der Waals (vdW) systems. Remarkably, the leading two- and three-body interactions are of the same order with respect to the distance (∝R-6) , in contrast to the usually weak vdW three-body effects (∝R-9 ). From a microscopic theory we show that the anisotropic cvdW many-body interactions drive the formation of low-dimensional structures such as chains, membranes, and vesicles with very unusual, nonlocal properties. In particular, cvdW chains display a logarithmically growing stiffness with the chain length, while cvdW membranes have a bending modulus growing linearly with their size. We argue that the cvdW anisotropic many-body forces cause local cohesion but also a negative effective "surface tension." We conclude by deriving the equation of state for cvdW materials and propose experiments to test the theory, in particular the unusual three-body nature of cvdW.

Adsorption structures and energetics of molecules on metal surfaces: Bridging experiment and theory

NASA Astrophysics Data System (ADS)

Maurer, Reinhard J.; Ruiz, Victor G.; Camarillo-Cisneros, Javier; Liu, Wei; Ferri, Nicola; Reuter, Karsten; Tkatchenko, Alexandre

2016-05-01

Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdWsurf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdWsurf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

Rapid estimation of the electron correlation energy for van der Waals complexes RgX (Rg = Kr, Xe, X = Br, I)

NASA Astrophysics Data System (ADS)

Xinying, Li; Yongfang, Zhao; Xiaogong, Jing; Fengli, Liu; Fengyou, Hao

2006-01-01

We present the rules of electron correlation energies for RgX (Rg = Kr, Xe, X = Br, I) van der Waals (vdW) complex systems at CCSD(T) theoretical level with SDB-cc-pVQZ basis set by the Gaussian 98 program. A new method to derive the dispersion coefficient C6 by fitting the intermonomer electron correlation energies to C6R-6 function is introduced. The present C6 values are compared with the corresponding theoretical ones.

Epitaxial graphene-encapsulated surface reconstruction of Ge(110)

NASA Astrophysics Data System (ADS)

Campbell, Gavin P.; Kiraly, Brian; Jacobberger, Robert M.; Mannix, Andrew J.; Arnold, Michael S.; Hersam, Mark C.; Guisinger, Nathan P.; Bedzyk, Michael J.

2018-04-01

Understanding and engineering the properties of crystalline surfaces has been critical in achieving functional electronics at the nanoscale. Employing scanning tunneling microscopy, surface x-ray diffraction, and high-resolution x-ray reflectivity experiments, we present a thorough study of epitaxial graphene (EG)/Ge(110) and report a Ge(110) "6 × 2" reconstruction stabilized by the presence of epitaxial graphene unseen in group-IV semiconductor surfaces. X-ray studies reveal that graphene resides atop the surface reconstruction with a 0.34 nm van der Waals (vdW) gap and provides protection from ambient degradation.

Anomalous van der Waals-Casimir interactions on graphene: A concerted effect of temperature, retardation, and non-locality

NASA Astrophysics Data System (ADS)

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2018-04-01

Dispersion forces play a major role in graphene, largely influencing adhesion of adsorbate moieties and stabilization of functional multilayered structures. However, the reliable prediction of dispersion interactions on graphene up to the relevant ˜10 nm scale is an extremely challenging task: in fact, electromagnetic retardation effects and the highly non-local character of π electrons can imply sizeable qualitative variations of the interaction with respect to known pairwise approaches. Here we address both issues, determining the finite-temperature van der Waals (vdW)-Casimir interaction for point-like and extended adsorbates on graphene, explicitly accounting for the non-local dielectric permittivity. We find that temperature, retardation, and non-locality play a crucial role in determining the actual vdW scaling laws and the stability of both atomic and larger molecular adsorbates. Our results highlight the importance of these effects for a proper description of systems of current high interest, such as graphene interacting with biomolecules, and self-assembly of complex nanoscale structures. Due to the generality of our approach and the observed non-locality of other 2D materials, our results suggest non-trivial vdW interactions from hexagonal mono-layered materials from group 14 of the periodic table, to transition metal dichalcogenides.

Anomalous van der Waals-Casimir interactions on graphene: A concerted effect of temperature, retardation, and non-locality.

PubMed

Ambrosetti, Alberto; Silvestrelli, Pier Luigi

2018-04-07

Dispersion forces play a major role in graphene, largely influencing adhesion of adsorbate moieties and stabilization of functional multilayered structures. However, the reliable prediction of dispersion interactions on graphene up to the relevant ∼10 nm scale is an extremely challenging task: in fact, electromagnetic retardation effects and the highly non-local character of π electrons can imply sizeable qualitative variations of the interaction with respect to known pairwise approaches. Here we address both issues, determining the finite-temperature van der Waals (vdW)-Casimir interaction for point-like and extended adsorbates on graphene, explicitly accounting for the non-local dielectric permittivity. We find that temperature, retardation, and non-locality play a crucial role in determining the actual vdW scaling laws and the stability of both atomic and larger molecular adsorbates. Our results highlight the importance of these effects for a proper description of systems of current high interest, such as graphene interacting with biomolecules, and self-assembly of complex nanoscale structures. Due to the generality of our approach and the observed non-locality of other 2D materials, our results suggest non-trivial vdW interactions from hexagonal mono-layered materials from group 14 of the periodic table, to transition metal dichalcogenides.

Combinatorial screening of organic electronic materials: thin film stability

NASA Astrophysics Data System (ADS)

Chattopadhyay, Santanu; Carson Meredith, J.

2005-01-01

Dewetting of thin polymeric semiconducting-insulating (and conducting-insulating) bilayers is a serious fundamental problem facing the fabrication of organic electronic devices such as transistors, light-emitting diodes and supercapacitors. This paper describes a high-throughput characterization method that utilizes orthogonal thickness-gradient libraries of the bilayer components poly(3-octylthiophene) (semiconductor) and poly(styrene) (insulator). The technique allows simultaneous observation of hundreds of combinations of thicknesses and has permitted rapid discovery of a previously-unknown VDW instability transition. We observe that the onset of VDW instability in the PS-P3OT bilayer is a complex function of P3OT thickness that cannot be predicted by Hamaker constant models for free energy. At low P3OT thickness, the semiconductor acts to stabilize the PS insulator. But above a P3OT thickness of 175 nm, this behaviour is switched and P3OT destabilizes the PS. These thickness-dependent effects are correlated very well with dramatic transitions in P3OT optical spectra and the P3OT-AFM tip interaction forces. This unusual behaviour places critical limitations on practical device thicknesses and interfacial combinations, and points to the need for a thin-film stability theory that accounts for thickness-dependent molecular-electronic effects.

Van der Waals MoS2/VO2 heterostructure junction with tunable rectifier behavior and efficient photoresponse.

PubMed

Oliva, Nicoló; Casu, Emanuele Andrea; Yan, Chen; Krammer, Anna; Rosca, Teodor; Magrez, Arnaud; Stolichnov, Igor; Schueler, Andreas; Martin, Olivier J F; Ionescu, Adrian Mihai

2017-10-27

Junctions between n-type semiconductors of different electron affinity show rectification if the junction is abrupt enough. With the advent of 2D materials, we are able to realize thin van der Waals (vdW) heterostructures based on a large diversity of materials. In parallel, strongly correlated functional oxides have emerged, having the ability to show reversible insulator-to-metal (IMT) phase transition by collapsing their electronic bandgap under a certain external stimulus. Here, we report for the first time the electronic and optoelectronic characterization of ultra-thin n-n heterojunctions fabricated using deterministic assembly of multilayer molybdenum disulphide (MoS 2 ) on a phase transition material, vanadium dioxide (VO 2 ). The vdW MoS 2 /VO 2 heterojunction combines the excellent blocking capability of an n-n junction with a high conductivity in on-state, and it can be turned into a Schottky rectifier at high applied voltage or at temperatures higher than 68 °C, exploiting the metal state of VO 2 . We report tunable diode-like current rectification with a good diode ideality factor of 1.75 and excellent conductance swing of 120 mV/dec. Finally, we demonstrate unique tunable photosensitivity and excellent junction photoresponse in the 500/650 nm wavelength range.

Prediction of radial breathing-like modes of double-walled carbon nanotubes with arbitrary chirality

NASA Astrophysics Data System (ADS)

Ghavanloo, Esmaeal; Fazelzadeh, S. Ahmad

2014-10-01

The radial breathing-like modes (RBLMs) of double-walled carbon nanotubes (DWCNTs) with arbitrary chirality are investigated by a simple analytical model. For this purpose, DWCNT is considered as double concentric elastic thin cylindrical shells, which are coupled through van der Waals (vdW) forces between two adjacent tubes. Lennard-Jones potential and a molecular mechanics model are used to calculate the vdW forces and to predict the mechanical properties, respectively. The validity of these theoretical results is confirmed through the comparison of the experimental results. Finally, a new approach is proposed to determine the diameters and the chiral indices of the inner and outer tubes of the DWCNTs with high precision.

Electrostatic contribution to the binding stability of protein-protein complexes.

PubMed

Dong, Feng; Zhou, Huan-Xiang

2006-10-01

To investigate roles of electrostatic interactions in protein binding stability, electrostatic calculations were carried out on a set of 64 mutations over six protein-protein complexes. These mutations alter polar interactions across the interface and were selected for putative dominance of electrostatic contributions to the binding stability. Three protocols of implementing the Poisson-Boltzmann model were tested. In vdW4 the dielectric boundary between the protein low dielectric and the solvent high dielectric is defined as the protein van der Waals surface and the protein dielectric constant is set to 4. In SE4 and SE20, the dielectric boundary is defined as the surface of the protein interior inaccessible to a 1.4-A solvent probe, and the protein dielectric constant is set to 4 and 20, respectively. In line with earlier studies on the barnase-barstar complex, the vdW4 results on the large set of mutations showed the closest agreement with experimental data. The agreement between vdW4 and experiment supports the contention of dominant electrostatic contributions for the mutations, but their differences also suggest van der Waals and hydrophobic contributions. The results presented here will serve as a guide for future refinement in electrostatic calculation and inclusion of nonelectrostatic effects. Proteins 2006. (c) 2006 Wiley-Liss, Inc.

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Yong-Hui; Huang, Jingsong; Sheng, Xiaolan

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by upmore » to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Analytical solution for static and dynamic analysis of magnetically affected viscoelastic orthotropic double-layered graphene sheets resting on viscoelastic foundation

NASA Astrophysics Data System (ADS)

Jalaei, M. H.; Arani, A. Ghorbanpour

2018-02-01

By considering the small scale effect based on the nonlocal Eringen's theory, the static and dynamic analysis of viscoelastic orthotropic double-layered graphene sheets subjected to longitudinal magnetic field and mechanical load is investigated analytically. For this objective, first order shear deformation theory (FSDT) is proposed. The surrounding medium is simulated by visco-Pasternak foundation model in which damping, normal and transverse shear loads are taken into account. The governing equations of motion are obtained via energy method and Hamilton's principle which are then solved analytically by means of Navier's approach and Laplace inversion technique in the space and time domains, respectively. Through various parametric studies, the influences of the nonlocal parameter, structural damping, van der Waals (vdW) interaction, stiffness and damping coefficient of the foundation, magnetic parameter, aspect ratio and length to thickness ratio on the static and dynamic response of the nanoplates are examined. The results depict that when the vdW interaction is considered to be zero, the upper layer deflection reaches a maximum point whereas the lower layer deflection becomes zero. In addition, it is observed that with growing the vdW interaction, the effect of magnetic field on the deflection of the lower layer increases while this effect reduces for the upper layer deflection.

Nitrogen-Doping Enables Covalent-Like pi-pi Bonding between Graphenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Yong-Hui; Huang, Jingsong; Sumpter, Bobby G

The neighboring layers in bi-layer (and few-layer) graphenes of both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene molecules . Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi pi bonding in bi-layer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can bemore » enhanced by up to 50% compared to the pristine graphene bi-layers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. The existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

DOE PAGES

Tian, Yong-Hui; Huang, Jingsong; Sheng, Xiaolan; ...

2015-07-07

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by upmore » to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Nanoparticle interaction potentials constructed by multiscale computation

NASA Astrophysics Data System (ADS)

Lee, Cheng K.; Hua, Chi C.

2010-06-01

The van der Waals (vdW) potentials governing macroscopic objects have long been formulated in the context of classical theories, such as Hamaker's microscopic theory and Lifshitz's continuum theory. This work addresses the possibility of constructing the vdW interaction potentials of nanoparticle species using multiscale simulation schemes. Amorphous silica nanoparticles were considered as a benchmark example for which a series of (SiO2)n (n being an integer) has been systematically surveyed as the potential candidates of the packing units that reproduce known bulk material properties in atomistic molecular dynamics simulations. This strategy led to the identification of spherical Si6O12 molecules, later utilized as the elementary coarse-grained (CG) particles to compute the pair interaction potentials of silica nanoparticles ranging from 0.62 to 100 nm in diameter. The model nanoparticles so built may, in turn, serve as the children CG particles to construct nanoparticles assuming arbitrary sizes and shapes. Major observations are as follows. The pair interaction potentials for all the investigated spherical silica nanoparticles can be cast into a semiempirical, generalized Lennard-Jones 2α-α potential (α being a size-dependent, large integral number). In its reduced form, we discuss the implied universalities for the vdW potentials governing a certain range of amorphous nanoparticle species as well as how thermodynamic transferability can be fulfilled automatically. In view of future applications with colloidal suspensions, we briefly evaluated the vdW potential in the presence of a "screening" medium mimicking the effects of electrical double layers or grafting materials atop the nanoparticle core. The general observations shed new light on strategies to attain a microscopic control over interparticle attractions. In future perspectives, the proposed multiscale computation scheme shall help bridge the current gap between the modeling of polymer chains and macroscopic objects by introducing molecular models coarse-grained at a similar level so that the interactions between these two can be treated in a consistent and faithful way.

Low-coverage surface diffusion in complex periodic energy landscapes: Analytical solution for systems with symmetric hops and application to intercalation in topological insulators

NASA Astrophysics Data System (ADS)

Gosálvez, Miguel A.; Otrokov, Mikhail M.; Ferrando, Nestor; Ryabishchenkova, Anastasia G.; Ayuela, Andres; Echenique, Pedro M.; Chulkov, Evgueni V.

2016-02-01

This is the first of two papers that introduce a general expression for the tracer diffusivity in complex, periodic energy landscapes with M distinct hop rates in one-, two-, and three-dimensional diluted systems (low-coverage, single-tracer limit). The present report focuses on the analysis of diffusion in systems where the end sites of the hops are located symmetrically with respect to the hop origins (symmetric hops), as encountered in many ideal surfaces and bulk materials. For diffusion in two dimensions, a number of formulas are presented for complex combinations of the different hops in systems with triangular, rectangular, and square symmetry. The formulas provide values in excellent agreement with kinetic Monte Carlo simulations, concluding that the diffusion coefficient can be directly determined from the proposed expressions without performing the simulations. Based on the diffusion barriers obtained from first-principles calculations and a physically meaningful estimate of the attempt frequencies, the proposed formulas are used to analyze the diffusion of Cu, Ag, and Rb adatoms on the surface and within the van der Waals (vdW) gap of a model topological insulator, Bi2Se3 . Considering the possibility of adsorbate intercalation from the terraces to the vdW gaps at morphological steps, we infer that, at low coverage and room temperature, (i) a majority of the Rb atoms bounce back at the steps and remain on the terraces, (ii) Cu atoms mostly intercalate into the vdW gap, the remaining fraction staying at the steps, and (iii) Ag atoms essentially accumulate at the steps and gradually intercalate into the vdW gap. These conclusions are in good qualitative agreement with previous experiments. The companion report (M. A. Gosálvez et al., Phys. Rev. B, submitted] extends the present study to the description of systems that contain asymmetric hops.

Supercooling of Hydrogen on Template Materials to Deterministically Seed Ignition-Quality Solid Fuel Layers

DOE PAGES

Shin, S. J.; Zepeda-Ruiz, L. A.; Lee, J. R. I.; ...

2016-09-01

In this study, we explored templating effects of various materials for hydrogen (H 2 and D 2) solidification by measuring the degree of supercooling required for liquid hydrogen to solidify below each triple point. The results show high supercooling (>100 mK) for most metallic, covalent, and ionic solids, and low supercooling (<100 mK) for van der Waals (vdW) solids. We attribute the low supercooling of vdW solids to the weak interaction of the substrate and hydrogen. Highly ordered pyrolytic graphite showed the lowest supercooling among materials that are solid at room temperature, but did not exhibit a templating effect withinmore » a fill-tube and capsule assembly.« less

van der Waals heterostructures of germanene, stanene, and silicene with hexagonal boron nitride and their topological domain walls

NASA Astrophysics Data System (ADS)

Wang, Maoyuan; Liu, Liping; Liu, Cheng-Cheng; Yao, Yugui

2016-04-01

We investigate van der Waals (vdW) heterostructures made of germanene, stanene, or silicene with hexagonal boron nitride (h-BN). The intriguing topological properties of these buckled honeycomb materials can be maintained and further engineered in the heterostructures, where the competition between the substrate effect and external electric fields can be used to control the tunable topological phase transitions. Using such heterostructures as building blocks, various vdW topological domain walls (DW) are designed, along which there exist valley polarized quantum spin Hall edge states or valley-contrasting edge states which are protected by valley(spin)- resolved topological charges and can be tailored by the patterning of the heterojunctions and by external fields.

Bandgap engineering and charge separation in two-dimensional GaS-based van der Waals heterostructures for photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Wang, Biao; Kuang, Anlong; Luo, Xukai; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong

2018-05-01

Two-dimensional (2D) gallium sulfide (GaS), hexagonal boron nitride (h-BN) and graphitic carbon nitride (g-C3N4) have been fabricated and expected to be promising photocatalysts under ultraviolet irradiation. Here, we employ hybrid density functional calculations to explore the potential of the 2D GaS-based heterojunctions GaS/h-BN (g-C3N4) for the design of efficient water redox photocatalysts. Both heterostructures can be formed via van der Waals (vdW) interaction and are direct bandgap semiconductors, whose bandgaps are reduced comparing with isolated GaS, h-BN or g-C3N4 monolayers and whose bandedges straddle water redox potentials. Furthermore, the optical absorption of GaS/h-BN (g-C3N4) heterostructures is observably enhanced in the ultraviolet-visible (UV-vis) light range. The electron-hole pairs in GaS/h-BN (g-C3N4) heterostructures are completely separated from different layers. In addition, the in-plane biaxial strain can effectively modulate the electronic properties of GaS/h-BN (g-C3N4) heterostructures. Thus the GaS/h-BN (g-C3N4) heterostructures are anticipated to be promising candidates for photocatalytic water splitting to produce hydrogen.

Sensing properties of pristine boron nitride nanostructures towards alkaloids: A first principles dispersion corrected study

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Dabhi, Shweta D.; Jha, Prafulla K.

2018-05-01

To understand the underlying physics behind the interaction of biomolecules with the nanomaterials to use them practically as bio-nanomaterials is very crucial. A first principles calculation under the frame work of density functional theory is executed to investigate the electronic structures and binding properties of alkaloids (Caffeine and Nicotine) over single walled boron nitride nanotube (BNNT) and boron nitride nanoribbon (BNNR) to determine their suitability towards filtration or sensing of these molecules. We have also used GGA-PBE scheme with the inclusion of Van der Waals (vdW) interaction based on DFT-D2. Increase in the accuracy by incorporating the dispersion correction in the calculation is observed for the long range Van der Waals interaction. Binding energy range of BNNT and BNNR with both alkaloids have been found to be -0.35 to -0.76 eV and -0.45 to -0.91 eV respectively which together with the binding distance shows physisorption binding of these molecules to the both nanostructures. The transfer of charge between the BN nanostructures and the adsorbed molecule has also been analysed by using Lowdin charge analysis. The sensitivity of both nanostructures BNNT and BNNR towards both alkaloids is observed through electronic structure calculations, density of states and quantum conductance. The binding of both alkaloids with BNNR is stronger. The analysis of the calculated properties suggests absence of covalent interaction between the considered species (BNNT/BNNR) and alkaloids. The study may be useful in designing the boron nitride nanostructure based sensing device for alkaloids.

Efficient band structure modulations in two-dimensional MnPSe3/CrSiTe3 van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Pei, Qi; Wang, Xiaocha; Zou, Jijun; Mi, Wenbo

2018-05-01

As a research upsurge, van der Waals (vdW) heterostructures give rise to numerous combined merits and novel applications in nanoelectronics fields. Here, we systematically investigate the electronic structure of MnPSe3/CrSiTe3 vdW heterostructures with various stacking patterns. Then, particular attention of this work is paid on the band structure modulations in MnPSe3/CrSiTe3 vdW heterostructures via biaxial strain or electric field. Under a tensile strain, the relative band edge positions of heterostructures transform from type-I (nested) to type-II (staggered). The relocation of conduction band minimum also brings about a transition from indirect to direct band gap. Under a compressive strain, the electronic properties change from semiconducting to metallic. The physical mechanism of strain-dependent band structure may be ascribed to the shifts of the energy bands impelled by different superposition of atomic orbitals. Meanwhile, our calculations manifest that band gap values of MnPSe3/CrSiTe3 heterostructures are insensitive to the electric field. Even so, by applying a suitable intensity of negative electric field, the band alignment transition from type-I to type-II can also be realized. The efficient band structure modulations via external factors endow MnPSe3/CrSiTe3 heterostructures with great potential in novel applications, such as strain sensors, photocatalysis, spintronic and photoelectronic devices.

Comparison of calculation and experiment implicates significant electrostatic contributions to the binding stability of barnase and barstar.

PubMed

Dong, Feng; Vijayakumar, M; Zhou, Huan-Xiang

2003-07-01

The contributions of electrostatic interactions to the binding stability of barnase and barstar were studied by the Poisson-Boltzmann model with three different protocols: a), the dielectric boundary specified as the van der Waals (vdW) surface of the protein along with a protein dielectric constant (epsilon (p)) of 4; b), the dielectric boundary specified as the molecular (i.e., solvent-exclusion (SE)) surface along with epsilon (p) = 4; and c), "SE + epsilon (p) = 20." The "vdW + epsilon (p) = 4" and "SE + epsilon (p) = 20" protocols predicted an overall electrostatic stabilization whereas the "SE + epsilon (p) = 4" protocol predicted an overall electrostatic destabilization. The "vdW + epsilon (p) = 4" protocol was most consistent with experiment. It quantitatively reproduced the observed effects of 17 mutations neutralizing charged residues lining the binding interface and the measured coupling energies of six charge pairs across the interface and reasonably rationalized the experimental ionic strength and pH dependences of the binding constant. In contrast, the "SE + epsilon (p) = 4" protocol predicted significantly larger coupling energies of charge pairs whereas the "SE + epsilon (p) = 20" protocol did not predict any pH dependence. This study calls for further scrutiny of the different Poisson-Boltzmann protocols and demonstrates potential danger in drawing conclusions on electrostatic contributions based on a particular calculation protocol.

Efficient band structure modulations in two-dimensional MnPSe3/CrSiTe3 van der Waals heterostructures.

PubMed

Pei, Qi; Wang, Xiaocha; Zou, Jijun; Mi, Wenbo

2018-05-25

As a research upsurge, van der Waals (vdW) heterostructures give rise to numerous combined merits and novel applications in nanoelectronics fields. Here, we systematically investigate the electronic structure of MnPSe 3 /CrSiTe 3 vdW heterostructures with various stacking patterns. Then, particular attention of this work is paid on the band structure modulations in MnPSe 3 /CrSiTe 3 vdW heterostructures via biaxial strain or electric field. Under a tensile strain, the relative band edge positions of heterostructures transform from type-I (nested) to type-II (staggered). The relocation of conduction band minimum also brings about a transition from indirect to direct band gap. Under a compressive strain, the electronic properties change from semiconducting to metallic. The physical mechanism of strain-dependent band structure may be ascribed to the shifts of the energy bands impelled by different superposition of atomic orbitals. Meanwhile, our calculations manifest that band gap values of MnPSe 3 /CrSiTe 3 heterostructures are insensitive to the electric field. Even so, by applying a suitable intensity of negative electric field, the band alignment transition from type-I to type-II can also be realized. The efficient band structure modulations via external factors endow MnPSe 3 /CrSiTe 3 heterostructures with great potential in novel applications, such as strain sensors, photocatalysis, spintronic and photoelectronic devices.

Electromagnetically induced grating with Rydberg atoms

NASA Astrophysics Data System (ADS)

Asghar, Sobia; Ziauddin, Qamar, Shahid; Qamar, Sajid

2016-09-01

We present a scheme to realize electromagnetically induced grating in an ensemble of strongly interacting Rydberg atoms, which act as superatoms due to the dipole blockade mechanism. The ensemble of three-level cold Rydberg-dressed (87Rb) atoms follows a cascade configuration where a strong standing-wave control field and a weak probe pulse are employed. The diffraction intensity is influenced by the strength of the probe intensity, the control field strength, and the van der Waals (vdW) interaction. It is noticed that relatively large first-order diffraction can be obtained for low-input intensity with a small vdW shift and a strong control field. The scheme can be considered as an amicable solution to realize the atomic grating at the microscopic level, which can provide background- and dark-current-free diffraction.

The role of particle-to-cell interactions in dictating nanoparticle aided magnetophoretic separation of microalgal cells.

PubMed

Toh, Pey Yi; Ng, Bee Wah; Ahmad, Abdul Latif; Chieh, Derek Chan Juinn; Lim, JitKang

2014-11-07

Successful application of a magnetophoretic separation technique for harvesting biological cells often relies on the need to tag the cells with magnetic nanoparticles. This study investigates the underlying principle behind the attachment of iron oxide nanoparticles (IONPs) onto microalgal cells, Chlorella sp. and Nannochloropsis sp., in both freshwater and seawater, by taking into account the contributions of various colloidal forces involved. The complex interplay between van der Waals (vdW), electrostatic (ES) and Lewis acid-base interactions (AB) in dictating IONP attachment was studied under the framework of extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) analysis. Our results showed that ES interaction plays an important role in determining the net interaction between the Chlorella sp. cells and IONPs in freshwater, while the AB and vdW interactions play a more dominant role in dictating the net particle-to-cell interaction in high ionic strength media (≥100 mM NaCl), such as seawater. XDLVO predicted effective attachment between cells and surface functionalized IONPs (SF-IONPs) with an estimated secondary minimum of -3.12 kT in freshwater. This prediction is in accordance with the experimental observation in which 98.89% of cells can be magnetophoretically separated from freshwater with SF-IONPs. We have observed successful magnetophoretic separation of microalgal cells from freshwater and/or seawater for all the cases as long as XDLVO analysis predicts particle attachment. For both the conditions, no pH adjustment is required for particle-to-cell attachment.

A crossover in anisotropic nanomechanochemistry of van der Waals crystals

NASA Astrophysics Data System (ADS)

Shimamura, Kohei; Misawa, Masaaki; Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Shimojo, Fuyuki; Vashishta, Priya

2015-12-01

In nanoscale mechanochemistry, mechanical forces selectively break covalent bonds to essentially control chemical reactions. An archetype is anisotropic detonation of layered energetic molecular crystals bonded by van der Waals (vdW) interactions. Here, quantum molecular dynamics simulations reveal a crossover of anisotropic nanomechanochemistry of vdW crystal. Within 10-13 s from the passage of shock front, lateral collision produces NO2 via twisting and bending of nitro-groups and the resulting inverse Jahn-Teller effect, which is mediated by strong intra-layer hydrogen bonds. Subsequently, as we transition from heterogeneous to homogeneous mechanochemical regimes around 10-12 s, shock normal to multilayers becomes more reactive, producing H2O assisted by inter-layer N-N bond formation. These time-resolved results provide much needed atomistic understanding of nanomechanochemistry that underlies a wider range of technologies.

Theoretical study on the gas adsorption capacity and selectivity of CPM-200-In/Mg and CPM-200-In/Mg-X (-X = -NH2, -OH, -N, -F).

PubMed

Liu, Xiao-le; Chen, Guang-Hui; Wang, Xiu-Jun; Li, Peng; Song, Yi-Bing; Li, Rui-Yan

2017-11-15

The adsorption capacities of a heterometallic metal-organic framework (CPM-200-In/Mg) to VOCs (HCHO, C 2 H 4 , CH 4 , C 2 H 2 , C 3 H 8 , C 2 H 6 , C 2 H 3 Cl, C 2 H 2 Cl 2 , CH 2 Cl 2 and CHCl 3 ) and some inorganic gas molecules (HCN, SO 2 , NO, CO 2 , CO, H 2 S and NH 3 ), as well as its selectivity in ternary mixture systems of natural gas and post-combustion flue gas are theoretically explored at the grand canonical Monte Carlo (GCMC) and density functional theory (DFT) levels. It is shown that CPM-200-In/Mg is suitable for the adsorption of VOCs, particularly for HCHO (up to 0.39 g g -1 at 298 K and 1 bar), and the adsorption capacities of some inorganic gas molecules such as SO 2 , H 2 S and CO 2 match well with the sequence of their polarizability (SO 2 > H 2 S > CO 2 ). The large adsorption capacities of HCN and HCHO in the framework result from the strong interaction between adsorbates and metal centers, based on analyzing the radial distribution functions (RDF). Comparing C 2 H 4 and CH 4 molecules interacting with CPM-200-In/Mg by VDW interaction, we speculate that the high adsorption capacities of their chlorine derivatives in the framework could be due to the existence of halogen bonding or strong electrostatic and VDW interactions. It is found that the basic groups, including -NH 2 , -N and -OH, can effectively improve both the adsorption capacities and selectivity of CPM-200-In/Mg for harmful gases. Note that the adsorption capacity of CPM-200-In/Mg-NH 2 (site 2) (245 cm 3 g -1 ) for CO 2 exceeded that of MOF-74-Mg (228 cm 3 g -1 ) at 273 K and 1 bar and that for HCHO can reach 0.41 g g -1 , which is almost twice that of 438-MOF and nearly 45 times of that in active carbon. Moreover, for natural gas mixtures, the decarburization and desulfurization abilities of CPM-200-In/Mg-NH 2 (site 2) have exceeded those of the MOF-74 series, while for post-combustion flue gas mixtures, the desulfurization ability of CPM-200-In/Mg-NH 2 (site 2) is still comparable to those of the MOF-74 series at 303 K and 4 MPa. We hope that the current theoretical study could guide experimental research in the future.

Structures, mechanical properties, equations of state, and electronic properties of β-HMX under hydrostatic pressures: a DFT-D2 study.

PubMed

Peng, Qing; Rahul; Wang, Guangyu; Liu, Gui-Rong; De, Suvranu

2014-10-07

We report the hydrostatic compression studies of the β-polymorph of a cyclotetramethylene tetranitramine (HMX) energetic molecular crystal using DFT-D2, a first-principles calculation based on density functional theory (DFT) with van der Waals (vdW) corrections. The molecular structure, mechanical properties, electronic properties, and equations of state of β-HMX are investigated. For the first time, we predict the elastic constants of β-HMX using DFT-D2 studies. The equations of state under hydrostatic compression are studied for pressures up to 100 GPa. We found that the N-N bonds along the minor axis are responsible for the sensitivity of β-HMX. The analysis of the charge distribution shows that the electronic charge is transferred from hydrogen atoms to nitro groups with the amount of 0.131 and 0.064e for the nitro groups along the minor axis and major axis, respectively, when pressure changes from 0 GPa to 100 GPa. The electronic energy band gap changes from direct at a pressure of 0 GPa to indirect at a pressure of 50 GPa and higher. The band gap decreases with respect to an increase in pressure, implying that the impact sensitivity increases with compression. Our study suggests that the van der Waals interactions are critically important in modeling the mechanical properties of this molecular crystal.

Investigation of the adsorption of ozone molecules on TiO2/WSe2 nanocomposites by DFT computations: Applications to gas sensor devices

NASA Astrophysics Data System (ADS)

Abbasi, Amirali; Sardroodi, Jaber Jahanbin

2018-04-01

The adsorption of O3 molecule on the undoped and N-doped TiO2/WSe2 nanocomposites was studied using first principles density functional theory calculations. O3 interaction with TiO2/WSe2 nanocomposites is considered so as to investigate WSe2 effects on the adsorption process. WSe2 favors the adsorption of O3 on TiO2 particles. In other words, WSe2 is conducive to the interaction of O3 molecule with fivefold coordinated titanium sites of TiO2. The effects of vdW interactions were taken into account in order to obtain equilibrium geometries of O3 molecules at TiO2/WSe2 interfaces. For all adsorption configurations, the binding site was positioned on the fivefold coordinated titanium atoms. The results show that the interactions between O3 and TiO2 in TiO2/WSe2 nanocomposites are stronger than those between O3 and bare TiO2, suggesting that WSe2 helps to strengthen the interaction of ozone molecule with TiO2 particles. The results also indicate that the adsorption of the O3 molecule on the N-doped TiO2/WSe2 nanocomposite is more energetically favorable than the adsorption of O3 on the pristine one, representing that the N-doped nanocomposites are more sensitive than the undoped ones. Our DFT results clearly show that the N-doped TiO2/WSe2 nanocomposite would be a promising O3 gas sensor. The electronic structure of the adsorption system was also investigated, including analysis of the total and projected density of states, and charge density differences of the TiO2/WSe2 with adsorbed O3 molecules. The charge density difference calculations indicate that the charges were accumulated over the adsorbed O3 molecule. Besides, the N-doped nanocomposites have better sensing response than the pristine ones. This work was devoted to provide the theory basis for the design and development of novel and advanced O3 sensors based on modified TiO2/WSe2 nanocomposites.

Van der Waals metal-semiconductor junction: Weak Fermi level pinning enables effective tuning of Schottky barrier

PubMed Central

Liu, Yuanyue; Stradins, Paul; Wei, Su-Huai

2016-01-01

Two-dimensional (2D) semiconductors have shown great potential for electronic and optoelectronic applications. However, their development is limited by a large Schottky barrier (SB) at the metal-semiconductor junction (MSJ), which is difficult to tune by using conventional metals because of the effect of strong Fermi level pinning (FLP). We show that this problem can be overcome by using 2D metals, which are bounded with 2D semiconductors through van der Waals (vdW) interactions. This success relies on a weak FLP at the vdW MSJ, which is attributed to the suppression of metal-induced gap states. Consequently, the SB becomes tunable and can vanish with proper 2D metals (for example, H-NbS2). This work not only offers new insights into the fundamental properties of heterojunctions but also uncovers the great potential of 2D metals for device applications. PMID:27152360

Dependence of the shape of graphene nanobubbles on trapped substance

NASA Astrophysics Data System (ADS)

Ghorbanfekr-Kalashami, H.; Vasu, K. S.; Nair, R. R.; Peeters, François M.; Neek-Amal, M.

2017-06-01

Van der Waals (vdW) interaction between two-dimensional crystals (2D) can trap substances in high pressurized (of order 1 GPa) on nanobubbles. Increasing the adhesion between the 2D crystals further enhances the pressure and can lead to a phase transition of the trapped material. We found that the shape of the nanobubble can depend critically on the properties of the trapped substance. In the absence of any residual strain in the top 2D crystal, flat nanobubbles can be formed by trapped long hydrocarbons (that is, hexadecane). For large nanobubbles with radius 130 nm, our atomic force microscopy measurements show nanobubbles filled with hydrocarbons (water) have a cylindrical symmetry (asymmetric) shape which is in good agreement with our molecular dynamics simulations. This study provides insights into the effects of the specific material and the vdW pressure on the microscopic details of graphene bubbles.

Dependence of the shape of graphene nanobubbles on trapped substance.

PubMed

Ghorbanfekr-Kalashami, H; Vasu, K S; Nair, R R; Peeters, François M; Neek-Amal, M

2017-06-16

Van der Waals (vdW) interaction between two-dimensional crystals (2D) can trap substances in high pressurized (of order 1 GPa) on nanobubbles. Increasing the adhesion between the 2D crystals further enhances the pressure and can lead to a phase transition of the trapped material. We found that the shape of the nanobubble can depend critically on the properties of the trapped substance. In the absence of any residual strain in the top 2D crystal, flat nanobubbles can be formed by trapped long hydrocarbons (that is, hexadecane). For large nanobubbles with radius 130 nm, our atomic force microscopy measurements show nanobubbles filled with hydrocarbons (water) have a cylindrical symmetry (asymmetric) shape which is in good agreement with our molecular dynamics simulations. This study provides insights into the effects of the specific material and the vdW pressure on the microscopic details of graphene bubbles.

Dependence of the shape of graphene nanobubbles on trapped substance

PubMed Central

Ghorbanfekr-Kalashami, H.; Vasu, K. S.; Nair, R. R.; Peeters, François M.; Neek-Amal, M.

2017-01-01

Van der Waals (vdW) interaction between two-dimensional crystals (2D) can trap substances in high pressurized (of order 1 GPa) on nanobubbles. Increasing the adhesion between the 2D crystals further enhances the pressure and can lead to a phase transition of the trapped material. We found that the shape of the nanobubble can depend critically on the properties of the trapped substance. In the absence of any residual strain in the top 2D crystal, flat nanobubbles can be formed by trapped long hydrocarbons (that is, hexadecane). For large nanobubbles with radius 130 nm, our atomic force microscopy measurements show nanobubbles filled with hydrocarbons (water) have a cylindrical symmetry (asymmetric) shape which is in good agreement with our molecular dynamics simulations. This study provides insights into the effects of the specific material and the vdW pressure on the microscopic details of graphene bubbles. PMID:28621311

Room-temperature ferroelectricity in CuInP 2S 6 ultrathin flakes

DOE PAGES

Liu, Fucai; You, Lu; Seyler, Kyle L.; ...

2016-08-11

In this study, two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP 2S 6 (CIPS) with a transition temperature of ~320 K. Switchable polarization is observed in thin CIPS of ~4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio ofmore » ~100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity.« less

Unraveling cellulose microfibrils: a twisted tale.

PubMed

Hadden, Jodi A; French, Alfred D; Woods, Robert J

2013-10-01

Molecular dynamics (MD) simulations of cellulose microfibrils are pertinent to the paper, textile, and biofuels industries for their unique capacity to characterize dynamic behavior and atomic-level interactions with solvent molecules and cellulase enzymes. While high-resolution crystallographic data have established a solid basis for computational analysis of cellulose, previous work has demonstrated a tendency for modeled microfibrils to diverge from the linear experimental structure and adopt a twisted conformation. Here, we investigate the dependence of this twisting behavior on computational approximations and establish the theoretical basis for its occurrence. We examine the role of solvent, the effect of nonbonded force field parameters [partial charges and van der Waals (vdW) contributions], and the use of explicitly modeled oxygen lone pairs in both the solute and solvent. Findings suggest that microfibril twisting is favored by vdW interactions, and counteracted by both intrachain hydrogen bonds and solvent effects at the microfibril surface. Copyright © 2013 Wiley Periodicals, Inc.

Unraveling Cellulose Microfibrils: A Twisted Tale

PubMed Central

Hadden, Jodi A.; French, Alfred D.; Woods, Robert J.

2014-01-01

Molecular dynamics (MD) simulations of cellulose microfibrils are pertinent to the paper, textile, and biofuels industries for their unique capacity to characterize dynamic behavior and atomic-level interactions with solvent molecules and cellulase enzymes. While high-resolution crystallographic data have established a solid basis for computational analysis of cellulose, previous work has demonstrated a tendency for modeled microfibrils to diverge from the linear experimental structure and adopt a twisted conformation. Here, we investigate the dependence of this twisting behavior on computational approximations and establish the theoretical basis for its occurrence. We examine the role of solvent, the effect of nonbonded force field parameters [partial charges and van der Waals (vdW) contributions], and the use of explicitly modeled oxygen lone pairs in both the solute and solvent. Findings suggest that microfibril twisting is favored by vdW interactions, and counteracted by both intrachain hydrogen bonds and solvent effects at the microfibril surface. PMID:23681971

Van der Waals metal-semiconductor junction: Weak Fermi level pinning enables effective tuning of Schottky barrier

DOE PAGES

Liu, Yuanyue; Stradins, Paul; Wei, Su -Huai

2016-04-22

Two-dimensional (2D) semiconductors have shown great potential for electronic and optoelectronic applications. However, their development is limited by a large Schottky barrier (SB) at the metal-semiconductor junction (MSJ), which is difficult to tune by using conventional metals because of the effect of strong Fermi level pinning (FLP). We show that this problem can be overcome by using 2D metals, which are bounded with 2D semiconductors through van der Waals (vdW) interactions. This success relies on a weak FLP at the vdW MSJ, which is attributed to the suppression of metal-induced gap states. Consequently, the SB becomes tunable and can vanishmore » with proper 2D metals (for example, H-NbS2). This work not only offers new insights into the fundamental properties of heterojunctions but also uncovers the great potential of 2D metals for device applications.« less

High-performance black phosphorus top-gate ferroelectric transistor for nonvolatile memory applications

NASA Astrophysics Data System (ADS)

Lee, Young Tack; Hwang, Do Kyung; Choi, Won Kook

2016-10-01

Two-dimensional (2D) van der Waals (vdW) atomic crystals have been extensively studied and significant progress has been made. The newest 2D vdW material, called black phosphorus (BP), has attracted considerable attention due to its unique physical properties, such as its being a singlecomponent material like graphene, and its having a high mobility and direct band gap. Here, we report on a high-performance BP nanosheet based ferroelectric field effect transistor (FeFET) with a poly(vinylidenefluoride-trifluoroethylene) top-gate insulator for a nonvolatile memory application. The BP FeFETs show the highest linear hole mobility of 563 cm2/Vs and a clear memory window of more than 15 V. For more advanced nonvolatile memory circuit applications, two different types of resistive-load and complementary ferroelectric memory inverters were implemented, which showed distinct memory on/off switching characteristics.

Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes

PubMed Central

Liu, Fucai; You, Lu; Seyler, Kyle L.; Li, Xiaobao; Yu, Peng; Lin, Junhao; Wang, Xuewen; Zhou, Jiadong; Wang, Hong; He, Haiyong; Pantelides, Sokrates T.; Zhou, Wu; Sharma, Pradeep; Xu, Xiaodong; Ajayan, Pulickel M.; Wang, Junling; Liu, Zheng

2016-01-01

Two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP2S6 (CIPS) with a transition temperature of ∼320 K. Switchable polarization is observed in thin CIPS of ∼4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio of ∼100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity. PMID:27510418

Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes

NASA Astrophysics Data System (ADS)

Liu, Fucai; You, Lu; Seyler, Kyle L.; Li, Xiaobao; Yu, Peng; Lin, Junhao; Wang, Xuewen; Zhou, Jiadong; Wang, Hong; He, Haiyong; Pantelides, Sokrates T.; Zhou, Wu; Sharma, Pradeep; Xu, Xiaodong; Ajayan, Pulickel M.; Wang, Junling; Liu, Zheng

2016-08-01

Two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP2S6 (CIPS) with a transition temperature of ~320 K. Switchable polarization is observed in thin CIPS of ~4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio of ~100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity.

Room-temperature ferroelectricity in CuInP2S6 ultrathin flakes.

PubMed

Liu, Fucai; You, Lu; Seyler, Kyle L; Li, Xiaobao; Yu, Peng; Lin, Junhao; Wang, Xuewen; Zhou, Jiadong; Wang, Hong; He, Haiyong; Pantelides, Sokrates T; Zhou, Wu; Sharma, Pradeep; Xu, Xiaodong; Ajayan, Pulickel M; Wang, Junling; Liu, Zheng

2016-08-11

Two-dimensional (2D) materials have emerged as promising candidates for various optoelectronic applications based on their diverse electronic properties, ranging from insulating to superconducting. However, cooperative phenomena such as ferroelectricity in the 2D limit have not been well explored. Here, we report room-temperature ferroelectricity in 2D CuInP2S6 (CIPS) with a transition temperature of ∼320 K. Switchable polarization is observed in thin CIPS of ∼4 nm. To demonstrate the potential of this 2D ferroelectric material, we prepare a van der Waals (vdW) ferroelectric diode formed by CIPS/Si heterostructure, which shows good memory behaviour with on/off ratio of ∼100. The addition of ferroelectricity to the 2D family opens up possibilities for numerous novel applications, including sensors, actuators, non-volatile memory devices, and various vdW heterostructures based on 2D ferroelectricity.

Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures

DOE PAGES

Song, Tiancheng; Cai, Xinghan; Tu, Matisse Wei-Yuan; ...

2018-05-03

Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI3) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance which is drastically enhanced with increasing CrI 3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI 3. In conclusion, ourmore » work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI 3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.« less

Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Tiancheng; Cai, Xinghan; Tu, Matisse Wei-Yuan

Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI3) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance which is drastically enhanced with increasing CrI 3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI 3. In conclusion, ourmore » work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI 3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.« less

Insight into the adsorption of chloramphenicol on a vermiculite surface

NASA Astrophysics Data System (ADS)

Tri, Nguyen Ngoc; Carvalho, A. J. P.; Dordio, A. V.; Nguyen, Minh Tho; Trung, Nguyen Tien

2018-05-01

Four stable configurations were found upon adsorption of the chloramphenicol on a period slab model of the vermiculite surface, using the PBE and C09-vdW functionals in a projector-augmented wave (PAW) method approach. The adsorption is a strong chemisorption process, characterized by an adsorption energy of -106.5 kcal mol-1 at the most stable configuration. Stability of configurations contributed mainly by Mg⋯O/Cl attractive electrostatic interactions and C/Osbnd H⋯O hydrogen bonds. It is remarkable that the vermiculite is found to be a solid material with good potential to be used for adsorption and consequent removal of this type of antibiotic drugs.

Twinned Growth of Metal-Free, Triazine-Based Photocatalyst Films as Mixed-Dimensional (2D/3D) van der Waals Heterostructures.

PubMed

Schwarz, Dana; Noda, Yu; Klouda, Jan; Schwarzová-Pecková, Karolina; Tarábek, Ján; Rybáček, Jiří; Janoušek, Jiří; Simon, Frank; Opanasenko, Maksym V; Čejka, Jiří; Acharjya, Amitava; Schmidt, Johannes; Selve, Sören; Reiter-Scherer, Valentin; Severin, Nikolai; Rabe, Jürgen P; Ecorchard, Petra; He, Junjie; Polozij, Miroslav; Nachtigall, Petr; Bojdys, Michael J

2017-10-01

Design and synthesis of ordered, metal-free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed-dimensional (2D/3D) metal-free van der Waals (vdW) heterostructures based on triazine (C 3 N 3 ) linkers grow as large area, transparent yellow-orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E g,opt = 1.91 eV, E g,elec = 1.84 eV) and are moderately porous (124 m 2 g -1 ). The material consists of a crystalline 2D phase that is fully sp 2 hybridized and provides structural stability, and an amorphous, porous phase with mixed sp 2 -sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one-pot reaction mixture: unprecedented for metal-free frameworks and a direct consequence of on-catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal-free, light-induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h -1 g -1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of "wet" chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance of the AMOEBA Water Model in the Vicinity of QM Solutes: A Diagnosis Using Energy Decomposition Analysis.

PubMed

Mao, Yuezhi; Shao, Yihan; Dziedzic, Jacek; Skylaris, Chris-Kriton; Head-Gordon, Teresa; Head-Gordon, Martin

2017-05-09

The importance of incorporating solvent polarization effects into the modeling of solvation processes has been well-recognized, and therefore a new generation of hybrid quantum mechanics/molecular mechanics (QM/MM) approaches that accounts for this effect is desirable. We present a fully self-consistent, mutually polarizable QM/MM scheme using the AMOEBA force field, in which the total energy of the system is variationally minimized with respect to both the QM electronic density and the MM induced dipoles. This QM/AMOEBA model is implemented through the Q-Chem/LibEFP code interface and then applied to the evaluation of solute-solvent interaction energies for various systems ranging from the water dimer to neutral and ionic solutes (NH 3 , NH 4 + , CN - ) surrounded by increasing numbers of water molecules (up to 100). In order to analyze the resulting interaction energies, we also utilize an energy decomposition analysis (EDA) scheme which identifies contributions from permanent electrostatics, polarization, and van der Waals (vdW) interaction for the interaction between the QM solute and the solvent molecules described by AMOEBA. This facilitates a component-wise comparison against full QM calculations where the corresponding energy components are obtained via a modified version of the absolutely localized molecular orbitals (ALMO)-EDA. The results show that the present QM/AMOEBA model can yield reasonable solute-solvent interaction energies for neutral and cationic species, while further scrutiny reveals that this accuracy highly relies on the delicate balance between insufficiently favorable permanent electrostatics and softened vdW interaction. For anionic solutes where the charge penetration effect becomes more pronounced, the QM/MM interface turns out to be unbalanced. These results are consistent with and further elucidate our findings in a previous study using a slightly different QM/AMOEBA model ( Dziedzic et al. J. Chem. Phys. 2016 , 145 , 124106 ). The implications of these results for further refinement of this model are also discussed.

Anisotropic mechanoresponse of energetic crystallites: a quantum molecular dynamics study of nano-collision

NASA Astrophysics Data System (ADS)

Li, Ying; Kalia, Rajiv K.; Misawa, Masaaki; Nakano, Aiichiro; Nomura, Ken-Ichi; Shimamura, Kohei; Shimojo, Fuyuki; Vashishta, Priya

2016-05-01

At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision was found to originate from the twisting and bending to breaking of nitro-groups mediated by strong intra-layer hydrogen bonds. This causes the closing of the electronic energy gap due to an inverse Jahn-Teller effect. On the other hand, the insensitive collisions normal to multilayers are accomplished by more delocalized molecular deformations mediated by inter-layer interactions. Our nano-collision studies provide a much needed atomistic understanding for the rational design of insensitive energetic nanomaterials and the detonation synthesis of novel nanomaterials.At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision was found to originate from the twisting and bending to breaking of nitro-groups mediated by strong intra-layer hydrogen bonds. This causes the closing of the electronic energy gap due to an inverse Jahn-Teller effect. On the other hand, the insensitive collisions normal to multilayers are accomplished by more delocalized molecular deformations mediated by inter-layer interactions. Our nano-collision studies provide a much needed atomistic understanding for the rational design of insensitive energetic nanomaterials and the detonation synthesis of novel nanomaterials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08769d

Free volume in ionic liquids: a connection of experimentally accessible observables from PALS and PVT experiments with the molecular structure from XRD data.

PubMed

Beichel, Witali; Yu, Yang; Dlubek, Günter; Krause-Rehberg, Reinhard; Pionteck, Jürgen; Pfefferkorn, Dirk; Bulut, Safak; Bejan, Dana; Friedrich, Christian; Krossing, Ingo

2013-06-14

In the current work, free volume concepts, primarily applied to glass formers in the literature, were transferred to ionic liquids (ILs). A series of 1-butyl-3-methylimidazolium ([C4MIM](+)) based ILs was investigated by Positron Annihilation Lifetime Spectroscopy (PALS). The phase transition and dynamic properties of the ILs [C4MIM][X] with [X](-) = [Cl](-), [BF4](-), [PF6](-), [OTf](-), [NTf2](-) and [B(hfip)4](-) were reported recently (Yu et al., Phys. Chem. Chem. Phys., 2012, 14, 6856-6868). In this subsequent work, attention was paid to the connection of the free volume from PALS (here the mean hole volume, ) with the molecular structure, represented by volumes derived from X-ray diffraction (XRD) data. These were the scaled molecular volume Vm,scaled and the van der Waals volume V(vdw). Linear correlations of at the "knee" temperature ((T(k))) with V(m,scaled) and V(vdw) gave good results for the [C4MIM](+) series. Further relationships between volumes from XRD data with the occupied volume Vocc determined from PALS/PVT (Pressure Volume Temperature) measurements and from Sanchez-Lacombe Equation of State (SL-EOS) fits were elaborated (V(occ)(SL-EOS) ≈ 1.63 V(vdw), R(2) = 0.981 and V(occ)(SL-EOS) ≈ 1.12 V(m,scaled), R(2) = 0.980). Finally, the usability of V(m,scaled) was justified in terms of the Cohen-Turnbull (CT) free volume theory. Empirical CT type plots of viscosity and electrical conductivity showed a systematic increase in the critical free volume with molecular size. Such correlations allow descriptions of IL properties with the easily accessible quantity V(m,scaled) within the context of the free volume.

Mixed Dimensional Van der Waals Heterostructures for Opto-Electronics.

NASA Astrophysics Data System (ADS)

Jariwala, Deep

The isolation of a growing number of two-dimensional (2D) materials has inspired worldwide efforts to integrate distinct 2D materials into van der Waals (vdW) heterostructures. While a tremendous amount of research activity has occurred in assembling disparate 2D materials into ``all-2D'' van der Waals heterostructures, this concept is not limited to 2D materials alone. Given that any passivated, dangling bond-free surface will interact with another via vdW forces, the vdW heterostructure concept can be extended to include the integration of 2D materials with non-2D materials that adhere primarily through noncovalent interactions. In the first part of this talk I will present our work on emerging mixed-dimensional (2D + nD, where n is 0, 1 or 3) heterostructure devices performed at Northwestern University. I will present two distinct examples of gate-tunable p-n heterojunctions 1. Single layer n-type MoS2\\ (2D) combined with p-type semiconducting single walled carbon nanotubes (1D) and 2. Single layer MoS2 combined with 0D molecular semiconductor, pentacene. I will present the unique electrical properties, underlying charge transport mechanisms and photocurrent responses in both the above systems using a variety of scanning probe microscopy techniques as well as computational analysis. This work shows that van der Waals interactions are robust across different dimensionalities of materials and can allow fabrication of semiconductor devices with unique geometries and properties unforeseen in bulk semiconductors. Finally, I will briefly discuss our recent work from Caltech on near-unity absorption in atomically-thin photovoltaic devices. This work is supported by the Materials Research Center at Northwestern University, funded by the National Science Foundation (NSF DMR-1121262) and the Resnick Sustainability Institute at Caltech.

Accurate electrostatic and van der Waals pull-in prediction for fully clamped nano/micro-beams using linear universal graphs of pull-in instability

NASA Astrophysics Data System (ADS)

Tahani, Masoud; Askari, Amir R.

2014-09-01

In spite of the fact that pull-in instability of electrically actuated nano/micro-beams has been investigated by many researchers to date, no explicit formula has been presented yet which can predict pull-in voltage based on a geometrically non-linear and distributed parameter model. The objective of present paper is to introduce a simple and accurate formula to predict this value for a fully clamped electrostatically actuated nano/micro-beam. To this end, a non-linear Euler-Bernoulli beam model is employed, which accounts for the axial residual stress, geometric non-linearity of mid-plane stretching, distributed electrostatic force and the van der Waals (vdW) attraction. The non-linear boundary value governing equation of equilibrium is non-dimensionalized and solved iteratively through single-term Galerkin based reduced order model (ROM). The solutions are validated thorough direct comparison with experimental and other existing results reported in previous studies. Pull-in instability under electrical and vdW loads are also investigated using universal graphs. Based on the results of these graphs, non-dimensional pull-in and vdW parameters, which are defined in the text, vary linearly versus the other dimensionless parameters of the problem. Using this fact, some linear equations are presented to predict pull-in voltage, the maximum allowable length, the so-called detachment length, and the minimum allowable gap for a nano/micro-system. These linear equations are also reduced to a couple of universal pull-in formulas for systems with small initial gap. The accuracy of the universal pull-in formulas are also validated by comparing its results with available experimental and some previous geometric linear and closed-form findings published in the literature.

Raman vibrational spectra of bulk to monolayer Re S 2 with lower symmetry

DOE PAGES

Feng, Yanqing; Zhou, Wei; Wang, Yaojia; ...

2015-08-26

Lattice structure and symmetry of two-dimensional (2D) layered materials are of key importance to their fundamental mechanical, thermal, electronic and optical properties. Raman spectroscopy, as a convenient and nondestructive tool, however has its limitations on identifying all symmetry allowing Raman modes and determining the corresponding crystal structure of 2D layered materials with high symmetry like graphene and MoS 2. Due to lower structural symmetry and extraordinary weak interlayer coupling of ReS 2, we successfully identified all 18 first-order Raman active modes for bulk and monolayer ReS 2. Without van der Waals (vdW) correction, our local density approximation (LDA) calculations successfullymore » reproduce all the Raman modes. Our calculations also suggest no surface reconstruction effect and the absence of low frequency rigid-layer Raman modes below 100 cm -1. As a result, combining with Raman and LDA thus provides a general approach for studying the vibrational and structural properties of 2D layered materials with lower symmetry.« less

Cavity-QED interactions of two correlated atoms

NASA Astrophysics Data System (ADS)

Esfandiarpour, Saeideh; Safari, Hassan; Bennett, Robert; Yoshi Buhmann, Stefan

2018-05-01

We consider the resonant van der Waals (vdW) interaction between two correlated identical two-level atoms (at least one of which being excited) within the framework of macroscopic cavity quantum electrodynamics in linear, dispersing and absorbing media. The interaction of both atoms with the body-assisted electromagnetic field of the cavity is assumed to be strong. Our time-independent evaluation is based on an extended Jaynes–Cummings model. For a system prepared in a superposition of its dressed states, we derive the general form of the vdW forces, using a Lorentzian single-mode approximation. We demonstrate the applicability of this approach by considering the case of a planar cavity and showing the position dependence of Rabi oscillations. We also show that in the limiting case of weak coupling, our results reproduce the perturbative ones for the case where the field is initially in vacuum state while the atomic state is in a superposition of two correlated states sharing one excitation.

Two-dimensional n -InSe/p -GeSe(SnS) van der Waals heterojunctions: High carrier mobility and broadband performance

NASA Astrophysics Data System (ADS)

Xia, Cong-xin; Du, Juan; Huang, Xiao-wei; Xiao, Wen-bo; Xiong, Wen-qi; Wang, Tian-xing; Wei, Zhong-ming; Jia, Yu; Shi, Jun-jie; Li, Jing-bo

2018-03-01

Recently, constructing van der Waals (vdW) heterojunctions by stacking different two-dimensional (2D) materials has been considered to be effective strategy to obtain the desired properties. Here, through first-principles calculations, we find theoretically that the 2D n -InSe/p -GeSe(SnS) vdW heterojunctions are the direct-band-gap semiconductor with typical type-II band alignment, facilitating the effective separation of photogenerated electron and hole pairs. Moreover, they possess the high optical absorption strength (˜105 ), broad spectrum width, and excellent carrier mobility (˜103c m2V-1s-1 ). Interestingly, under the influences of the interlayer coupling and external electric field, the characteristics of type-II band alignment is robust, while the band-gap values and band offset are tunable. These results indicate that 2D n -InSe/p -GeSe(SnS) heterojunctions possess excellent optoelectronic and transport properties, and thus can become good candidates for next-generation optoelectronic nanodevices.

Pressure induced structural phase transition in IB transition metal nitrides compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soni, Shubhangi; Kaurav, Netram, E-mail: netramkaurav@yahoo.co.uk; Jain, A.

2015-06-24

Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbormore » ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.« less

Exfoliation and van der Waals heterostructure assembly of intercalated ferromagnet Cr1/3TaS2

NASA Astrophysics Data System (ADS)

Yamasaki, Yuji; Moriya, Rai; Arai, Miho; Masubuchi, Satoru; Pyon, Sunseng; Tamegai, Tsuyoshi; Ueno, Keiji; Machida, Tomoki

2017-12-01

Ferromagnetic van der Waals (vdW) materials are in demand for spintronic devices with all-two-dimensional-materials heterostructures. Here, we demonstrate mechanical exfoliation of magnetic-atom-intercalated transition metal dichalcogenide Cr1/3TaS2 from its bulk crystal; previously such intercalated materials were thought difficult to exfoliate. Magnetotransport in exfoliated tens-of-nanometres-thick flakes revealed ferromagnetic ordering below its Curie temperature T C ~ 110 K as well as strong in-plane magnetic anisotropy; these are identical to its bulk properties. Further, van der Waals heterostructure assembly of Cr1/3TaS2 with another intercalated ferromagnet Fe1/4TaS2 is demonstrated using a dry-transfer method. The fabricated heterojunction composed of Cr1/3TaS2 and Fe1/4TaS2 with a native Ta2O5 oxide tunnel barrier in between exhibits tunnel magnetoresistance (TMR), revealing possible spin injection and detection with these exfoliatable ferromagnetic materials through the vdW junction.

Isotopologue-selective excitation studied via optical-optical double resonance using the E3 Σ1+(63S1) ←A3Π0+(53P1) ←X1Σ0+(51S0) transitions in CdAr and CdKr van der Waals complexes

NASA Astrophysics Data System (ADS)

Urbańczyk, T.; Dudek, J.; Koperski, J.

2018-06-01

A method of experimental selection of molecular isotopologues using optical-optical double resonance (OODR) scheme and supersonic beam source of van der Waals (vdW) complexes is presented. Due to an appropriately large isotopic shift, the proper choice of a wavenumber of a sufficiently narrowband laser in the first transition of OODR scheme can lead to a selective isotopologue excitation to the intermediate state. Thanks to this approach, it is possible to select some of the isotopologues which subsequently give a contribution to laser induced fluorescence (LIF) signal originated from the final state of OODR. In this article, results of tests of the proposed method that employs the E3 Σ1+ ←A3Π0+ ←X1Σ0+ transitions in two vdW complexes, CdKr and CdAr, are presented and analysed.

Photocurrent measurements in Coupled Quantum Well van der Waals Heterostructures made of 2D Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Joe, Andrew; Jauregui, Luis; High, Alex; Dibos, Alan; Gulpinar, Elgin; Pistunova, Kateryna; Park, Hongkun; Kim, Philip

, Luis A. Jauregui, Alex A. High, Alan Dibos, Elgin Gulpinar, Kateryna Pistunova, Hongkun Park, Philip Kim Harvard University, Physics Department -abstract- Single layer transition metal dichalcogenides (TMDC) are 2-dimensional (2D) semiconductors van der Waals (vdW) characterized by a direct optical bandgap in the visible wavelength (~2 eV). Characterization of the band alignment between TMDC and the barrier is important for the fabrication of tunneling devices. Here, we fabricate coupled quantum well (CQW) heterostructures made of 2D TMDCs with hexagonal Boron nitride (hBN) as an atomically thin barrier and gate dielectric and with top and bottom metal (or graphite) as gate electrodes. We observe a clear dependence of the photo-generated current with varying hBN thickness, electrode workfunctions, electric field, laser excitation power, excitation wavelength, and temperature. We will discuss the implication of photocurrent in relation to quantum transport process across the vdW interfaces.

Theoretical analysis of the structural phase transformation from B3 to B1 in BeO under high pressure

NASA Astrophysics Data System (ADS)

Jain, Arvind; Verma, Saligram; Nagarch, R. K.; Shah, S.; Kaurav, Netram

2018-05-01

We have performed the phase transformation and elastic properties of BeO at high pressure by formulating effective interionic interaction potential. The elastic constants, including the long-range Coulomb and van der Waals (vdW) interactions and the short-range repulsive interaction of up to second-neighbor ions within the Hafemeister and Flygare approach, are derived. Assuming that both the ions are polarizable, we employed the Slater-Kirkwood variational method to estimate the vdW coefficients, a structural phase transition (Pt) from ZnS structure (B3) to NaCl structure (B1) at 108 GPa has been predicted for BeO. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the theoretical data. The variations of elastic constants with pressure follow a systematic trend identical to that observed in others compounds of ZnS type structure family.

First-principles study of Cs/Rb co-doped FAPbI3 stability and degradation in the presence of water and oxygen

NASA Astrophysics Data System (ADS)

Guo, Yao; Li, Chengbo; Xue, Yuanbin; Geng, Cuihuan; Tian, Dayong

2018-02-01

The poor stability of organometallic halide perovskite in humid environments is one of the biggest challenges for its commercialization in light harvesting and electroluminescent displays. Understanding the atomic detail of the perovskite/water (oxygen) interface is a critical way to explore the practicability of perovskite. In this work, we report a density functional study of water and oxygen adsorption on the Cs/Rb incorporated FAPbI3 (001) surface. The role played by water and oxygen molecules has been extensively studied in the initial degradation processes, where the strong interactions between adsorbates and perovskite surfaces are confirmed. Our results show that the dopant-terminated surface was relatively more stable than PbI2-termination one. The effects of doping on the optoelectronic properties were slight at low concentrations. The calculations showed that the molecule tend to adsorb on the I-top site of the Cs-terminated surface and the Pb-top site of the PbI2 (Cs)-terminated surface. The vdW contribution on the bonding between bare surface and molecule can be observed. The degradation-induced optical absorption decrease in the visible region could be found. Water and oxygen molecule destroy the perovskite surface structures and subsequently reduce its conversion efficiency. These findings contribute molecular-level insight into the initial stage of perovskite degradation, which should be helpful to inspire new interfacial modifications to improve the stability of corresponding perovskite materials under wet conditions.

Behavior of Halogen Bonds of the Y-X⋅⋅⋅π Type (X, Y=F, Cl, Br, I) in the Benzene π System, Elucidated by Using a Quantum Theory of Atoms in Molecules Dual-Functional Analysis.

PubMed

Sugibayashi, Yuji; Hayashi, Satoko; Nakanishi, Waro

2016-08-18

The nature of halogen bonds of the Y-X-✶-π(C6 H6 ) type (X, Y=F, Cl, Br, and I) have been elucidated by using the quantum theory of atoms in molecules (QTAIM) dual-functional analysis (QTAIM-DFA), which we proposed recently. Asterisks (✶) emphasize the presence of bond-critical points (BCPs) in the interactions in question. Total electron energy densities, Hb (rc ), are plotted versus Hb (rc )-Vb (rc )/2 [=(ħ(2) /8m)∇(2) ρb (rc )] for the interactions in QTAIM-DFA, in which Vb (rc ) are potential energy densities at the BCPs. Data for perturbed structures around fully optimized structures were used for the plots, in addition to those of the fully optimized ones. The plots were analyzed by using the polar (R, θ) coordinate for the data of fully optimized structures with (θp , κp ) for those that contained the perturbed structures; θp corresponds to the tangent line of the plot and κp is the curvature. Whereas (R, θ) corresponds to the static nature, (θp , κp ) represents the dynamic nature of the interactions. All interactions in Y-X-✶-π(C6 H6 ) are classified by pure closed-shell interactions and characterized to have vdW nature, except for Y-I-✶-π(C6 H6 ) (Y=F, Cl, Br) and F-Br-✶-π(C6 H6 ), which have typical hydrogen-bond nature without covalency. I-I-✶-π(C6 H6 ) has a borderline nature between the two. Y-F-✶-π(C6 H6 ) (Y=Br, I) were optimized as bent forms, in which Y-✶-π interactions were detected. The Y-✶-π interactions in the bent forms are predicted to be substantially weaker than those in the linear F-Y-✶-π(C6 H6 ) forms. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of plasma membrane surface charges in dictating the feasibility of membrane-nanoparticle interactions

NASA Astrophysics Data System (ADS)

Sinha, Shayandev; Jing, Haoyuan; Sachar, Harnoor Singh; Das, Siddhartha

2017-12-01

Receptor-ligand (R-L) binding mediated interactions between the plasma membrane (PM) and a nanoparticle (NP) require the ligand-functionalized NPs to come to a distance of separation (DOS) of at least dRL (length of the R-L complex) from the receptor-bearing membranes. In this letter, we establish that the membrane surface charges and the surrounding ionic environment dictate whether or not the attainment of such a critical DOS is possible. The negatively charged membrane invariably induces a negative electrostatic potential at the NP surface, repelling the NP from the membrane. This is countered by the attractive influences of the thermal fluctuations and van der Waals (vdw) interactions that drive the NP close to the membrane. For a NP approaching the membrane from a distance, the ratio of the repulsive (electrostatic) and attractive (thermal and vdW) effects balances at a critical NP-membrane DOS of dg,c. For a given set of parameters, there can be two possible values of dg,c, namely, dg,c,1 and dg,c,2 with dg,c,1 ≫ dg,c,2. We establish that any R-L mediated NP-membrane interaction is possible only if dRL > dg,c,1. Therefore, our study proposes a design criterion for engineering ligands for a NP that will ensure the appropriate length of the R-L complex in order to ensure the successful membrane-NP interaction in the presence of a given electrostatic environment. Finally, we discuss the manner in which our theory can help designing ligand-grafted NPs for targeted drug delivery, design biomimetics NPs, and also explain various experimental results.

The role of the anionic and cationic pt sites in the adsorption site preference of water and ethanol on defected Pt4/Pt(111) substrates: A density functional theory investigation within the D3 van der waals corrections

NASA Astrophysics Data System (ADS)

Seminovski, Yohanna; Amaral, Rafael C.; Tereshchuk, Polina; Da Silva, Juarez L. F.

2018-01-01

Platinum (Pt) atoms in the bulk face-centered cubic structure have neutral charge because they are equivalent by symmetry, however, in clean Pt surfaces, the effective charge on Pt atoms can turn slightly negative (anionic) or positive (cationic) while increasing substantially in magnitude for defected (low-coordinated) Pt sites. The effective charge affect the adsorption properties of molecular species on Pt surfaces and it can compete in importance with the coupling of the substrate-molecule electronic states. Although several studies have been reported due to the importance of Pt for catalysis, our understanding of the role played by low-coordinated sites is still limited. Here, we employ density functional theory within the Perdew-Burke-Ernzerhof exchange-correlation functional and the D3 van der Waals (vdW) correction to investigate the role of the cationic and anionic Pt sites on the adsorption properties of ethanol and water on defected Pt4/Pt(111) substrates. Four substrates were carefully selected, namely, two two-dimensional (2D) Pt4 configurations (2D-strand and 2D-island) and two tri-dimensional (3D) Pt4 (3D-fcc and 3D-hcp), to understand the role of coordination, effective charge, and coupling of the electronic states in the adsorption properties. From the Bader charge analysis, we identified the cationic and anionic sites among the Pt atoms exposed to the vacuum region in the Pt4/Pt(111) substrates. We found that ethanol and water bind via the anionic O atoms to the low-coordinated defected Pt sites of the substrates, where the angle PtOH is nearly 100° for most configurations. In the 3D-fcc or 3D-hcp defected configurations, the lowest-coordinated Pt atoms are anionic, hence, those Pt sites are not preferable for the adsorption of O atoms. The charge transfer from water and ethanol to the Pt substrates has similar magnitude for all cases, which implies similar Coulomb contribution to the adsorption energy. Moreover, we found a correlation of the adsorption energy with the shift of the center of gravity of the occupied d-states of Pt sites.

In silico carbon molecular beam epitaxial growth of graphene on the h-BN substrate: carbon source effect on van der Waals epitaxy

NASA Astrophysics Data System (ADS)

Lee, Jonghoon; Varshney, Vikas; Park, Jeongho; Farmer, Barry L.; Roy, Ajit K.

2016-05-01

Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested.Against the presumption that hexagonal boron-nitride (h-BN) should provide an ideal substrate for van der Waals (vdW) epitaxy to grow high quality graphene films, carbon molecular beam epitaxy (CMBE) techniques using solid carbon sublimation have reported relatively poor quality of the graphene. In this article, the CMBE growth of graphene on the h-BN substrate is numerically studied in order to identify the effect of the carbon source on the quality of the graphene film. The carbon molecular beam generated by the sublimation of solid carbon source materials such as graphite and glassy carbon is mostly composed of atomic carbon, carbon dimers and carbon trimers. Therefore, the graphene film growth becomes a complex process involving various deposition characteristics of a multitude of carbon entities. Based on the study of surface adsorption and film growth characteristics of these three major carbon entities comprising graphite vapour, we report that carbon trimers convey strong traits of vdW epitaxy prone to high quality graphene growth, while atomic carbon deposition is a surface-reaction limited process accompanied by strong chemisorption. The vdW epitaxial behaviour of carbon trimers is found to be substantial enough to nucleate and develop into graphene like planar films within a nanosecond of high flux growth simulation, while reactive atomic carbons tend to impair the structural integrity of the crystalline h-BN substrate upon deposition to form an amorphous interface between the substrate and the growing carbon film. The content of reactive atomic carbons in the molecular beam is suspected to be the primary cause of low quality graphene reported in the literature. A possible optimization of the molecular beam composition towards the synthesis of better quality graphene films is suggested. Electronic supplementary information (ESI) available: Three movie files: 3mer-physorption.mpg and 3mer-chemisorption.mpg feature examples of the adsorption state sampling of a carbon trimer on the heated h-BN substrate as mentioned in the ``Single Molecule Adsorption Study'' section. In 3mer-film-growth.mpg, an instance of honey comb formation during the initial phase of graphene growth simulation using a carbon trimer beam is captured. An initially sp hybridized carbon atom (red colored) becomes sp2 hybridized as a result of additional covalent bonding with the impinging carbon trimer. As the bond angle around the red carbon changes from 180 degree (sp) to 120 degree (sp2), nearby carbon atoms enclose to form a hexagon structure composed of 6 carbon atoms. See DOI: 10.1039/c6nr01396a

Thioarsenides: A case for long-range Lewis acid-base-directed van der Waals interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gibbs, Gerald V.; Wallace, Adam F.; Downs, R. T.

2011-04-01

Electron density distributions, bond paths, Laplacian and local energy density properties have been calculated for a number of As4Sn (n = 3,4,5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As-S and As-As interactions classify as shared bonded interactions and the intermolecular As-S, As-As and S-S interactions classify as closed-shell van der Waals bonded interactions. The bulk of the intermolecular As-S bond paths link regions of locally concentrated electron density (Lewis base regions) with aligned regions of locally depleted electron density (Lewis acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for severalmore » other molecular crystals that link aligned Lewis base and acid regions in a key-lock fashion, interactions that classified as long range Lewis acid-base directed van der Waals interactions. As the bulk of the intermolecular As-S bond paths (~70%) link Lewis acid-base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As-S Lewis acid-base intermolecular bonded interactions. The maximization of the number of Lewis acid-base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long range Lewis acid-base vdW As-S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.« less

Optical properties of carbon nanotubes

NASA Astrophysics Data System (ADS)

Chen, Gugang

This thesis addresses the optical properties of novel carbon filamentary nanomaterials: single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), and SWNTs with interior C60 molecules ("peapods"). Optical reflectance spectra of bundled SWNTs are discussed in terms of their electronic energy band structure. An Effective Medium Model for a composite material was found to provide a reasonable description of the spectra. Furthermore, we have learned from optical absorption studies of DWNTs and C60-peapods that the host tube and the encapsulant interact weakly; small shifts in interband absorption structure were observed. Resonant Raman scattering studies on SWNTs synthesized via the HiPCO process show that the "zone-folding" approximation for phonons and electrons works reasonably well, even for small diameter (d < 1 nm) tubes. The energy of optical transitions between van Hove singularities in the electronic density of states computed from the "zone-folding" model (with gamma0 = 2.9 eV) agree well with the resonant conditions for Raman scattering. Small diameter tubes were found to exhibit additional sharp Raman bands in the frequency range 500-1200 cm-1 with an, as yet, undetermined origin. The Raman spectrum of a DWNT was found to be well described by a superposition of the Raman spectra expected for inner and outer tubes, i.e., no charge transfer occurs and the weak van der Waals (vdW) interaction between tubes does not have significant impact on the phonons. A ˜7 cm-1 downshift of the small diameter, inner-tube tangential mode frequency was observed, however, but attributed to a tube wall curvature effect, rather than the vdW interaction. Finally, we studied the chemical doping of DWNTs, where the dopant (Br anions) is chemically bound to the outside of the outer tube. The doped DWNT system is a model for a cylindrical molecular capacitor. We found experimentally that 90% of the positive charge resides on the outer tube, so that most of electric field on the inner tube is screened, i.e., we have observed a molecular Faraday cage effect. A self-consistent theoretical model in the tight-binding approximation with a classical electrostatic energy term is in good agreement with our experimental results.

Deformation Response of Conformally Coated Carbon Nanotube Forests

DTIC Science & Technology

2013-11-05

forces between bare CNTs compared to coated CNTs that keep them together when bent. The vdW forces are proportional to the Hamaker constant [49...Chemistry 3rd edn (New York: Dekker) p 650 [50] Lefèvre G and Jolivet A 2009 Calculation of Hamaker constants applied to the deposition of metallic oxide

Tuning the p-type Schottky barrier in 2D metal/semiconductor interface:boron-sheet on MoSe2, and WSe2

NASA Astrophysics Data System (ADS)

Couto, W. R. M.; Miwa, R. H.; Fazzio, A.

2017-10-01

Van der Waals (vdW) metal/semiconductor heterostructures have been investigated through first-principles calculations. We have considered the recently synthesized borophene (Mannix et al 2015 Science 350 1513), and the planar boron sheets (S1 and S2) (Feng et al 2016 Nat. Chem. 8 563) as the 2D metal layer, and the transition metal dichalcogenides (TMDCs) MoSe2, and WSe2 as the semiconductor monolayer. We find that the energetic stability of those 2D metal/semiconductor heterojunctions is mostly ruled by the vdW interactions; however, chemical interactions also take place in borophene/TMDC. The electronic charge transfer at the metal/semiconductor interface has been mapped, where we find a a net charge transfer from the TMDCs to the boron sheets. Further electronic structure calculations reveal that the metal/semiconductor interfaces, composed by planar boron sheets S1 and S2, present a p-type Schottky barrier which can be tuned to a p-type ohmic contact by an external electric field.

Tunneling Photocurrent Assisted by Interlayer Excitons in Staggered van der Waals Hetero-Bilayers.

PubMed

Luong, Dinh Hoa; Lee, Hyun Seok; Neupane, Guru Prakash; Roy, Shrawan; Ghimire, Ganesh; Lee, Jin Hee; Vu, Quoc An; Lee, Young Hee

2017-09-01

Vertically stacked van der Waals (vdW) heterostructures have been suggested as a robust platform for studying interfacial phenomena and related electric/optoelectronic devices. While the interlayer Coulomb interaction mediated by the vdW coupling has been extensively studied for carrier recombination processes in a diode transport, its correlation with the interlayer tunneling transport has not been elucidated. Here, a contrast is reported between tunneling and drift photocurrents tailored by the interlayer coupling strength in MoSe 2 /MoS 2 hetero-bilayers (HBs). The interfacial coupling modulated by thermal annealing is identified by the interlayer phonon coupling in Raman spectra and the emerging interlayer exciton peak in photoluminescence spectra. In strongly coupled HBs, positive photocurrents are observed owing to the inelastic band-to-band tunneling assisted by interlayer excitons that prevail over exciton recombinations. By contrast, weakly coupled HBs exhibit a negative photovoltaic diode behavior, manifested as a drift current without interlayer excitonic emissions. This study sheds light on tailoring the tunneling transport for numerous optoelectronic HB devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sb2Te3 and Its Superlattices: Optimization by Statistical Design.

PubMed

Behera, Jitendra K; Zhou, Xilin; Ranjan, Alok; Simpson, Robert E

2018-05-02

The objective of this work is to demonstrate the usefulness of fractional factorial design for optimizing the crystal quality of chalcogenide van der Waals (vdW) crystals. We statistically analyze the growth parameters of highly c axis oriented Sb 2 Te 3 crystals and Sb 2 Te 3 -GeTe phase change vdW heterostructured superlattices. The statistical significance of the growth parameters of temperature, pressure, power, buffer materials, and buffer layer thickness was found by fractional factorial design and response surface analysis. Temperature, pressure, power, and their second-order interactions are the major factors that significantly influence the quality of the crystals. Additionally, using tungsten rather than molybdenum as a buffer layer significantly enhances the crystal quality. Fractional factorial design minimizes the number of experiments that are necessary to find the optimal growth conditions, resulting in an order of magnitude improvement in the crystal quality. We highlight that statistical design of experiment methods, which is more commonly used in product design, should be considered more broadly by those designing and optimizing materials.

Modulation of Metal and Insulator States in 2D Ferromagnetic VS2 by van der Waals Interaction Engineering.

PubMed

Guo, Yuqiao; Deng, Haitao; Sun, Xu; Li, Xiuling; Zhao, Jiyin; Wu, Junchi; Chu, Wangsheng; Zhang, Sijia; Pan, Haibin; Zheng, Xusheng; Wu, Xiaojun; Jin, Changqing; Wu, Changzheng; Xie, Yi

2017-08-01

2D transition-metal dichalcogenides (TMDCs) are currently the key to the development of nanoelectronics. However, TMDCs are predominantly nonmagnetic, greatly hindering the advancement of their spintronic applications. Here, an experimental realization of intrinsic magnetic ordering in a pristine TMDC lattice is reported, bringing a new class of ferromagnetic semiconductors among TMDCs. Through van der Waals (vdW) interaction engineering of 2D vanadium disulfide (VS 2 ), dual regulation of spin properties and bandgap brings about intrinsic ferromagnetism along with a small bandgap, unravelling the decisive role of vdW gaps in determining the electronic states in 2D VS 2 . An overall control of the electronic states of VS 2 is also demonstrated: bond-enlarging triggering a metal-to-semiconductor electronic transition and bond-compression inducing metallization in 2D VS 2 . The pristine VS 2 lattice thus provides a new platform for precise manipulation of both charge and spin degrees of freedom in 2D TMDCs availing spintronic applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free energy decomposition of protein-protein interactions.

PubMed

Noskov, S Y; Lim, C

2001-08-01

A free energy decomposition scheme has been developed and tested on antibody-antigen and protease-inhibitor binding for which accurate experimental structures were available for both free and bound proteins. Using the x-ray coordinates of the free and bound proteins, the absolute binding free energy was computed assuming additivity of three well-defined, physical processes: desolvation of the x-ray structures, isomerization of the x-ray conformation to a nearby local minimum in the gas-phase, and subsequent noncovalent complex formation in the gas phase. This free energy scheme, together with the Generalized Born model for computing the electrostatic solvation free energy, yielded binding free energies in remarkable agreement with experimental data. Two assumptions commonly used in theoretical treatments; viz., the rigid-binding approximation (which assumes no conformational change upon complexation) and the neglect of vdW interactions, were found to yield large errors in the binding free energy. Protein-protein vdW and electrostatic interactions between complementary surfaces over a relatively large area (1400--1700 A(2)) were found to drive antibody-antigen and protease-inhibitor binding.

Adsorption of GA module onto graphene and graphene oxide: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Chen, Junlang; Wang, Xiaogang; Dai, Chaoqing; Chen, Shude; Tu, Yusong

2014-08-01

Using all-atom molecular dynamics (MD) simulation, we have investigated the adsorption of protein GA module (GA53) onto graphene oxide (GO), compared with similar adsorption onto pristine graphene (PG). We find that: (1) the protein GA53 can be easily and firmly adsorbed onto the surface of GO and PG, but the binding sites are not specific; the main difference is that the secondary structure of GA53 can be well preserved in protein-GO system, while GA53 will partially lose its secondary structure after adsorbed on PG. (2) in protein-GO system, hydroxyl and epoxy groups increase the distance between protein and GO, which weaken their vdW interactions, meanwhile, hydrogen bonds and electrostatic interactions enhance their binding affinity. In protein-PG system, strong vdW interactions between residues of GA53 and PG have destroyed its secondary structure. (3) π-π stacking interactions still exist between aromatic residues and both the basal plane of GO and PG. In comparison with PG, our results suggest that GO presents better biocompatibility to preserve protein secondary structure when simultaneously absorbing protein.

Dual-gated MoS2/WSe2 van der Waals tunnel diodes and transistors.

PubMed

Roy, Tania; Tosun, Mahmut; Cao, Xi; Fang, Hui; Lien, Der-Hsien; Zhao, Peida; Chen, Yu-Ze; Chueh, Yu-Lun; Guo, Jing; Javey, Ali

2015-02-24

Two-dimensional layered semiconductors present a promising material platform for band-to-band-tunneling devices given their homogeneous band edge steepness due to their atomically flat thickness. Here, we experimentally demonstrate interlayer band-to-band tunneling in vertical MoS2/WSe2 van der Waals (vdW) heterostructures using a dual-gate device architecture. The electric potential and carrier concentration of MoS2 and WSe2 layers are independently controlled by the two symmetric gates. The same device can be gate modulated to behave as either an Esaki diode with negative differential resistance, a backward diode with large reverse bias tunneling current, or a forward rectifying diode with low reverse bias current. Notably, a high gate coupling efficiency of ∼80% is obtained for tuning the interlayer band alignments, arising from weak electrostatic screening by the atomically thin layers. This work presents an advance in the fundamental understanding of the interlayer coupling and electron tunneling in semiconductor vdW heterostructures with important implications toward the design of atomically thin tunnel transistors.

Volatile anesthetic binding to proteins is influenced by solvent and aliphatic residues.

PubMed

Streiff, John H; Jones, Keith A

2008-10-01

The main objective of this work was to characterize VA binding sites in multiple anesthetic target proteins. A computational algorithm was used to quantify the solvent exclusion and aliphatic character of amphiphilic pockets in the structures of VA binding proteins. VA binding sites in the protein structures were defined as the pockets with solvent exclusion and aliphatic character that exceeded minimum values observed in the VA binding sites of serum albumin, firefly luciferase, and apoferritin. We found that the structures of VA binding proteins are enriched in these pockets and that the predicted binding sites were consistent with experimental determined binding locations in several proteins. Autodock3 was used to dock the simulated molecules of 1,1,1,2,2-pentafluoroethane, difluoromethyl 1,1,1,2-tetrafluoroethyl ether, and sevoflurane and the isomers of halothane and isoflurane into these potential binding sites. We found that the binding of the various VA molecules to the amphiphilic pockets is driven primarily by VDW interactions and to a lesser extent by weak hydrogen bonding and electrostatic interactions. In addition, the trend in Delta G binding values follows the Meyer-Overton rule. These results suggest that VA potencies are related to the VDW interactions between the VA ligand and protein target. It is likely that VA bind to sites with a high degree of solvent exclusion and aliphatic character because aliphatic residues provide favorable VDW contacts and weak hydrogen bond donors. Water molecules occupying these sites maintain pocket integrity, associate with the VA ligand, and diminish the unfavorable solvation enthalpy of the VA. Water molecules displaced into the bulk by the VA ligand may provide an additional favorable enthalpic contribution to VA binding. Anesthesia is a component of many health related procedures, the outcomes of which could be improved with a better understanding of the molecular targets and mechanisms of anesthetic action.

Adsorption of DNA/RNA nucleobases onto single-layer MoS2 and Li-Doped MoS2: A dispersion-corrected DFT study

NASA Astrophysics Data System (ADS)

Sadeghi, Meisam; Jahanshahi, Mohsen; Ghorbanzadeh, Morteza; Najafpour, Ghasem

2018-03-01

The kind of sensing platform in nano biosensor plays an important role in nucleic acid sequence detection. It has been demonstrated that graphene does not have an intrinsic band gap; therefore, transition metal dichalcogenides (TMDs) are desirable materials for electronic base detection. In the present work, a comparative study of the adsorption of the DNA/RNA nucleobases [Adenine (A), Cytosine (C) Guanine (G), Thymine (T) and Uracil (U)] onto the single-layer molybdenum disulfide (MoS2) and Li-doped MoS2 (Li-MoS2) as a sensing surfaces was investigated by using Dispersion-corrected Density Functional Theory (D-DFT) calculations and different measure of equilibrium distances, charge transfers and binding energies for the various nucleobases were calculated. The results revealed that the interactions between the nucleobases and the MoS2 can be strongly enhanced by introducing metal atom, due to significant charge transfer from the Li atom to the MoS2 when Lithium is placed on top of the MoS2. Furthermore, the binding energies of the five nucleobases were in the range of -0.734 to -0.816 eV for MoS2 and -1.47 to -1.80 eV for the Li-MoS2. Also, nucleobases were adsorbed onto MoS2 sheets via the van der Waals (vdW) force. This high affinity and the renewable properties of the biosensing platform demonstrated that Li-MoS2 nanosheet is biocompatible and suitable for nucleic acid analysis.

Estimation of polymer-surface interfacial interaction strength by a contact AFM technique.

PubMed

Dvir, H; Jopp, J; Gottlieb, M

2006-12-01

Atomic force microscopy (AFM) measurements were employed to assess polymer-surface interfacial interaction strength. The main feature of the measurement is the use of contact-mode AFM as a tool to scratch off the polymer monolayer adsorbed on the solid surface. Tapping-mode AFM was used to determine the depth of the scraped recess. Independent determination of the layer thickness obtained from optical phase interference microscopy (OPIM) confirmed the depth of the AFM scratch. The force required for the complete removal of the polymer layer with no apparent damage to the substrate surface was determined. Polypropylene (PP), low-density polyethylene (PE), and PP-grafted-maleic anhydride (PP-g-ma) were scraped off silane-treated glass slabs, and the strength of surface interaction of the polymer layer was determined. In all cases it was determined that the magnitude of surface interaction force is of the order of van der Waals (VDW) interactions. The interaction strength is influenced either by polymer ability to wet the surface (hydrophobic or hydrophilic interactions) or by hydrogen bonding between the polymer and the surface treatment.

Molecular dynamics investigation of the physisorption and interfacial characteristics of NBR chains on carbon nanotubes with different characteristics

NASA Astrophysics Data System (ADS)

Li, Kun; Gu, Boqin

2017-07-01

The present study investigates the physisorption and interfacial interactions between multiwalled carbon nanotubes (MWNTs) with different characteristics, including different numbers of walls and different functional groups, and acrylonitrile-butadiene rubber (NBR) polymer chains based on molecular dynamics simulations performed using modeled MWNT/NBR compound systems. The effects of the initial orientation of NBR chains and their relative distances to nanotubes, number of nanotube layers, and the surface functional groups of nanotubes on nanotube/polymer interactions are examined. Analysis is conducted according to the final configuration obtained in conjunction with the binding energy (Eb), radius of gyration (Rg) and end-to-end distance (h). The results show that the final conformations of NBR chains adsorbed on MWNT surfaces is associated with the initial relative angle of the NBR chains and their distance from the nanotubes. For non-functionalized MWNTs, Eb is almost directly proportional to Rg under equivalent parameters. Moreover, it is observed that functional groups hinder the wrapping of NBR chains on the MWNT surfaces. This indicates that functional groups do not always benefit the macro-mechanical properties of the composites. Moreover, the type of the major interaction force has been dramatically changed into electrostatic force from vdW force because of functionalization.

Geometrothermodynamics of Van der Waals black hole

NASA Astrophysics Data System (ADS)

Hu, Yumin; Chen, Juhua; Wang, Yongjiu

2017-12-01

We study the geometrothermodynamics of a special asymptotically AdS black hole, i.e. Van der Waals ( VdW) black hole, in the extended phase space where the negative cosmological constant Λ can be regarded as thermodynamic pressure. Analysing some special conditions of this black hole with geometrothermodynamical method, we find a good correlation with ordinary cases according to the state equation.

Surface Wave Dynamics in the Coastal Zone

DTIC Science & Technology

2013-09-30

summarized in Figure 1. Scatter index # DDD 󈨙 0.73 Mad󈨐 Ting󈧅+ T&M󈧆 S&Hol󈨙 S&How󈨝 Lipp󈨤+ vdW󈧍 FA󈧐 R&S󈧇/07 Slopes J&B󈧋...Battjes & Janssen [1978] TG󈨗 = Thornton & Guza [1983] Bald󈨦 = Baldock et al. [1998] DDD 󈨙 = Dally et al. [1985] J&B󈧋 = Janssen & Battjes

Vertical MoSe2-MoO x p-n heterojunction and its application in optoelectronics.

PubMed

Chen, Xiaoshuang; Liu, Guangbo; Hu, Yunxia; Cao, Wenwu; Hu, PingAn; Hu, Wenping

2018-01-26

The hybrid n-type 2D transition-metal dichalcogenide (TMD)/p-type oxide van der Waals (vdW) heterojunction nanosheets consist of 2D layered MoSe 2 (the n-type 2D material) and MoO x (the p-type oxide) which are grown on SiO 2 /Si substrates for the first time via chemical vapor deposition technique, displaying the regular hexagon structures with the average length dimension of sides of ∼8 μm. Vertical MoSe 2 -MoO x p-n heterojunctions demonstrate obviously current-rectifying characteristic, and it can be tuned via gate voltage. What is more, the photodetector based on vertical MoSe 2 -MoO x heterojunctions displays optimal photoresponse behavior, generating the responsivity, detectivity, and external quantum efficiency to 3.4 A W -1 , 0.85 × 10 8 Jones, and 1665.6%, respectively, at V ds  = 5 V with the light wavelength of 254 nm under 0.29 mW cm -2 . These results furnish a building block on investigating the flexible and transparent properties of vdW and further optimizing the structure of the devices for better optoelectronic and electronic performance.

Unusual exciton–phonon interactions at van der Waals engineered interfaces

DOE PAGES

Chow, Colin M.; Yu, Hongyi; Jones, Aaron M.; ...

2017-01-13

Raman scattering is a ubiquitous phenomenon in light–matter interactions, which reveals a material’s electronic, structural, and thermal properties. Controlling this process would enable new ways of studying and manipulating fundamental material properties. Here, we report a novel Raman scattering process at the interface between different van der Waals (vdW) materials as well as between a monolayer semiconductor and 3D crystalline substrates. We find that interfacing a WSe 2 monolayer with materials such as SiO 2, sapphire, and hexagonal boron nitride (hBN) enables Raman transitions with phonons that are either traditionally inactive or weak. This Raman scattering can be amplified bymore » nearly 2 orders of magnitude when a foreign phonon mode is resonantly coupled to the A exciton in WSe 2 directly or via an A 1' optical phonon from WSe 2. We further showed that the interfacial Raman scattering is distinct between hBN-encapsulated and hBN-sandwiched WSe 2 sample geometries. Finally, this cross-platform electron–phonon coupling, as well as the sensitivity of 2D excitons to their phononic environments, will prove important in the understanding and engineering of optoelectronic devices based on vdW heterostructures.« less

Vertical MoSe2-MoO x p-n heterojunction and its application in optoelectronics

NASA Astrophysics Data System (ADS)

Chen, Xiaoshuang; Liu, Guangbo; Hu, Yunxia; Cao, Wenwu; Hu, PingAn; Hu, Wenping

2018-01-01

The hybrid n-type 2D transition-metal dichalcogenide (TMD)/p-type oxide van der Waals (vdW) heterojunction nanosheets consist of 2D layered MoSe2 (the n-type 2D material) and MoO x (the p-type oxide) which are grown on SiO2/Si substrates for the first time via chemical vapor deposition technique, displaying the regular hexagon structures with the average length dimension of sides of ˜8 μm. Vertical MoSe2-MoO x p-n heterojunctions demonstrate obviously current-rectifying characteristic, and it can be tuned via gate voltage. What is more, the photodetector based on vertical MoSe2-MoO x heterojunctions displays optimal photoresponse behavior, generating the responsivity, detectivity, and external quantum efficiency to 3.4 A W-1, 0.85 × 108 Jones, and 1665.6%, respectively, at V ds = 5 V with the light wavelength of 254 nm under 0.29 mW cm-2. These results furnish a building block on investigating the flexible and transparent properties of vdW and further optimizing the structure of the devices for better optoelectronic and electronic performance.

A van der Waals pn heterojunction with organic/inorganic semiconductors

NASA Astrophysics Data System (ADS)

He, Daowei; Pan, Yiming; Nan, Haiyan; Gu, Shuai; Yang, Ziyi; Wu, Bing; Luo, Xiaoguang; Xu, Bingchen; Zhang, Yuhan; Li, Yun; Ni, Zhenhua; Wang, Baigeng; Zhu, Jia; Chai, Yang; Shi, Yi; Wang, Xinran

2015-11-01

van der Waals (vdW) heterojunctions formed by two-dimensional (2D) materials have attracted tremendous attention due to their excellent electrical/optical properties and device applications. However, current 2D heterojunctions are largely limited to atomic crystals, and hybrid organic/inorganic structures are rarely explored. Here, we fabricate the hybrid 2D heterostructures with p-type dioctylbenzothienobenzothiophene (C8-BTBT) and n-type MoS2. We find that few-layer C8-BTBT molecular crystals can be grown on monolayer MoS2 by vdW epitaxy, with pristine interface and controllable thickness down to monolayer. The operation of the C8-BTBT/MoS2 vertical heterojunction devices is highly tunable by bias and gate voltages between three different regimes: interfacial recombination, tunneling, and blocking. The pn junction shows diode-like behavior with rectifying ratio up to 105 at the room temperature. Our devices also exhibit photovoltaic responses with a power conversion efficiency of 0.31% and a photoresponsivity of 22 mA/W. With wide material combinations, such hybrid 2D structures will offer possibilities for opto-electronic devices that are not possible from individual constituents.

Endodontic treatment of mandibular molar with root dilaceration using Reciproc single-file system.

PubMed

Meireles, Daniely Amorin; Bastos, Mariana Mena Barreto; Marques, André Augusto Franco; Garcia, Lucas da Fonseca Roberti; Sponchiado, Emílio Carlos

2013-08-01

Biomechanical preparation of root canals with accentuated curvature is challenging. New rotatory systems, such as Reciproc, require a shorter period of time to prepare curved canals, and became a viable alternative for endodontic treatment of teeth with root dilaceration. Thus, this study aimed to report a clinical case of endodontic therapy of root with accentuated dilaceration using Reciproc single-file system. Mandibular right second molar was diagnosed as asymptomatic irreversible pulpitis. Pulp chamber access was performed, and glide path was created with #10 K-file (Dentsply Maillefer) and PathFile #13, #16 and #19 (Dentsply Maillefer) up to the temporary working length. The working length measured corresponded to 20 mm in the mesio-buccal and mesio-lingual canals, and 22 mm in the distal canal. The R25 file (VDW GmbH) was used in all the canals for instrumentation and final preparation, followed by filling with Reciproc gutta-percha cones (VDW GmbH) and AH Plus sealer (Dentsply Maillefer), using thermal compaction technique. The case has been receiving follow-up for 6 mon and no painful symptomatology or periapical lesions have been found. Despite the difficulties, the treatment could be performed in a shorter period of time than the conventional methods.

Unusual exciton–phonon interactions at van der Waals engineered interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chow, Colin M.; Yu, Hongyi; Jones, Aaron M.

Raman scattering is a ubiquitous phenomenon in light–matter interactions, which reveals a material’s electronic, structural, and thermal properties. Controlling this process would enable new ways of studying and manipulating fundamental material properties. Here, we report a novel Raman scattering process at the interface between different van der Waals (vdW) materials as well as between a monolayer semiconductor and 3D crystalline substrates. We find that interfacing a WSe 2 monolayer with materials such as SiO 2, sapphire, and hexagonal boron nitride (hBN) enables Raman transitions with phonons that are either traditionally inactive or weak. This Raman scattering can be amplified bymore » nearly 2 orders of magnitude when a foreign phonon mode is resonantly coupled to the A exciton in WSe 2 directly or via an A 1' optical phonon from WSe 2. We further showed that the interfacial Raman scattering is distinct between hBN-encapsulated and hBN-sandwiched WSe 2 sample geometries. Finally, this cross-platform electron–phonon coupling, as well as the sensitivity of 2D excitons to their phononic environments, will prove important in the understanding and engineering of optoelectronic devices based on vdW heterostructures.« less

Graphene-based vdW heterostructure Induced High-efficiency Thermoelectric Devices

NASA Astrophysics Data System (ADS)

Liang, Shijun; Ang, Lay Kee

Thermoelectric material (TE) can convert the heat into electricity to provide green energy source and its performance is characterized by a figure of merit (ZT) parameter. Traditional TE materials only give ZT equal to around 1 at room temperature. But, it is believed that materials with ZT >3 will find wide applications at this low temperature range. Prior studies have implied that the interrelation between electric conductivity and lattice thermal conductivity renders the goal of engineering ZT of bulk materials to reach ZT >3. In this work, we propose a high-efficiency van del Waals (vdW) heterostructure-based thermionic device with graphene electrodes, which is able to harvest wasted heat (around 400K) based on the newly established thermionic emission law of graphene electrodes instead of Seebeck effect, to boost the efficiency of power generation over 10% around room temperature. The efficiency can be above 20% if the Schottky barrier height and cross-plane lattice thermal conductivity of transition metal dichacogenides (TMD) materials can be fine-engineered. As a refrigerator at 260 K, the efficiency is 50% to 80% of Carnot efficiency. Finally, we identify two TMD materials as the ideal candidates of graphene/TMD/graphene devices based on the state-of-art technology.

Study of interactions between metal ions and protein model compounds by energy decomposition analyses and the AMOEBA force field

NASA Astrophysics Data System (ADS)

Jing, Zhifeng; Qi, Rui; Liu, Chengwen; Ren, Pengyu

2017-10-01

The interactions between metal ions and proteins are ubiquitous in biology. The selective binding of metal ions has a variety of regulatory functions. Therefore, there is a need to understand the mechanism of protein-ion binding. The interactions involving metal ions are complicated in nature, where short-range charge-penetration, charge transfer, polarization, and many-body effects all contribute significantly, and a quantitative description of all these interactions is lacking. In addition, it is unclear how well current polarizable force fields can capture these energy terms and whether these polarization models are good enough to describe the many-body effects. In this work, two energy decomposition methods, absolutely localized molecular orbitals and symmetry-adapted perturbation theory, were utilized to study the interactions between Mg2+/Ca2+ and model compounds for amino acids. Comparison of individual interaction components revealed that while there are significant charge-penetration and charge-transfer effects in Ca complexes, these effects can be captured by the van der Waals (vdW) term in the AMOEBA force field. The electrostatic interaction in Mg complexes is well described by AMOEBA since the charge penetration is small, but the distance-dependent polarization energy is problematic. Many-body effects were shown to be important for protein-ion binding. In the absence of many-body effects, highly charged binding pockets will be over-stabilized, and the pockets will always favor Mg and thus lose selectivity. Therefore, many-body effects must be incorporated in the force field in order to predict the structure and energetics of metalloproteins. Also, the many-body effects of charge transfer in Ca complexes were found to be non-negligible. The absorption of charge-transfer energy into the additive vdW term was a main source of error for the AMOEBA many-body interaction energies.

Theoretical analysis of the structural phase transformation in the ZnO under high pressure

NASA Astrophysics Data System (ADS)

Verma, Saligram; Jain, Arvind; Nagarch, R. K.; Shah, S.; Kaurav, Netram

2018-05-01

We report a phenomenological model based calculation of pressure-induced structural phase transition and elastic properties of ZnO compound. Gibb's free energy is obtained as a function of pressure by applying an effective inter ionic interaction potential, which includes the long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach. From the present study, we predict a structural phase transition from ZnS structure (B3) to NaCl structure (B1) at 8.5 GPa. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data. The variations of elastic constants with pressure follow a systematic trend identical to that observed in others compounds of ZnS type structure family.

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Fernández-Perea, Ricardo; Madzharova, Fani

2016-06-28

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet thismore » challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He–Mg pair potentials is also presented, as an improvement of the approximation using isolated He–Mg pairs.« less

Adsorption and substitution effects of Mg on the growth of calcium sulfate hemihydrate: An ab initio DFT study

NASA Astrophysics Data System (ADS)

Xin, Yan; Hou, S. C.; Xiang, Lan; Yu, Yang-Xin

2015-12-01

Calcium sulfate hemihydrate (CaSO4·0.5H2O, CSH) whiskers with high aspect ratio are promising reinforce materials which have drawn much attention. In order to obtain high quality CSH materials, effect of Mg2+ ions on properties of the (0 0 2), (2 0 0)1 and (2 0 0)2 planes of CSH is investigated using an ab initio density functional theory (DFT) with a van der Waals (vdW) dispersion-correction. The computed results show that strong adsorption and substitution effects take place between Mg2+ ion and (2 0 0)1 plane. The adsorption energies of an Mg2+ ion on the (0 0 2), (2 0 0)1 and (2 0 0)2 planes are -0.066, -0.571 and -0.047 eV, respectively. An insight into the electrostatic potential of pristine CSH planes has demonstrated that the (2 0 0)1 plane is much more negatively charged than the (0 0 2) and (2 0 0)2 planes. The energies of the substitution of a Ca atom with an Mg atom on the CSH (0 0 2), (2 0 0)1 and (2 0 0)2 planes are 1.572, 0.063 and 1.349 eV, respectively. It is found that Ca atoms on the (2 0 0)1 plane are relatively easy to be substituted by Mg atoms. The calculation results of a Ca2+ ion adsorption on the Mg-doped (2 0 0)1 plane indicate that the adsorption energies increase apparently as the doping ratio varies from 0 to 1.0. Compared with K+, Na+ and Al3+ ions, Mg2+ ion is the most promising additive to promote the growth of CSH along c axis.

Interfacial Interactions in Monolayer and Few-Layer SnS/CH3 NH3 PbI3 Perovskite van der Waals Heterostructures and Their Effects on Electronic and Optical Properties.

PubMed

Li, Jian-Cai; Wei, Zeng-Xi; Huang, Wei-Qing; Ma, Li-Li; Hu, Wangyu; Peng, Ping; Huang, Gui-Fang

2018-02-05

A high light-absorption coefficient and long-range hot-carrier transport of hybrid organic-inorganic perovskites give huge potential to their composites in solar energy conversion and environmental protection. Understanding interfacial interactions and their effects are paramount for designing perovskite-based heterostructures with desirable properties. Herein, we systematically investigated the interfacial interactions in monolayer and few-layer SnS/CH 3 NH 3 PbI 3 heterostructures and their effects on the electronic and optical properties of these structures by density functional theory. It was found that the interfacial interactions in SnS/CH 3 NH 3 PbI 3 heterostructures were van der Waals (vdW) interactions, and they were found to be insensitive to the layer number of 2D SnS sheets. Interestingly, although their band gap decreased upon increasing the layer number of SnS, the near-gap electronic states and optical absorption spectra of these heterostructures were found to be strikingly similar. This feature was determined to be critical for the design of 2D layered SnS-based heterostructures. Strong absorption in the ultraviolet and visible-light regions, type II staggered band alignment at the interface, and few-layer SnS as an active co-catalyst make 2D SnS/CH 3 NH 3 PbI 3 heterostructures promising candidates for photocatalysis, photodetectors, and solar energy harvesting and conversion. These results provide first insight into the nature of interfacial interactions and are useful for designing hybrid organic-inorganic perovskite-based devices with novel properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

NASA Astrophysics Data System (ADS)

de Lara-Castells, María Pilar; Fernández-Perea, Ricardo; Madzharova, Fani; Voloshina, Elena

2016-06-01

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet this challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He-Mg pair potentials is also presented, as an improvement of the approximation using isolated He-Mg pairs.

Thermodynamics of a lattice gas with linear attractive potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pirjol, Dan; Schat, Carlos

We study the equilibrium thermodynamics of a one-dimensional lattice gas with interaction V(|i−j|)=−1/(μn) (ξ−1/n |i−j|) given by the superposition of a universal attractive interaction with strength −1/(μn) ξ<0, and a linear attractive potential 1/(μn{sup 2}) |i−j|. The interaction is rescaled with the lattice size n, such that the thermodynamical limit n → ∞ is well-behaved. The thermodynamical properties of the system can be found exactly, both for a finite size lattice and in the thermodynamical limit n → ∞. The lattice gas can be mapped to a system of non-interacting bosons which are placed on known energy levels. The exactmore » solution shows that the system has a liquid-gas phase transition for ξ > 0. In the large temperature limit T ≫ T{sub 0}(ρ) = ρ{sup 2}/(4μ) with ρ the density, the system becomes spatially homogeneous, and the equation of state is given to a good approximation by a lattice version of the van der Waals equation, with critical temperature T{sub c}{sup (vdW)}=1/(12μ) (3ξ−1)« less

Theoretical studies on lattice-oriented growth of single-walled carbon nanotubes on sapphire

NASA Astrophysics Data System (ADS)

Li, Zhengwei; Meng, Xianhong; Xiao, Jianliang

2017-09-01

Due to their excellent mechanical and electrical properties, single-walled carbon nanotubes (SWNTs) can find broad applications in many areas, such as field-effect transistors, logic circuits, sensors and flexible electronics. High-density, horizontally aligned arrays of SWNTs are essential for high performance electronics. Many experimental studies have demonstrated that chemical vapor deposition growth of nanotubes on crystalline substrates such as sapphire offers a promising route to achieve such dense, perfectly aligned arrays. In this work, a theoretical study is performed to quantitatively understand the van der Waals interactions between SWNTs and sapphire substrates. The energetically preferred alignment directions of SWNTs on A-, R- and M-planes and the random alignment on the C-plane predicted by this study are all in good agreement with experiments. It is also shown that smaller SWNTs have better alignment than larger SWNTs due to their stronger interaction with sapphire substrate. The strong vdW interactions along preferred alignment directions can be intuitively explained by the nanoscale ‘grooves’ formed by atomic lattice structures on the surface of sapphire. This study provides important insights to the controlled growth of nanotubes and potentially other nanomaterials.

Phonon-coupled ultrafast interlayer charge oscillation at van der Waals heterostructure interfaces

NASA Astrophysics Data System (ADS)

Zheng, Qijing; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V.; Saidi, Wissam A.; Zhao, Jin

2018-05-01

Van der Waals (vdW) heterostructures of transition-metal dichalcogenide (TMD) semiconductors are central not only for fundamental science, but also for electro- and optical-device technologies where the interfacial charge transfer is a key factor. Ultrafast interfacial charge dynamics has been intensively studied, however, the atomic scale insights into the effects of the electron-phonon (e-p) coupling are still lacking. In this paper, using time dependent ab initio nonadiabatic molecular dynamics, we study the ultrafast interfacial charge transfer dynamics of two different TMD heterostructures MoS2/WS2 and MoSe2/WSe2 , which have similar band structures but different phonon frequencies. We found that MoSe2/WSe2 has softer phonon modes compared to MoS2/WS2 , and thus phonon-coupled charge oscillation can be excited with sufficient phonon excitations at room temperature. In contrast, for MoS2/WS2 , phonon-coupled interlayer charge oscillations are not easily excitable. Our study provides an atomic level understanding on how the phonon excitation and e-p coupling affect the interlayer charge transfer dynamics, which is valuable for both the fundamental understanding of ultrafast dynamics at vdW hetero-interfaces and the design of novel quasi-two-dimensional devices for optoelectronic and photovoltaic applications.

Revealing the preferred interlayer orientations and stackings of two-dimensional bilayer gallium selenide crystals

DOE PAGES

Li, Xufan; Basile Carrasco, Leonardo A.; Yoon, Mina; ...

2015-01-21

Characterizing and controlling the interlayer orientations and stacking order of bilayer two-dimensional (2D) crystals and van der Waals (vdW) heterostructure is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) that result from different layer stacking provide an ideal platform to study the stacking configurations in bilayer 2D crystals. Here, through a controllable vapor-phase deposition method we selectively grow bilayer GaSe crystals and investigate their two preferred 0° or 60° interlayer rotations. The commensurate stacking configurations (AA' and AB-stacking) in as-grown 2D bilayer GaSe crystals are clearly observed at the atomic scale andmore » the Ga-terminated edge structure are identified for the first time by using atomic-resolution scanning transmission electron microscopy (STEM). Theoretical analysis of the interlayer coupling energetics vs. interlayer rotation angle reveals that the experimentally-observed orientations are energetically preferred among the bilayer GaSe crystal polytypes. Here, the combined experimental and theoretical characterization of the GaSe bilayers afforded by these growth studies provide a pathway to reveal the atomistic relationships in interlayer orientations responsible for the electronic and optical properties of bilayer 2D crystals and vdW heterostructures.« less

Toward a Mechanistic Understanding of Vertical Growth of van der Waals Stacked 2D Materials: A Multiscale Model and Experiments.

PubMed

Ye, Han; Zhou, Jiadong; Er, Dequan; Price, Christopher C; Yu, Zhongyuan; Liu, Yumin; Lowengrub, John; Lou, Jun; Liu, Zheng; Shenoy, Vivek B

2017-12-26

Vertical stacking of monolayers via van der Waals (vdW) interaction opens promising routes toward engineering physical properties of two-dimensional (2D) materials and designing atomically thin devices. However, due to the lack of mechanistic understanding, challenges remain in the controlled fabrication of these structures via scalable methods such as chemical vapor deposition (CVD) onto substrates. In this paper, we develop a general multiscale model to describe the size evolution of 2D layers and predict the necessary growth conditions for vertical (initial + subsequent layers) versus in-plane lateral (monolayer) growth. An analytic thermodynamic criterion is established for subsequent layer growth that depends on the sizes of both layers, the vdW interaction energies, and the edge energy of 2D layers. Considering the time-dependent growth process, we find that temperature and adatom flux from vapor are the primary criteria affecting the self-assembled growth. The proposed model clearly demonstrates the distinct roles of thermodynamic and kinetic mechanisms governing the final structure. Our model agrees with experimental observations of various monolayer and bilayer transition metal dichalcogenides grown by CVD and provides a predictive framework to guide the fabrication of vertically stacked 2D materials.

Highly Stable, Dual-Gated MoS2 Transistors Encapsulated by Hexagonal Boron Nitride with Gate-Controllable Contact, Resistance, and Threshold Voltage.

PubMed

Lee, Gwan-Hyoung; Cui, Xu; Kim, Young Duck; Arefe, Ghidewon; Zhang, Xian; Lee, Chul-Ho; Ye, Fan; Watanabe, Kenji; Taniguchi, Takashi; Kim, Philip; Hone, James

2015-07-28

Emerging two-dimensional (2D) semiconductors such as molybdenum disulfide (MoS2) have been intensively studied because of their novel properties for advanced electronics and optoelectronics. However, 2D materials are by nature sensitive to environmental influences, such as temperature, humidity, adsorbates, and trapped charges in neighboring dielectrics. Therefore, it is crucial to develop device architectures that provide both high performance and long-term stability. Here we report high performance of dual-gated van der Waals (vdW) heterostructure devices in which MoS2 layers are fully encapsulated by hexagonal boron nitride (hBN) and contacts are formed using graphene. The hBN-encapsulation provides excellent protection from environmental factors, resulting in highly stable device performance, even at elevated temperatures. Our measurements also reveal high-quality electrical contacts and reduced hysteresis, leading to high two-terminal carrier mobility (33-151 cm(2) V(-1) s(-1)) and low subthreshold swing (80 mV/dec) at room temperature. Furthermore, adjustment of graphene Fermi level and use of dual gates enable us to separately control contact resistance and threshold voltage. This novel vdW heterostructure device opens up a new way toward fabrication of stable, high-performance devices based on 2D materials.

Optical population of iodine molecule ion-pair states via MI2 vdW complexes, M = I2, Xe, of valence states correlating with the third, I(2 P 1/2) + I(2 P 1/2), dissociation limit

NASA Astrophysics Data System (ADS)

Lukashov, S. S.; Poretsky, S. A.; Pravilov, A. M.; Khadikova, E. I.; Shevchenko, E. V.

2010-10-01

The first results of measurements and analysis of excitation spectra of the λlum = 3250 Å luminescence corresponding to I2( D0{/u +} → X0{/g +}) transition as well as luminescence at λlum = 3400 Å, where I2( D'2 g → A'2 u and/or β1 g → A1 u ) transitions occur, observed after three-step, λ1 + λ f + λ1, λ1 = 5321-5508.2 Å, λ f = 10644.0 Å, laser excitation of pure iodine vapour and I2 + Xe mixtures at room temperature via MI2 vdW complexes, M = I2, Xe, of the I2(0{/g +}, 1 u ( bb)) valence states correlating with the third, I(2 P 1/2) + I(2 P 1/2) (I2( bb)), dissociation limit are presented. Luminescence spectra in the λlum = 2200-3500 Å spectral range are also analyzed. Strong luminescence from the I2(D) and, probably, I2(D' and β) states is observed. We discuss three alternative mechanisms of optical population of the IP state. In our opinion, the mechanism including the MI2 complexes is the most probable.

Optical population of iodine molecule ion-pair states via valence states correlating with the third, I(2 P 1/2) + I(2 P 1/2), dissociation limit and their MI2 vdW complexes, M = I2, Xe

NASA Astrophysics Data System (ADS)

Lukashov, S. S.; Poretsky, S. A.; Pravilov, A. M.; Khadikova, E. I.; Shevchenko, E. V.

2010-10-01

The first results of measurements and analysis of excitation spectra of the I2( D0{/u +} → X0{/g +}) and I2( D0{/u +} → X0{/g +} and/or β1 g → A1 u ) luminescence, observed after three-step, λ1 + λ f + λ1, λ1 = 5508-5530 Å, λ f = 10644.0 Å, laser excitation of pure iodine vapour and I2 + Xe mixtures at room temperature via bound parts of the I2(0{/g +}, 1 u ( bb)) valence states correlating with the third, I(2 P 1/2) + I(2 P 1/2), dissociation limit and their MI2 vdW complexes, M = I2, Xe, are presented. Luminescence spectra in the λlum = 2200-5000 Å spectral range are also analyzed. Strong luminescence from the I2( D, γ, D', and/or β) states is observed, though the two latter may be populated in optical transitions in a free iodine molecule if hyperfine coupling of the I2(0{/g +} and 1 u ( bb)) state rovibronic levels occurs. We discuss possible mechanisms of optical population of the IP state.

Synthesis of Ti3AuC2, Ti3Au2C2 and Ti3IrC2 by noble metal substitution reaction in Ti3SiC2 for high-temperature-stable Ohmic contacts to SiC

NASA Astrophysics Data System (ADS)

Fashandi, Hossein; Dahlqvist, Martin; Lu, Jun; Palisaitis, Justinas; Simak, Sergei I.; Abrikosov, Igor A.; Rosen, Johanna; Hultman, Lars; Andersson, Mike; Lloyd Spetz, Anita; Eklund, Per

2017-08-01

The large class of layered ceramics encompasses both van der Waals (vdW) and non-vdW solids. While intercalation of noble metals in vdW solids is known, formation of compounds by incorporation of noble-metal layers in non-vdW layered solids is largely unexplored. Here, we show formation of Ti3AuC2 and Ti3Au2C2 phases with up to 31% lattice swelling by a substitutional solid-state reaction of Au into Ti3SiC2 single-crystal thin films with simultaneous out-diffusion of Si. Ti3IrC2 is subsequently produced by a substitution reaction of Ir for Au in Ti3Au2C2. These phases form Ohmic electrical contacts to SiC and remain stable after 1,000 h of ageing at 600 °C in air. The present results, by combined analytical electron microscopy and ab initio calculations, open avenues for processing of noble-metal-containing layered ceramics that have not been synthesized from elemental sources, along with tunable properties such as stable electrical contacts for high-temperature power electronics or gas sensors.

Interlayer Coupling and Gate-Tunable Excitons in Transition Metal Dichalcogenide Heterostructures

DOE PAGES

Gao, Shiyuan; Yang, Li; Spataru, Catalin Dan

2017-11-22

Bilayer van der Waals (vdW) heterostructures such as MoS 2/WS 2 and MoSe 2/WSe 2 have attracted much attention recently, particularly because of their type II band alignments and the formation of interlayer exciton as the lowest-energy excitonic state. In this work, we calculate the electronic and optical properties of such heterostructures with the first-principles GW+Bethe–Salpeter Equation (BSE) method and reveal the important role of interlayer coupling in deciding the excited-state properties, including the band alignment and excitonic properties. Our calculation shows that due to the interlayer coupling, the low energy excitons can be widely tuned by a vertical gatemore » field. In particular, the dipole oscillator strength and radiative lifetime of the lowest energy exciton in these bilayer heterostructures is varied by over an order of magnitude within a practical external gate field. We also build a simple model that captures the essential physics behind this tunability and allows the extension of the ab initio results to a large range of electric fields. In conclusion, our work clarifies the physical picture of interlayer excitons in bilayer vdW heterostructures and predicts a wide range of gate-tunable excited-state properties of 2D optoelectronic devices.« less

Capturing RNA Folding Free Energy with Coarse-Grained Molecular Dynamics Simulations

PubMed Central

Bell, David R.; Cheng, Sara Y.; Salazar, Heber; Ren, Pengyu

2017-01-01

We introduce a coarse-grained RNA model for molecular dynamics simulations, RACER (RnA CoarsE-gRained). RACER achieves accurate native structure prediction for a number of RNAs (average RMSD of 2.93 Å) and the sequence-specific variation of free energy is in excellent agreement with experimentally measured stabilities (R2 = 0.93). Using RACER, we identified hydrogen-bonding (or base pairing), base stacking, and electrostatic interactions as essential driving forces for RNA folding. Also, we found that separating pairing vs. stacking interactions allowed RACER to distinguish folded vs. unfolded states. In RACER, base pairing and stacking interactions each provide an approximate stability of 3–4 kcal/mol for an A-form helix. RACER was developed based on PDB structural statistics and experimental thermodynamic data. In contrast with previous work, RACER implements a novel effective vdW potential energy function, which led us to re-parameterize hydrogen bond and electrostatic potential energy functions. Further, RACER is validated and optimized using a simulated annealing protocol to generate potential energy vs. RMSD landscapes. Finally, RACER is tested using extensive equilibrium pulling simulations (0.86 ms total) on eleven RNA sequences (hairpins and duplexes). PMID:28393861

Dirac electrons in Moiré superlattice: From two to three dimensions

NASA Astrophysics Data System (ADS)

Hu, Chen; Michaud-Rioux, Vincent; Kong, Xianghua; Guo, Hong

2017-11-01

Moiré patterns in van der Waals (vdW) heterostructures bring novel physical effects to the materials. We report theoretical investigations of the Moiré pattern formed by graphene (Gr) on hexagonal boron nitride (h BN). For both the two-dimensional (2D) flat-sheet and the freestanding three-dimensional (3D) wavelike film geometries, the behaviors of Dirac electrons are strongly modulated by the local high-symmetry stacking configurations of the Moiré pattern. In the 2D flat sheet, the secondary Dirac cone (SDC) dispersion emerges due to the stacking-selected localization of SDC wave functions, while the original Dirac cone (ODC) gap is suppressed due to an overall effect of ODC wave functions. In the freestanding 3D wavelike Moiré structure, we predict that a specific local stacking in the Moiré superlattice is promoted at the expense of other local stackings, leading to an electronic structure more similar to that of the perfectly matching flat Gr/h BN than that of the flat-sheet 2D Moiré pattern. To capture the overall picture of the Moiré superlattice, supercells containing 12 322 atoms are simulated by first principles.

Infrared photodetectors based on graphene van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Ryzhii, V.; Ryzhii, M.; Svintsov, D.; Leiman, V.; Mitin, V.; Shur, M. S.; Otsuji, T.

2017-08-01

We propose and evaluate the graphene layer (GL) infrared photodetectors (GLIPs) based on the van der Waals (vdW) heterostructures with the radiation absorbing GLs. The operation of the GLIPs is associated with the electron photoexcitation from the GL valence band to the continuum states above the inter-GL barriers (either via tunneling or direct transitions to the continuum states). Using the developed device model, we calculate the photodetector characteristics as functions of the GL-vdW heterostructure parameters. We show that due to a relatively large efficiency of the electron photoexcitation and low capture efficiency of the electrons propagating over the barriers in the inter-GL layers, GLIPs should exhibit the elevated photoelectric gain and detector responsivity as well as relatively high detectivity. The possibility of high-speed operation, high conductivity, transparency of the GLIP contact layers, and the sensitivity to normally incident IR radiation provides additional potential advantages in comparison with other IR photodetectors. In particular, the proposed GLIPs can compete with unitravelling-carrier photodetectors.

Patterns of Carbon Nanotubes by Flow-Directed Deposition on Substrates with Architectured Topographies.

PubMed

K Jawed, M; Hadjiconstantinou, N G; Parks, D M; Reis, P M

2018-03-14

We develop and perform continuum mechanics simulations of carbon nanotube (CNT) deployment directed by a combination of surface topography and rarefied gas flow. We employ the discrete elastic rods method to model the deposition of CNT as a slender elastic rod that evolves in time under two external forces, namely, van der Waals (vdW) and aerodynamic drag. Our results confirm that this self-assembly process is analogous to a previously studied macroscopic system, the "elastic sewing machine", where an elastic rod deployed onto a moving substrate forms nonlinear patterns. In the case of CNTs, the complex patterns observed on the substrate, such as coils and serpentines, result from an intricate interplay between van der Waals attraction, rarefied aerodynamics, and elastic bending. We systematically sweep through the multidimensional parameter space to quantify the pattern morphology as a function of the relevant material, flow, and geometric parameters. Our findings are in good agreement with available experimental data. Scaling analysis involving the relevant forces helps rationalize our observations.

Flexible GaN for High Performance, Strainable Radio Frequency Devices (Postprint)

DTIC Science & Technology

2017-11-02

devices on van der Waals (vdW) layers has been facilitated by the recent avail - ability of high -quality atomically smooth BN and graphene epi- taxial...AFRL-RX-WP-JA-2017-0333 FLEXIBLE GaN FOR HIGH PERFORMANCE, STRAINABLE RADIO FREQUENCY DEVICES (POSTPRINT) Elizabeth A. Moore and Timothy...2. REPORT TYPE 3. DATES COVERED (From - To) 5 April 2017 Interim 8 September 2014 – 5 March 2017 4. TITLE AND SUBTITLE FLEXIBLE GaN FOR HIGH

Calculations of predissociative lifetimes of RG...Hal2 Van der Waals complexes

NASA Astrophysics Data System (ADS)

Buchachenko, Alexei A.; Stepanov, N. F.

1992-07-01

Good examples of combined energy- and time-resolved techniques linked by the theoretical solution of a nuclear problem may be found in investigations of the dynamics of weakly bound Van der Waals (VdW) complexes, such as Ar-OH and He-stilbene. Our report concerns only the theoretical aspect of this complex approach. However, we shall stress the importance of energy-resolved spectroscopy for the dynamics and try to illustrate this with some numerical results.

Engineering p-n junctions and bandgap tuning of InSe nanolayers by controlled oxidation

NASA Astrophysics Data System (ADS)

Balakrishnan, Nilanthy; Kudrynskyi, Zakhar R.; Smith, Emily F.; Fay, Michael W.; Makarovsky, Oleg; Kovalyuk, Zakhar D.; Eaves, Laurence; Beton, Peter H.; Patanè, Amalia

2017-06-01

Exploitation of two-dimensional (2D) van der Waals (vdW) crystals can be hindered by the deterioration of the crystal surface over time due to oxidation. On the other hand, the existence of a stable oxide at room temperature can offer prospects for several applications. Here we report on the chemical reactivity of γ-InSe, a recent addition to the family of 2D vdW crystals. We demonstrate that, unlike other 2D materials, InSe nanolayers can be chemically stable under ambient conditions. However, both thermal- and photo-annealing in air induces the oxidation of the InSe surface, which converts a few surface layers of InSe into In2O3, thus forming an InSe/In2O3 heterostructure with distinct and interesting electronic properties. The oxidation can be activated in selected areas of the flake by laser writing or prevented by capping the InSe surface with an exfoliated flake of hexagonal boron nitride. We exploit the controlled oxidation of p-InSe to fabricate p-InSe/n-In2O3 junction diodes with room temperature electroluminescence and spectral response from the near-infrared to the visible and near-ultraviolet ranges. These findings reveal the limits and potential of thermal- and photo-oxidation of InSe in future technologies.

Size-tunable band alignment and optoelectronic properties of transition metal dichalcogenide van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Zhao, Yipeng; Yu, Wangbing; Ouyang, Gang

2018-01-01

2D transition metal dichalcogenide (TMDC)-based heterostructures exhibit several fascinating properties that can address the emerging market of energy conversion and storage devices. Current achievements show that the vertical stacked TMDC heterostructures can form type II band alignment and possess significant optoelectronic properties. However, a detailed analytical understanding of how to quantify the band alignment and band offset as well as the optimized power conversion efficiency (PCE) is still lacking. Herein, we propose an analytical model to exhibit the PCEs of TMDC van der Waals (vdW) heterostructures and explore the intrinsic mechanism of photovoltaic conversion based on the detailed balance principle and atomic-bond-relaxation correlation mechanism. We find that the PCE of monolayer MoS2/WSe2 can be up to 1.70%, and that of the MoS2/WSe2 vdW heterostructures increases with thickness, owing to increasing optical absorption. Moreover, the results are validated by comparing them with the available evidence, providing realistic efficiency targets and design principles. Highlights • Both electronic and optoelectronic models are developed for vertical stacked MoS2/WSe2 heterostructures. • The underlying mechanism on size effect of electronic and optoelectronic properties for vertical stacked MoS2/WSe2 heterostructures is clarified. • The macroscopically measurable quantities and the microscopical bond identities are connected.

Carbon-Nanotube-Confined Vertical Heterostructures with Asymmetric Contacts.

PubMed

Zhang, Jin; Zhang, Kenan; Xia, Bingyu; Wei, Yang; Li, Dongqi; Zhang, Ke; Zhang, Zhixing; Wu, Yang; Liu, Peng; Duan, Xidong; Xu, Yong; Duan, Wenhui; Fan, Shoushan; Jiang, Kaili

2017-10-01

Van der Waals (vdW) heterostructures have received intense attention for their efficient stacking methodology with 2D nanomaterials in vertical dimension. However, it is still a challenge to scale down the lateral size of vdW heterostructures to the nanometer and make proper contacts to achieve optimized performances. Here, a carbon-nanotube-confined vertical heterostructure (CCVH) is employed to address this challenge, in which 2D semiconductors are asymmetrically sandwiched by an individual metallic single-walled carbon nanotube (SWCNT) and a metal electrode. By using WSe 2 and MoS 2 , the CCVH can be made into p-type and n-type field effect transistors with high on/off ratios even when the channel length is 3.3 nm. A complementary inverter was further built with them, indicating their potential in logic circuits with a high integration level. Furthermore, the Fermi level of SWCNTs can be efficiently modulated by the gate voltage, making it competent for both electron and hole injection in the CCVHs. This unique property is shown by the transition of WSe 2 CCVH from unipolar to bipolar, and the transition of WSe 2 /MoS 2 from p-n junction to n-n junction under proper source-drain biases and gate voltages. Therefore, the CCVH, as a member of 1D/2D mixed heterostructures, shows great potentials in future nanoelectronics and nano-optoelectronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual-Gated MoTe2/MoS2 van der Waals Heterojunction p-n Diode

NASA Astrophysics Data System (ADS)

Rai, Amritesh; Movva, Hema C. P.; Kang, Sangwoo; Larentis, Stefano; Roy, Anupam; Tutuc, Emanuel; Banerjee, Sanjay K.

2D materials are promising for future electronic and optoelectronic applications. In this regard, it is important to realize p-n diodes, the most fundamental building block of all modern semiconductor devices, based on these 2D materials. While it is challenging to achieve homojunction diodes in 2D semiconductors due to lack of reliable selective doping techniques, it is relatively easier to achieve diode-like behavior in van der Waals (vdW) heterostructures comprising different 2D semiconductors. Here, we demonstrate dual-gated vdW heterojunction p-n diodes based on p-type MoTe2 and n-type MoS2, with hBN as the top and bottom gate dielectric. The heterostructure stack is assembled using a polymer-based `dry-transfer' technique. Pt contact is used for hole injection in MoTe2, whereas Ag is used for electron injection in MoS2. The dual-gates allow for independent electrostatic tuning of the carriers in MoTe2 and MoS2. Room temperature interlayer current-voltage characteristics reveal a strong gate-tunable rectification behavior. At low temperatures, the diode turn-on voltage increases, whereas the reverse saturation current decreases, in accordance with conventional p-n diode behavior. Dual-Gated MoTe2/MoS2 van der Waals Heterojunction p-n Diode.

A New Method for Determining Hamaker Constants of Solids Based on the Dynamic Approach Behavior of an Atomic Force Microscope

NASA Astrophysics Data System (ADS)

Fronczak, Sean G.

The Hamaker constant, A, is a quantitative measure of the fundamental attractive van der Waals (vdW) interaction for microscale and nanoscale materials. This parameter captures each material's compositional effects on the vdW force, which is often needed as input for predicting the vdW interactions between particles and surfaces. Experimental attempts to determine A using an atomic force microscope (AFM) are typically hindered by issues inherent to the cantilever-tip-surface contact regime, such as surface roughness and deformation, and contact separation distance. Thus, we developed a new method for estimating Hamaker constants from the non-contact approach regime of an AFM experiment (Fronczak et al., 2017, Langmuir 33, 714-725). This method invokes a quasi-dynamic description of the cantilever tip's approach to contact, in which the inertial effects of the tip motion are accounted for when analyzing the trajectory of the tip's approach towards the substrate. The method was tested experimentally using silica, alumina and polystyrene substrates, and was demonstrated to yield estimates of A for these materials that were in very good agreement with previously published Lifshitz calculations. As with various other approaches to determining A, our new method relies heavily on the accuracy of the geometric model used to predict the interaction between the AFM tip and the substrate. For the initial validation experiments of our new method, we therefore focused on describing the shape of the cantilever tip as closely as possible, utilizing a complex model of a truncated pyramid with a spherical cap. Although this pyramidal geometry can be confirmed and the dimensions estimated via scanning electron microscopy (SEM), even high-resolution SEM images of the tip cannot provide sufficient detail to allow precise enough determination of the tip's geometric parameters. Consequently, we also propose an adaptation of the method, in which these difficult to quantify geometric effects are still fully captured via the convenient description of the tip as an 'effective' perfect sphere. Hence, the geometric complexity of the cantilever tip is no longer explicitly required for the determination of A. First, a tip is 'calibrated', whereby the deflection at first contact between the cantilever tip and a smooth surface of known vdW properties is determined and an effective radius, Reff, of the tip is calculated. The tip's approach to contact toward other similarly smooth surfaces can then be well-described by using only this single geometric parameter. We demonstrate the practicality and accuracy of this updated method by comparing the results with both the original pyramid model and Lifshitz approximations (when available) for flat substrates composed of silica, polystyrene, highly ordered pyrolytic graphite (HOPG), sapphire (alpha-Al3O2), Plexiglas (PMMA), and acrylonitrile butadiene styrene (ABS). Then, the modified quasi-dynamic model was employed to study the strength of the adhesive interaction between TNT and several swab materials which are used as explosive detection devices at security checkpoints. This information is crucial for the development and improvement of next-generation swab detection protocols to further advance this field. Finally, we also include the effects of thermal noise into our quasi-dynamic description of the cantilever motion to better understand how such noise might influence the accuracy of our method. We likewise determine, for the first time, the effects of instrument noise on the accuracy of other approach-to-contact methodologies for determining A.

A comparative study on top-gated and bottom-gated multilayer MoS2 transistors with gate stacked dielectric of Al2O3/HfO2.

PubMed

Zou, Xiao; Xu, Jingping; Huang, Hao; Zhu, Ziqang; Wang, Hongjiu; Li, Borui; Liao, Lei; Fang, Guojia

2018-06-15

Top-gated and bottom-gated transistors with multilayer MoS 2 channel fully encapsulated by stacked Al 2 O 3 /HfO 2 (9 nm/6 nm) were fabricated and comparatively studied. Excellent electrical properties are demonstrated for the TG transistors with high on-off current ratio of 10 8 , high field-effect mobility of 10 2 cm 2 V -1 s -1 , and low subthreshold swing of 93 mV dec -1 . Also, enhanced reliability has been achieved for the TG transistors with threshold voltage shift of 10 -3 -10 -2 V MV -1 cm -1 after 6 MV cm -1 gate-biased stressing. All improvement for the TG device can be ascribed to the formed device structure and dielectric environment. Degradation of the performance for the BG transistors should be attributed to reduced gate capacitance density and deteriorated interface properties related to vdW gap with a thickness about 0.4 nm. So, the TG transistor with MoS 2 channel fully encapsulated by stacked Al 2 O 3 /HfO 2 is a promising way to fabricate high-performance ML MoS 2 field-effect transistors for practical electron device applications.

A comparative study on top-gated and bottom-gated multilayer MoS2 transistors with gate stacked dielectric of Al2O3/HfO2

NASA Astrophysics Data System (ADS)

Zou, Xiao; Xu, Jingping; Huang, Hao; Zhu, Ziqang; Wang, Hongjiu; Li, Borui; Liao, Lei; Fang, Guojia

2018-06-01

Top-gated and bottom-gated transistors with multilayer MoS2 channel fully encapsulated by stacked Al2O3/HfO2 (9 nm/6 nm) were fabricated and comparatively studied. Excellent electrical properties are demonstrated for the TG transistors with high on–off current ratio of 108, high field-effect mobility of 102 cm2 V‑1 s‑1, and low subthreshold swing of 93 mV dec–1. Also, enhanced reliability has been achieved for the TG transistors with threshold voltage shift of 10‑3–10‑2 V MV–1 cm–1 after 6 MV cm‑1 gate-biased stressing. All improvement for the TG device can be ascribed to the formed device structure and dielectric environment. Degradation of the performance for the BG transistors should be attributed to reduced gate capacitance density and deteriorated interface properties related to vdW gap with a thickness about 0.4 nm. So, the TG transistor with MoS2 channel fully encapsulated by stacked Al2O3/HfO2 is a promising way to fabricate high-performance ML MoS2 field-effect transistors for practical electron device applications.

Host-guest complex of N-(2-chloroethyl), N-nitroso, N‧, N‧ -dicyclohexylsulfamid with β-cyclodextrin: Fluorescence, QTAIM analysis and structure-chemical reactivity

NASA Astrophysics Data System (ADS)

Bensouilah, Nadjia; Fisli, Hassina; Bensouilah, Hamza; Zaater, Sihem; Abdaoui, Mohamed; Boutemeur-Kheddis, Baya

2017-10-01

In this work, the inclusion complex of DCY/CENS: N-(2-chloroethyl), N-nitroso, N‧, N‧-dicyclohexylsulfamid and β-cyclodextrin (β-CD) is investigated using the fluorescence spectroscopy, PM3, ONIOM2 and DFT methods. The experimental part reveals that DCY/CENS forms a 1:1 stoichiometric ratio inclusion complex with β-CD. The constant of stability is evaluated using the Benesi-Hildebrand equation. The results of the theoretical optimization showed that the lipophilic fraction of molecule (cyclohexyl group) is inside of β-CD. Accordingly, the Nitroso-Chloroethyl moiety is situated outside the cavity of the macromolecule host. The favorable structure of the optimized complex indicates the existence of weak intermolecular hydrogen bonds and the most important van der Waals (vdW) interactions which are studied on the basis of Natural Bonding Orbital (NBO) analysis. The NBO is employed to compute the electronic donor-acceptor exchanges between drug and β-CD. Furthermore, a detailed topological charge density analysis based on the quantum theory of atoms in molecules (QTAIM), has been accomplished on the most favorable complex using B3LYP/6-31G(d) method. The presence of stabilizing intermolecular hydrogen bonds and van der Waals interactions in the most favorable complex is predicted. Also, the energies of these interactions are estimated with Espinosa's formula. The findings of this investigation reveal that the correlation between the structural parameters and the electronic density is good. Finally, and based on DFT calculations, the reactivity of the interesting molecule in free state was studied and compared with that in the complexed state using chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors.

Intra-manufacture Diameter Variability of Rotary Files and Their Corresponding Gutta-Percha Cones Using Laser Scan Micrometre.

PubMed

Mirmohammadi, Hesam; Sitarz, Monika; Shemesh, Hagay

2018-01-01

Manufacturers offer gutta-percha (GP) cones matched with different sizes of endodontic files as an attempt to simplify the obturation process and create a tight seal in the canal. The purpose of this study was to evaluate whether intra-manufacture GP diameters matched the diameters of their corresponding files at different levels using laser micrometre. Twenty files and corresponding GP master cones of Reciproc R40 (40/0.06) (VDW, Munich, Germany), WaveOne Large(40/0.08)(Dentsply Maillefer, Ballaigues, Switzerland), ProTaper F3 (30/0.09) (Dentsply Maillefer, Ballaigues, Switzerland), and Mtwo 40/0.06 (VDW, Munich, Germany) were examined using laser micrometre (LSM 6000 by Mitutoyo, Japan) with accuracy of 1 nm to establish their actual diameter at D 0 , D 1 , D 3 and D 6 . The data was analysed using the independent t -test. The differences were considered at 0.05. The diameter of GP master cones was significantly larger than that of the corresponding files at all levels in all brands. ProTaper GP diameter was closest to the file diameter at D1 (GP=0.35, File=0.35 mm), and D3 (GP=0.48, File=0.49). Within the same manufacturer, GP cone diameters do not match the diameters of their corresponding files. Clinicians are advised to use a GP gauge to cut the tip so as to appropriate the diameter from a smaller sized GP cone.

Cyclic Fatigue Resistance of Reciproc Blue and Reciproc Files in an S-shaped Canal.

PubMed

Topçuoğlu, Hüseyin Sinan; Topçuoğlu, Gamze

2017-10-01

This study evaluated the cyclic fatigue resistance (CFR) of Reciproc (R25 and R40; VDW, Munich, Germany) and Reciproc Blue (R25 and R40, VDW) instruments used in an artificial S-shaped canal. A total of 80 files were tested in an S-shaped canal (n = 20 for each file, Reciproc R25 and R40 and Reciproc Blue R25 and R40). This study compared Reciproc R25 with Reciproc Blue R25 files and Reciproc R40 with Reciproc Blue R40 files. All files were rotated in an S-shaped artificial canal until fracture. CFR was determined by recording the time to fracture in the artificial canal. The length of each fractured fragment was measured in millimeters. An independent sample t test was used to analyze the data. Between the R25 files, Reciproc Blue instruments showed significantly greater CFR than the Reciproc files in the apical and coronal curves (P < .05). Between the R40 files, Reciproc Blue instruments exhibited greater CFR in the apical and coronal curves (P < .05). There was no difference in the fractured fragment lengths of the Reciproc Blue files compared with the Reciproc files (P > .05). The Reciproc Blue R25 and R40 files showed greater CFR than the Reciproc R25 and R40 files in an S-shaped canal. Copyright © 2017 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Drug-polymer interactions at water-crystal interfaces and implications for crystallization inhibition: molecular dynamics simulations of amphiphilic block copolymer interactions with tolazamide crystals.

PubMed

Gao, Yi; Olsen, Kenneth W

2015-07-01

A diblock copolymer, poly(ethylene glycol)-block-poly(lactic acid) (PEG-b-PLA), modulates the crystal growth of tolazamide (TLZ), resulting in a crystal morphology change from needles to plates in aqueous media. To understand this crystal surface drug-polymer interaction, we conducted molecular dynamics simulations on crystal surfaces of TLZ in water containing PEG-b-PLA. A 130-ns simulation of the polymer in a large water box was run before initiating 50 ns simulations with each of the crystal surfaces. The simulations demonstrated differentiated drug-polymer interactions that are consistent with experimental studies. Interaction of PEG-b-PLA with the (001) face occurred more rapidly (≤10 ns) and strongly (total interaction energy of -121.1 kJ/mol/monomer) than that with the (010) face (∼35 ns, -85.4 kJ/mol/monomer). There was little interaction with the (100) face. Hydrophobic and van der Waals (VDW) interactions were the dominant forces, accounting for more than 90% of total interaction energies. It suggests that polymers capable of forming strong hydrophobic and VDW interactions might be more effective in inhibiting crystallization of poorly water-soluble and hydrophobic drugs in aqueous media (such as gastrointestinal fluid) than those with hydrogen-bonding capacities. Such in-depth analysis and understanding facilitate the rational selection of polymers in designing supersaturation-based enabling formulations. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

A new device to test cutting efficiency of mechanical endodontic instruments.

PubMed

Giansiracusa Rubini, Alessio; Plotino, Gianluca; Al-Sudani, Dina; Grande, Nicola M; Sonnino, Gianpaolo; Putorti, Ermanno; Cotti, Elisabetta; Testarelli, Luca; Gambarini, Gianluca

2014-03-06

The purpose of the present study was to introduce a new device specifically designed to evaluate the cutting efficiency of mechanically driven endodontic instruments. Twenty new Reciproc R25 (VDW, Munich, Germany) files were used to be investigated in the new device developed to test the cutting ability of endodontic instruments. The device consists of a main frame to which a mobile plastic support for the hand-piece is connected and a stainless-steel block containing a Plexiglas block against which the cutting efficiency of the instruments was tested. The length of the block cut in 1 minute was measured in a computerized program with a precision of 0.1mm. The instruments were activated by using a torque-controlled motor (Silver Reciproc; VDW, Munich, Germany) in a reciprocating movement by the "Reciproc ALL" program (Group 1) and in counter-clockwise rotation at 300 rpm (Group 2). Mean and standard deviations of each group were calculated and data were statistically analyzed with a one-way ANOVA test (P<0.05). Reciproc in reciprocation (Group 1) mean cut in the Plexiglas block was 8.6 mm (SD=0.6 mm), while Reciproc in rotation mean cut was 8.9 mm (SD=0.7 mm). There was no statistically significant difference between the 2 groups investigated (P>0.05). The cutting testing device evaluated in the present study was reliable and easy to use and may be effectively used to test cutting efficiency of both rotary and reciprocating mechanical endodontic instruments.

Effect of surfactants on the interaction of phenol with laccase: Molecular docking and molecular dynamics simulation studies.

PubMed

Liu, Yujie; Liu, Zhifeng; Zeng, Guangming; Chen, Ming; Jiang, Yilin; Shao, Binbin; Li, Zhigang; Liu, Yang

2018-05-22

Some surfactants can enhance the removal of phenol by laccase (Lac) in various industrial effluents. Their behavior and function in the biodegradation of phenolic wastewater have been experimentally reported by many researchers, but the underlying molecular mechanism is still unclear. Therefore, the interaction mechanisms of phenol with Lac from Trametes versicolor were investigated in the presence or absence of Triton X-100 (TX100) or rhamnolipid (RL) by molecular docking and molecular dynamics (MD) simulations. The results indicate that phenol contacts with an active site of Lac by hydrogen bonds (HBs) and van der Waals (vdW) interactions in aqueous solution for maintaining its stability. The presence of TX100 or RL results in the significant changes of enzymatic conformations. Meanwhile, the hydrophobic parts of surfactants contact with the outside surface of Lac. These changes lead to the decrease of binding energy between phenol and Lac. The migration behavior of water molecules within hydration shell is also inevitably affected. Therefore, the amphipathic TX100 or RL may influence the phenol degradation ability of Lac by modulating their interactions and water environment. This study offers molecular level of understanding on the function of surfactants in biosystem. Copyright © 2018 Elsevier B.V. All rights reserved.

Recent Advances in Two-Dimensional Materials beyond Graphene.

PubMed

Bhimanapati, Ganesh R; Lin, Zhong; Meunier, Vincent; Jung, Yeonwoong; Cha, Judy; Das, Saptarshi; Xiao, Di; Son, Youngwoo; Strano, Michael S; Cooper, Valentino R; Liang, Liangbo; Louie, Steven G; Ringe, Emilie; Zhou, Wu; Kim, Steve S; Naik, Rajesh R; Sumpter, Bobby G; Terrones, Humberto; Xia, Fengnian; Wang, Yeliang; Zhu, Jun; Akinwande, Deji; Alem, Nasim; Schuller, Jon A; Schaak, Raymond E; Terrones, Mauricio; Robinson, Joshua A

2015-12-22

The isolation of graphene in 2004 from graphite was a defining moment for the "birth" of a field: two-dimensional (2D) materials. In recent years, there has been a rapidly increasing number of papers focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement. Here, we review significant recent advances and important new developments in 2D materials "beyond graphene". We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 2D layers in bulk solids, as well as their excitonic properties and growth morphologies. Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 2D materials (i.e., silicene, phosphorene, etc.) and transition metal carbide- and carbon nitride-based MXenes. We then discuss the doping and functionalization of 2D materials beyond graphene that enable device applications, followed by advances in electronic, optoelectronic, and magnetic devices and theory. Finally, we provide perspectives on the future of 2D materials beyond graphene.

Jet-Cooled Infrared Laser Spectroscopy in the Umbrella νb{2} Vibration Region of NH_3: Improving the Potential Energy Surface Model of the NH_3-Ar Van Der Waals Complex

NASA Astrophysics Data System (ADS)

Asselin, Pierre; Jabri, Atef; Potapov, Alexey; Loreau, Jérome; van der Avoird, Ad

2017-06-01

Taking advantage of our sensitive laser spectrometer coupled to a pulsed slit jet, we recorded near the νb{2} vibration a series of rovibrational transitions of the NH_3-Ar van der Waals (vdW) complex. These transitions involve in the ground vibrational state several internal rotor states corresponding to the ortho{NH_3} and para{NH_3} spin modifications of the complex. They are labeled by Σ_{a}(j,k), Σ_{s}(j,k), Π_{a}(j,k) and Π_{s}(j,k) where Σ(K=0) and Π(K=1) indicate the projection K of the total rotational angular momentum J on the vdW axis, the superscripts s and a designate a symmetric or antisymmetric NH_3 inversion wave function, and j, k quantum numbers indicate the correlation between the internal-rotor state of the complex and the j, k rotational state of the free NH_3 monomer. Five bands have been identified, only one of which was partly observed before. They include transitions starting from the Σ_{a}(j=0 or j=1) state without any internal angular momentum, consequently they can be assigned from the band contour of a linear-molecule-like K=0, ΔJ=1 transition. The energies and splittings of the rovibrational levels of the νb{2}=1←0 spectrum derived from the analysis of the Π_{s}, Σ_{s}(j=1)← Σ_{a}(j=0), k=0 bands and mostly of the Σ_{s}, Π_{s} and Σ_{a}(j=1)←Σ_{a}(j=1), k=1 bands bring relevant information about the νb{2} dependence of the NH_3-Ar interaction, the rovibrational dynamics of the NH_3-Ar complex and provide a sensitive test of a recently developed 4D potential energy surface that includes explicitly its dependence on the umbrella motion. P. Asselin, Y. Berger, T. R. Huet, R. Motiyenko, L. Margulès, R. J. Hendricks, M. R. Tarbutt, S. Tokunaga, B. Darquié, PCCP 19, 4576 (2017), G. T. Fraser, A.S. Pine and W. A. Kreiner, J. Chem. Phys. 94, 7061 (1991). J. Loreau, J. Liévin, Y. Scribano and A. van der Avoird, J. Chem. Phys. 141, 224303 (2014).

Apically extruded debris with reciprocating single-file and full-sequence rotary instrumentation systems.

PubMed

Bürklein, Sebastian; Schäfer, Edgar

2012-06-01

The purpose of this in vitro study was to assess the amount of apically extruded debris using rotary and reciprocating nickel-titanium instrumentation systems. Eighty human mandibular central incisors were randomly assigned to 4 groups (n = 20 teeth per group). The root canals were instrumented according to the manufacturers' instructions using the 2 reciprocating single-file systems Reciproc (VDW, Munich, Germany) and WaveOne (Dentsply Maillefer, Ballaigues, Switzerland) and the 2 full-sequence rotary Mtwo (VDW, Munich, Germany) and ProTaper (Dentsply Maillefer, Ballaigues, Switzerland) instruments. Bidistilled water was used as irrigant. The apically extruded debris was collected in preweighted glass vials using the Myers and Montgomery method. After drying, the mean weight of debris was assessed with a microbalance and statistically analyzed using analysis of variance and the post hoc Student-Newman-Keuls test. The time required to prepare the canals with the different instruments was also recorded. The reciprocating files produced significantly more debris compared with both rotary systems (P < .05). Although no statistically significant difference was obtained between the 2 rotary instruments (P > .05), the reciprocating single-file system Reciproc produced significantly more debris compared with all other instruments (P < .05). Instrumentation was significantly faster using Reciproc than with all other instrument (P < .05). Under the condition of this study, all systems caused apical debris extrusion. Full-sequence rotary instrumentation was associated with less debris extrusion compared with the use of reciprocating single-file systems. Copyright © 2012 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

A new device to test cutting efficiency of mechanical endodontic instruments

PubMed Central

Rubini, Alessio Giansiracusa; Plotino, Gianluca; Al-Sudani, Dina; Grande, Nicola M.; Putorti, Ermanno; Sonnino, GianPaolo; Cotti, Elisabetta; Testarelli, Luca; Gambarini, Gianluca

2014-01-01

Background The purpose of the present study was to introduce a new device specifically designed to evaluate the cutting efficiency of mechanically driven endodontic instruments. Material/Methods Twenty new Reciproc R25 (VDW, Munich, Germany) files were used to be investigated in the new device developed to test the cutting ability of endodontic instruments. The device consists of a main frame to which a mobile plastic support for the hand-piece is connected and a stainless-steel block containing a Plexiglas block against which the cutting efficiency of the instruments was tested. The length of the block cut in 1 minute was measured in a computerized program with a precision of 0.1mm. The instruments were activated by using a torque-controlled motor (Silver Reciproc; VDW, Munich, Germany) in a reciprocating movement by the “Reciproc ALL” program (Group 1) and in counter-clockwise rotation at 300 rpm (Group 2). Mean and standard deviations of each group were calculated and data were statistically analyzed with a one-way ANOVA test (P<0.05). Results Reciproc in reciprocation (Group 1) mean cut in the Plexiglas block was 8.6 mm (SD=0.6 mm), while Reciproc in rotation mean cut was 8.9 mm (SD=0.7 mm). There was no statistically significant difference between the 2 groups investigated (P>0.05). Conclusions The cutting testing device evaluated in the present study was reliable and easy to use and may be effectively used to test cutting efficiency of both rotary and reciprocating mechanical endodontic instruments. PMID:24603777

Shaping ability of reciprocating single-file systems in severely curved canals: WaveOne and Reciproc versus WaveOne Gold and Reciproc blue.

PubMed

Bürklein, Sebastian; Flüch, Stefanie; Schäfer, Edgar

2018-05-18

The aim was to compare the canal straightening of M-wire [Reciproc (VDW, Munich, Germany) and WaveOne (Dentsply Maillefer, Ballaigues, Switzerland)] and gold- and blue-wire heat-treated [Reciproc blue (VDW) and WaveOne Gold (Dentsply Maillefer)] instruments in severely curved root canals. A total of 80 root canals in extracted human teeth with angles of curvatures ranging between 25° and 35° and radii ranging between 3.1 and 8.5 mm were divided into four groups (n = 20). Based on radiographs taken prior to instrumentation, the groups were balanced with respect to the angle and the radius of canal curvature (P = 1.0 and P = 1.0, respectively). All canals were prepared to an apical size 25 according to the manufacturers' instructions. Pre- and post-instrumentation radiographs were superimposed and canal straightening was analysed using a computer imaging programme. Preparation time and instrument failure were also recorded. Data were analysed statistically using ANOVA and Student-Newman-Keuls test. During preparation no instrument fractured. All instruments maintained the original canal curvature well with no significant differences between the instruments (P = 0.278). Regarding preparation time, no significant differences between the four instruments were obtained (P > 0.05). Under the conditions of this study, all instruments respected the original canal curvature well. Instruments were safe to use. The use of the gold- and blue-wire heat-treated instruments was not associated with an improved shaping ability.

DFT investigation on two-dimensional GeS/WS2 van der Waals heterostructure for direct Z-scheme photocatalytic overall water splitting

NASA Astrophysics Data System (ADS)

Ju, Lin; Dai, Ying; Wei, Wei; Li, Mengmeng; Huang, Baibiao

2018-03-01

Recently, extensive attention has been paid to the direct Z-scheme systems for photocatalytic water splitting where carriers migrate directly between the two semiconductors without a redox mediator. In the present work, the electronic structure and related properties of two-dimensional (2D) van de Waals (vdW) GeS/WX2 (X = O, S, Se, Te) heterojunction are systematically investigated by first-principles calculations. Our results demonstrate that, the GeS/WS2 heterojunction could form a direct Z-scheme system for photocatalytic water splitting, whereas the GeS/WX2 (X = O, Se, Te) can't, because of their respective unsuitable electronic structures. For the GeS/WS2 heterojunction, the GeS and WS2 monolayers serve as photocatalysts for the hydrogen evolution reactionand oxygen evolution reaction, respectively. The internal electric field induced by the electron transfer at the interface can promote the separation of photo-generated charge carriers and formation of the interface Z-scheme electron transfer. Remarkably, the designed GeS/WS2 heterojunction not only enhances the hydrogen production activity of GeS and the oxygen production ability of WS2 but also improves the light absorption of the two monolayers by reducing the band gaps. Moreover, it is found that narrowing the interlayer distance could enhance the internal electric field, improving the photocatalytic ability of the vdW heterojunction. This work provides fundamental insights for further design and preparation of emergent metal dichalcogenide catalysts, beneficial for the development in clean energy.

Effects of geometry and chemistry on hydrophobic solvation

PubMed Central

Harris, Robert C.; Pettitt, B. Montgomery

2014-01-01

Inserting an uncharged van der Waals (vdw) cavity into water disrupts the distribution of water and creates attractive dispersion interactions between the solvent and solute. This free-energy change is the hydrophobic solvation energy (ΔGvdw). Frequently, it is assumed to be linear in the solvent-accessible surface area, with a positive surface tension (γ) that is independent of the properties of the molecule. However, we found that γ for a set of alkanes differed from that for four configurations of decaalanine, and γ = −5 was negative for the decaalanines. These findings conflict with the notion that ΔGvdw favors smaller A. We broke ΔGvdw into the free energy required to exclude water from the vdw cavity (ΔGrep) and the free energy of forming the attractive interactions between the solute and solvent (ΔGatt) and found that γ < 0 for the decaalanines because −γatt > γrep and γatt < 0. Additionally, γatt and γrep for the alkanes differed from those for the decaalanines, implying that none of ΔGatt, ΔGrep, and ΔGvdw can be computed with a constant surface tension. We also showed that ΔGatt could not be computed from either the initial or final water distributions, implying that this quantity is more difficult to compute than is sometimes assumed. Finally, we showed that each atom’s contribution to γrep depended on multibody interactions with its surrounding atoms, implying that these contributions are not additive. These findings call into question some hydrophobic models. PMID:25258413

Screw-in forces during instrumentation by various file systems.

PubMed

Ha, Jung-Hong; Kwak, Sang Won; Kim, Sung-Kyo; Kim, Hyeon-Cheol

2016-11-01

The purpose of this study was to compare the maximum screw-in forces generated during the movement of various Nickel-Titanium (NiTi) file systems. Forty simulated canals in resin blocks were randomly divided into 4 groups for the following instruments: Mtwo size 25/0.07 (MTW, VDW GmbH), Reciproc R25 (RPR, VDW GmbH), ProTaper Universal F2 (PTU, Dentsply Maillefer), and ProTaper Next X2 (PTN, Dentsply Maillefer, n = 10). All the artificial canals were prepared to obtain a standardized lumen by using ProTaper Universal F1. Screw-in forces were measured using a custom-made experimental device (AEndoS- k , DMJ system) during instrumentation with each NiTi file system using the designated movement. The rotation speed was set at 350 rpm with an automatic 4 mm pecking motion at a speed of 1 mm/sec. The pecking depth was increased by 1 mm for each pecking motion until the file reach the working length. Forces were recorded during file movement, and the maximum force was extracted from the data. Maximum screw-in forces were analyzed by one-way ANOVA and Tukey's post hoc comparison at a significance level of 95%. Reciproc and ProTaper Universal files generated the highest maximum screw-in forces among all the instruments while M-two and ProTaper Next showed the lowest ( p < 0.05). Geometrical differences rather than shaping motion and alloys may affect the screw-in force during canal instrumentation. To reduce screw-in forces, the use of NiTi files with smaller cross-sectional area for higher flexibility is recommended.

Does the Reciproc file remove root canal bacteria and endotoxins as effectively as multifile rotary systems?

PubMed

Marinho, A C S; Martinho, F C; Gonçalves, L M; Rabang, H R C; Gomes, B P F A

2015-06-01

To evaluate the effectiveness of Reciproc for the removal of cultivable bacteria and endotoxins from root canals in comparison with multifile rotary systems. The root canals of forty human single-rooted mandibular pre-molars were contaminated with an Escherichia coli suspension for 21 days and randomly assigned to four groups according to the instrumentation system: GI - Reciproc (VDW); GII - Mtwo (VDW); GIII - ProTaper Universal (Dentsply Maillefer); and GIV -FKG Race(™) (FKG Dentaire) (n = 10 per group). Bacterial and endotoxin samples were taken with a sterile/apyrogenic paper point before (s1) and after instrumentation (s2). Culture techniques determined the colony-forming units (CFU) and the Limulus Amebocyte Lysate assay was used for endotoxin quantification. Results were submitted to paired t-test and anova. At s1, bacteria and endotoxins were recovered in 100% of the root canals investigated (40/40). After instrumentation, all systems were associated with a highly significant reduction of the bacterial load and endotoxin levels, respectively: GI - Reciproc (99.34% and 91.69%); GII - Mtwo (99.86% and 83.11%); GIII - ProTaper (99.93% and 78.56%) and GIV - FKG Race(™) (99.99% and 82.52%) (P < 0.001). No statistical difference were found amongst the instrumentation systems regarding bacteria and endotoxin removal (P > 0.01). The reciprocating single file, Reciproc, was as effective as the multifile rotary systems for the removal of bacteria and endotoxins from root canals. © 2014 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite

PubMed Central

2017-01-01

Understanding strength and nature of noncovalent binding to surfaces imposes significant challenge both for computations and experiments. We explored the adsorption of five small nonpolar organic molecules (acetone, acetonitrile, dichloromethane, ethanol, ethyl acetate) to fluorographene and fluorographite using inverse gas chromatography and theoretical calculations, providing new insights into the strength and nature of adsorption of small organic molecules on these surfaces. The measured adsorption enthalpies on fluorographite range from −7 to −13 kcal/mol and are by 1–2 kcal/mol lower than those measured on graphene/graphite, which indicates higher affinity of organic adsorbates to fluorographene than to graphene. The dispersion-corrected functionals performed well, and the nonlocal vdW DFT functionals (particularly optB86b-vdW) achieved the best agreement with the experimental data. Computations show that the adsorption enthalpies are controlled by the interaction energy, which is dominated by London dispersion forces (∼70%). The calculations also show that bonding to structural features, like edges and steps, as well as defects does not significantly increase the adsorption enthalpies, which explains a low sensitivity of measured adsorption enthalpies to coverage. The adopted Langmuir model for fitting experimental data enabled determination of adsorption entropies. The adsorption on the fluorographene/fluorographite surface resulted in an entropy loss equal to approximately 40% of the gas phase entropy. PMID:28145699

Infrared Spectroscopy of C_6D_6-Rg_n(n=1,2)

NASA Astrophysics Data System (ADS)

George, Jobin; Yousefi, Mahdi; Rezaei, Mojtaba; McKellar, Bob; Moazzen-Ahmadi, Nasser

2014-06-01

Benzene-noble gas complexes were one of the earliest topics of interest in spectroscopic investigation of van der Waals (vdW) complexes. Smalley et al. observed C_6H_6-(He)1,2 vdW complexes in the late 1970s by means of electronic spectroscopy. A recent study on the same species was done by M. Hayashi et al. Here, we present the infrared observation of C_6D_6-Rg_n (n=1,2) with the rare gas being He, Ne, or Ar, in the regions of νb{12} fundamental band of C_6D_6 (˜2289 wn) and the νb{2} + νb{13} combination band (˜2275 wn) which are coupled by a Fermi resonance. The spectra were observed at a resolution of 60 MHz using a tunable optical parametric oscillator to probe a pulsed supersonic-jet expansion from a slit nozzle. In the case of C_6D_6-Rg dimers, the spectra were assigned to a symmetric top with C6v symmetry with the rare gas atom being located on the C6 symmetry axis. To observe C_6D_6-Rg_2 trimers, the nozzle was cooled using a closed-cycle methanol refrigerator and the spectra were simulated with a rotational temperature of 1.3K. The spectra of the C_6D_6-Rg_2 trimers were in agreement with a D6h symmetry structure, where the rare gas atoms are positioned above and below the C_6D_6 plane. Data analysis and observation are presently ongoing. S. M. Beck, M. G. Liverman, D. L. Monts and R. E. Smalley, J. Chem. Phys. 70, 232 (1979). M. Hayashi, Y. Ohshima, Chem. Phys. 419, 131 (2013).

Quantum Chemical Study of CH3 + O2 Combustion Reaction System: Catalytic Effects of Additional CO2 Molecule.

PubMed

Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

2017-08-03

The supercritical carbon dioxide diluent is used to control the temperature and to increase the efficiency in oxycombustion fossil fuel energy technology. It may affect the rates of combustion by altering mechanisms of chemical reactions, compared to the ones at low CO 2 concentrations. Here, we investigate potential energy surfaces of the four elementary reactions in the CH 3 + O 2 reactive system in the presence of one CO 2 molecule. In the case of reaction CH 3 + O 2 → CH 2 O + OH (R1 channel), van der Waals (vdW) complex formation stabilizes the transition state and reduces the activation barrier by ∼2.2 kcal/mol. Alternatively, covalently bonded CO 2 may form a six-membered ring transition state and reduce the activation barrier by ∼0.6 kcal/mol. In case of reaction CH 3 + O 2 → CH 3 O + O (R2 channel), covalent participation of CO 2 lowers the barrier for the rate limiting step by 3.9 kcal/mol. This is expected to accelerate the R2 process, important for the branching step of the radical chain reaction mechanism. For the reaction CH 3 + O 2 → CHO + H 2 O (R3 channel) with covalent participation of CO 2 , the activation barrier is lowered by 0.5 kcal/mol. The reaction CH 2 O + OH → CHO + H 2 O (R4 channel) involves hydrogen abstraction from formaldehyde by OH radical. Its barrier is reduced from 7.1 to 0.8 kcal/mol by formation of vdW complex with spectator CO 2 . These new findings are expected to improve the kinetic reaction mechanism describing combustion processes in supercritical CO 2 medium.

Postoperative Pain after Endodontic Retreatment Using Rotary or Reciprocating Instruments: A Randomized Clinical Trial.

PubMed

Comparin, Daniel; Moreira, Edson Jorge Lima; Souza, Erick M; De-Deus, Gustavo; Arias, Ana; Silva, Emmanuel João Nogueira Leal

2017-07-01

The aim of this randomized clinical trial was to evaluate the influence of rotary or reciprocating retreatment techniques on the incidence, intensity, duration of postoperative pain, and medication intake. After power analysis calculations, 65 patients who needed endodontic retreatment were randomly assigned to 1 of 2 groups according to the instrumentation system used: Mtwo (VDW, Munich, Germany) or Reciproc (VDW). Retreatments were performed in a single visit by an endodontic specialist. Participants were asked to rate the incidence and intensity of the postoperative pain on a verbal rating scale 24, 48, and 72 hours after treatment. Patients were also asked to record the number of prescribed analgesic medication tablets (ibuprofen 400 mg) taken. A logistic regression analysis was used to assess both the incidence and duration of pain. Differences in the intensity of pain were analyzed using the ordinal (linear) chi-square test, and the Mann-Whitney U test was used to assess differences in the intake of analgesic medication between groups. No statistically significant difference was found among the 2 groups in relation to postoperative pain or analgesic medication intake at the 3 time points assessed (P > .05). Multivariate analysis showed a significantly higher incidence of pain after 24 hours when preoperative pain was present and a significantly longer duration of pain for men than women independently of the retreatment technique used. The reciprocating system and the continuous rotary system were found to be equivalent regarding the incidence, intensity, duration of postoperative pain, and intake of analgesic medication. Copyright © 2017 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Clinical comparison of the effectiveness of single-file reciprocating systems and rotary systems for removal of endotoxins and cultivable bacteria from primarily infected root canals.

PubMed

Martinho, Frederico C; Gomes, Ana P M; Fernandes, Aletéia M M; Ferreira, Nádia S; Endo, Marcos S; Freitas, Lilian F; Camões, Izabel C G

2014-05-01

This clinical study was conducted to compare the effectiveness of single-file reciprocating systems and rotary systems in removing endotoxins and cultivable bacteria from primarily infected root canals. Forty-eight primarily infected root canals were selected and randomly divided into 4 groups: WaveOne (Dentsply Maillefer, Ballaigues, Switzerland) (n = 12); Reciproc (VDW, Munich, Germany) (n = 12), ProTaper (Dentsply Maillefer) (n = 12), and Mtwo (VDW) (n = 12). Samples were collected before and after chemomechanical preparation. The irrigation was performed by using 2.5% sodium hypochlorite. A chromogenic limulus amebocyte lysate assay test was used to quantify endotoxins. Culture techniques were used to determine bacterial colony-forming unit counts. In the baseline samples (ie, samples collected before chemomechanical preparation), endotoxins and cultivable bacteria were recovered from 100% of the root canal samples. No differences were found in the median percentage values of endotoxin reduction achieved with reciprocating systems (ie, WaveOne [95.15%] and Reciproc [96.21%]) and with rotary systems (ie, ProTaper [97.98%] and Mtwo [96.34%]) (P < .05). Both single-file reciprocating systems (ie, WaveOne [99.45%] and Reciproc [99.93%]) and rotary systems (ProTaper [99.85%] and Mtwo [99.41%]) were effective in reducing the cultivable bacteria (all P < .05). Moreover, the culture analysis revealed no differences in bacterial load reduction (P > .05). Both single-file reciprocating systems (ie, WaveOne and Reciproc instruments) and rotary systems (ie, ProTaper and Mtwo instruments) showed similar effectiveness in reducing endotoxins and cultivable bacteria from primarily infected root canals, but they were not able to eliminate them from all root canals analyzed. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Comparison of working length control consistency between hand K-files and Mtwo NiTi rotary system.

PubMed

Krajczár, Károly; Varga, Enikő; Marada, Gyula; Jeges, Sára; Tóth, Vilmos

2016-04-01

The purpose of this study was to investigate the consistency of working length control between hand instrumentation in comparison to engine driven Mtwo nickel-titanium rotary files. Forty extracted maxillary molars were selected and divided onto two parallel groups. The working lengths of the mesiobuccal root canals were estimated. The teeth were fixed in a phantom head. The root canal preparation was carried out group 1 (n=20) with hand K-files, (VDW, Munich, Germany) and group 2 (n=20) with Mtwo instruments (VDW, Munich, Germany). Vestibulo-oral and mesio-distal directional x-ray images were taken before the preparation with #10 K-file, inserted into the mesiobuccal root canal to the working length, and after preparation with #25, #30 and #40 files. Working lenght changes were detected with measurements between the radiological apex and the instrument tips. In the Mtwo group a difference in the working competency (p<0.05) could be noticed only in the vestibulo-oral direction from #10 to #40 file. The hand instrument group showed a significant difference in working length competency for each larger file size (p<0.05) (ANOVA). Regression analysis in the hand instrumentation group indicated a working length decrease with a mean of 0,2 mm after each consecutive file size (p<0.01). The outcome of our trial indicated a high consistency in working length control for root canal preparation under simulated clinical condition using Mtwo rotary files. Mtwo NiTi rotary file did therefore proved to be more accurate in comparison to the conventional hand instrumentation. Working length, Mtwo, nickel-titanium, hand preparation, engine driven preparation.

Comparison of working length control consistency between hand K-files and Mtwo NiTi rotary system

PubMed Central

Krajczár, Károly; Varga, Enikő; Jeges, Sára; Tóth, Vilmos

2016-01-01

Background The purpose of this study was to investigate the consistency of working length control between hand instrumentation in comparison to engine driven Mtwo nickel-titanium rotary files. Material and Methods Forty extracted maxillary molars were selected and divided onto two parallel groups. The working lengths of the mesiobuccal root canals were estimated. The teeth were fixed in a phantom head. The root canal preparation was carried out group 1 (n=20) with hand K-files, (VDW, Munich, Germany) and group 2 (n=20) with Mtwo instruments (VDW, Munich, Germany). Vestibulo-oral and mesio-distal directional x-ray images were taken before the preparation with #10 K-file, inserted into the mesiobuccal root canal to the working length, and after preparation with #25, #30 and #40 files. Working lenght changes were detected with measurements between the radiological apex and the instrument tips. Results In the Mtwo group a difference in the working competency (p<0.05) could be noticed only in the vestibulo-oral direction from #10 to #40 file. The hand instrument group showed a significant difference in working length competency for each larger file size (p<0.05) (ANOVA). Regression analysis in the hand instrumentation group indicated a working length decrease with a mean of 0,2 mm after each consecutive file size (p<0.01). Conclusions The outcome of our trial indicated a high consistency in working length control for root canal preparation under simulated clinical condition using Mtwo rotary files. Mtwo NiTi rotary file did therefore proved to be more accurate in comparison to the conventional hand instrumentation. Key words:Working length, Mtwo, nickel-titanium, hand preparation, engine driven preparation. PMID:27034752

Shaping ability of the conventional nickel-titanium and reciprocating nickel-titanium file systems: a comparative study using micro-computed tomography.

PubMed

Hwang, Young-Hye; Bae, Kwang-Shik; Baek, Seung-Ho; Kum, Kee-Yeon; Lee, WooCheol; Shon, Won-Jun; Chang, Seok Woo

2014-08-01

This study used micro-computed tomographic imaging to compare the shaping ability of Mtwo (VDW, Munich, Germany), a conventional nickel-titanium file system, and Reciproc (VDW), a reciprocating file system morphologically similar to Mtwo. Root canal shaping was performed on the mesiobuccal and distobuccal canals of extracted maxillary molars. In the RR group (n = 15), Reciproc was used in a reciprocating motion (150° counterclockwise/30° clockwise, 300 rpm); in the MR group, Mtwo was used in a reciprocating motion (150° clockwise/30° counterclockwise, 300 rpm); and in the MC group, Mtwo was used in a continuous rotating motion (300 rpm). Micro-computed tomographic images taken before and after canal shaping were used to analyze canal volume change and the degree of transportation at the cervical, middle, and apical levels. The time required for canal shaping was recorded. Afterward, each file was analyzed using scanning electron microscopy. No statistically significant differences were found among the 3 groups in the time for canal shaping or canal volume change (P > .05). Transportation values of the RR and MR groups were not significantly different at any level. However, the transportation value of the MC group was significantly higher than both the RR and MR groups at the cervical and apical levels (P < .05). In the scanning electron microscopic analysis, file deformation was observed for 1 file in group RR (1/15), 3 files in group MR (3/15), and 5 files in group MC (5/15). In terms of shaping ability, Mtwo used in a reciprocating motion was not significantly different from the Reciproc system. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Atomic radii for atoms with the 6s shell outermost: The effective atomic radius and the van der Waals radius from {sub 55}Cs to {sub 80}Hg

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tatewaki, Hiroshi, E-mail: htatewak@nsc.nagoya-cu.ac.jp; Institute of Advanced Studies in Artificial Intelligence, Chukyo University, Toyota, Aichi 470-0393; Hatano, Yasuyo

We consider, for atoms from {sub 55}Cs to {sub 80}Hg, the effective atomic radius (r{sub ear}), which is defined as the distance from the nucleus at which the magnitude of the electric field is equal to that in He at one half of the equilibrium bond length of He{sub 2}. The values of r{sub ear} are about 50% larger than the mean radius of the outermost occupied orbital of 6s, . The value of r{sub ear} decreases from {sub 55}Cs to {sub 56}Ba and undergoes increases and decreases with rising nuclear charge from {sub 57}La to {sub 70}Y b. Inmore » fact r{sub ear} is understood as comprising two interlaced sequences; one consists of {sub 57}La, {sub 58}Ce, and {sub 64}Gd, which have electronic configuration (4f{sup n−1})(5d{sup 1})(6s{sup 2}), and the remaining atoms have configuration (4f{sup n})(6s{sup 2}). The sphere defined by r{sub ear} contains 85%–90% of the 6s electrons. From {sub 71}Lu to {sub 80}Hg the radius r{sub ear} also involves two sequences, corresponding to the two configurations 5d{sup n+1}6s{sup 1} and 5d{sup n}6s{sup 2}. The radius r{sub ear} according to the present methodology is considerably larger than r{sub vdW} obtained by other investigators, some of who have found values of r{sub vdW} close to .« less

Structural, electronic and optical properties of well-known primary explosive: Mercury fulminate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2015-11-28

Mercury Fulminate (MF) is one of the well-known primary explosives since 17th century and it has rendered invaluable service over many years. However, the correct molecular and crystal structures are determined recently after 300 years of its discovery. In the present study, we report pressure dependent structural, elastic, electronic and optical properties of MF. Non-local correction methods have been employed to capture the weak van der Waals interactions in layered and molecular energetic MF. Among the non-local correction methods tested, optB88-vdW method works well for the investigated compound. The obtained equilibrium bulk modulus reveals that MF is softer than themore » well known primary explosives Silver Fulminate (SF), silver azide and lead azide. MF exhibits anisotropic compressibility (b > a > c) under pressure, consequently the corresponding elastic moduli decrease in the following order: C{sub 22} > C{sub 11} > C{sub 33}. The structural and mechanical properties suggest that MF is more sensitive to detonate along c-axis (similar to RDX) due to high compressibility of Hg⋯O non-bonded interactions along that axis. Electronic structure and optical properties were calculated including spin-orbit (SO) interactions using full potential linearized augmented plane wave method within recently developed Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. The calculated TB-mBJ electronic structures of SF and MF show that these compounds are indirect bandgap insulators. Also, SO coupling is found to be more pronounced for 4d and 5d-states of Ag and Hg atoms of SF and MF, respectively. Partial density of states and electron charge density maps were used to describe the nature of chemical bonding. Ag—C bond is more directional than Hg—C bond which makes SF to be more unstable than MF. The effect of SO coupling on optical properties has also been studied and found to be significant for both (SF and MF) of the compounds.« less

Telescopic nanotube device for hot nanolithography

DOEpatents

Popescu, Adrian; Woods, Lilia M

2014-12-30

A device for maintaining a constant tip-surface distance for producing nanolithography patterns on a surface using a telescopic nanotube for hot nanolithography. An outer nanotube is attached to an AFM cantilever opposite a support end. An inner nanotube is telescopically disposed within the outer nanotube. The tip of the inner nanotube is heated to a sufficiently high temperature and brought in the vicinity of the surface. Heat is transmitted to the surface for thermal imprinting. Because the inner tube moves telescopically along the outer nanotube axis, a tip-surface distance is maintained constant due to the vdW force interaction, which in turn eliminates the need of an active feedback loop.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions.

PubMed

Wu, Bing; Zhao, Yinghe; Nan, Haiyan; Yang, Ziyi; Zhang, Yuhan; Zhao, Huijuan; He, Daowei; Jiang, Zonglin; Liu, Xiaolong; Li, Yun; Shi, Yi; Ni, Zhenhua; Wang, Jinlan; Xu, Jian-Bin; Wang, Xinran

2016-06-08

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

Does Hooke's law work in helical nanosprings?

PubMed

Ben, Sudong; Zhao, Junhua; Rabczuk, Timon

2015-08-28

Hooke's law is a principle of physics that states that the force needed to extend a spring by some distance is proportional to that distance. The law is always valid for an initial portion of the elastic range for nearly all helical macrosprings. Here we report the sharp nonlinear force-displacement relation of tightly wound helical carbon nanotubes at even small displacement via a molecular mechanics model. We demonstrate that the van der Waals (vdW) interaction between the intertube walls dominates the nonlinear relation based on our analytical expressions. This study provides physical insights into the origin of huge nonlinearity of the helical nanosprings.

Ground-state densities from the Rayleigh-Ritz variation principle and from density-functional theory.

PubMed

Kvaal, Simen; Helgaker, Trygve

2015-11-14

The relationship between the densities of ground-state wave functions (i.e., the minimizers of the Rayleigh-Ritz variation principle) and the ground-state densities in density-functional theory (i.e., the minimizers of the Hohenberg-Kohn variation principle) is studied within the framework of convex conjugation, in a generic setting covering molecular systems, solid-state systems, and more. Having introduced admissible density functionals as functionals that produce the exact ground-state energy for a given external potential by minimizing over densities in the Hohenberg-Kohn variation principle, necessary and sufficient conditions on such functionals are established to ensure that the Rayleigh-Ritz ground-state densities and the Hohenberg-Kohn ground-state densities are identical. We apply the results to molecular systems in the Born-Oppenheimer approximation. For any given potential v ∈ L(3/2)(ℝ(3)) + L(∞)(ℝ(3)), we establish a one-to-one correspondence between the mixed ground-state densities of the Rayleigh-Ritz variation principle and the mixed ground-state densities of the Hohenberg-Kohn variation principle when the Lieb density-matrix constrained-search universal density functional is taken as the admissible functional. A similar one-to-one correspondence is established between the pure ground-state densities of the Rayleigh-Ritz variation principle and the pure ground-state densities obtained using the Hohenberg-Kohn variation principle with the Levy-Lieb pure-state constrained-search functional. In other words, all physical ground-state densities (pure or mixed) are recovered with these functionals and no false densities (i.e., minimizing densities that are not physical) exist. The importance of topology (i.e., choice of Banach space of densities and potentials) is emphasized and illustrated. The relevance of these results for current-density-functional theory is examined.

Interfacial properties of black phosphorus/transition metal carbide van der Waals heterostructures

NASA Astrophysics Data System (ADS)

Yuan, Hao; Li, Zhenyu

2018-06-01

Owing to its outstanding electronic properties, black phosphorus (BP) is considered as a promising material for next-generation optoelectronic devices. In this work, devices based on BP/MXene (Zr n+1C n T2, T = O, F, OH, n = 1, 2) van der Waals (vdW) heterostructures are designed via first-principles calculations. Zr n+1C n T2 compositions with appropriate work functions lead to the formation of Ohmic contact with BP in the vertical direction. Low Schottky barriers are found along the lateral direction in BP/Zr2CF2, BP/Zr2CO2H2, BP/Zr3C2F2, and BP/Zr3C2O2H2 bilayers, and BP/Zr3C2O2 even exhibits Ohmic contact behavior. BP/Zr2CO2 is a semiconducting heterostructure with type-II band alignment, which facilitates the separation of electron-hole pairs. The band structure of BP/Zr2CO2 can be effectively tuned via a perpendicular electric field, and BP is predicted to undergo a transition from donor to acceptor at a 0.4 V/Å electric field. The versatile electronic properties of the BP/MXene heterostructures examined in this work highlight their promising potential for applications in electronics.

Spherical solid model system: Exact evaluation of the van der Waals interaction between a microscopic or submacroscopic spherical solid and a deformable fluid interface

NASA Astrophysics Data System (ADS)

Wang, Y. Z.; Wang, B.; Xiong, X. M.; Zhang, J. X.

2011-03-01

In many previous research work associated with studying the deformation of the fluid interface interacting with a solid, the theoretical calculation of the surface energy density on the deformed fluid interface (or its interaction surface pressure) is often approximately obtained by using the expression for the interaction energy per unit area (or pressure) between two parallel macroscopic plates, e.g. σ(D) = - A / 12 πD2or π(D) = - A / 6 πD3for the van der Waals (vdW) interaction, through invoking the Derjaguin approximation (DA). This approximation however would result in over- or even inaccurate-prediction of the interaction force and the corresponding deformation of the fluid interface due to the invalidation of Derjaguin approximation in cases of microscopic or submacroscopic solids. To circumvent the above limitations existing in the previous DA-based theoretical work, a more accurate and quantitative theoretical model, available for exactly calculating the vdW-induced deformation of a planar fluid interface interacting with a sphere, and the interaction forces taking into account its change, is presented in this paper. The validity and advantage of the new mathematical and physical technique is rigorously verified by comparison with the numerical results on basis of the previous Paraboloid solid (PS) model and the Hamaker's sphere-flat expression (viz. F = - 2 Aa3 / (3 D2( D + 2 a) 2)), as well as its well-known DA-based general form of F / a = - A / 6z p02.

Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.

PubMed

Grofe, Adam; Chen, Xin; Liu, Wenjian; Gao, Jiali

2017-10-05

Kohn-Sham density functional theory has been tremendously successful in chemistry and physics. Yet, it is unable to describe the energy degeneracy of spin-multiplet components with any approximate functional. This work features two contributions. (1) We present a multistate density functional theory (MSDFT) to represent spin-multiplet components and to determine multiplet energies. MSDFT is a hybrid approach, taking advantage of both wave function theory and density functional theory. Thus, the wave functions, electron densities and energy density-functionals for ground and excited states and for different components are treated on the same footing. The method is illustrated on valence excitations of atoms and molecules. (2) Importantly, a key result is that for cases in which the high-spin components can be determined separately by Kohn-Sham density functional theory, the transition density functional in MSDFT (which describes electronic coupling) can be defined rigorously. The numerical results may be explored to design and optimize transition density functionals for configuration coupling in multiconfigurational DFT.

Interfacial electronic structure and full spectral Hamaker constants of Si{sub 3}N{sub 4} intergranular films from VUV and SR-VEEL spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

French, R.H.; Scheu, C.; Duscher, G.

1995-09-01

The interfacial electronic structure, presented as the interband transition strength J{sub cv}({omega}) of the interatomic bonds, can be determined by Kramers Kronig (KK) analysis of vacuum ultraviolet (VUV) reflectance or spatially resolved valence electron energy loss (SR-VEEL) spectra. For the wetted interfaces in Si{sub 3}N{sub 4}, equilibrium thin glass films are formed whose thickness is determined by a force balance between attractive and repulsive force terms KK analysis of J{sub cv}({omega}) to yield {var_epsilon}{sub 2}({xi}) for the phases present, permits the direct calculation of the configuration-dependent Hamaker constants for the attractive vdW forces from the interfacial electronic structure. Interband transitionmore » strengths and full spectral Hamaker constants for Si{sub 3}N{sub 4}samples containing a SiYAlON glass have been determined using SR-VEELS from grains and grain boundaries and compared with results from bulk VUV spectroscopy on separate samples of glass and nitride. The A{sub 121}Hamaker constant for Si{sub 3}N{sub 4} with glass of the bulk composition is 8 zJ (zJ = 10{sup {minus}21}J) from the more established optical method. The EELS method permits the determination of vdW forces based upon actual local compositions and structure, which may differ noticeably from bulk standards. Current results show that full spectral Hamaker constants determined from VUV and SR-VEEL measurements of uniform bulk samples agree, but care must be take in the single scattering and zero loss subtraction corrections, and more work is ongoing in this area. Still the results show that for the grain boundary films present in these polycrystalline Si{sub 3}N{sub 4} samples the glass composition is of lower index of refraction. This can arise from increased oxygen content in determined in situ from the SR-VEELS of a particular grain boundary film. 45 refs.« less

Computational Modeling Approach in Probing the Effects of Cytosine Methylation on the Transcription Factor Binding to DNA.

PubMed

Tenayuca, John; Cousins, Kimberley; Yang, Shumei; Zhang, Lubo

2017-01-01

Cytosine methylation at CpG dinucleotides is a chief mechanism in epigenetic modification of gene expression patterns. Previous studies demonstrated that increased CpG methylation of Sp1 sites at -268 and -346 of protein kinase C ε promoter repressed the gene expression. The present study investigated the impact of CpG methylation on the Sp1 binding via molecular modeling and electrophoretic mobility shift assay. Each of the Sp1 sites contain two CpGs. Methylation of either CpG lowered the binding affinity of Sp1, whereas methylation of both CpGs produced a greater decrease in the binding affinity. Computation of van der Waals (VDW) energy of Sp1 in complex with the Sp1 sites demonstrated increased VDW values from one to two sites of CpG methylation. Molecular modeling indicated that single CpG methylation caused underwinding of the DNA fragment, with the phosphate groups at C1, C4 and C5 reoriented from their original positions. Methylation of both CpGs pinched the minor groove and increased the helical twist concomitant with a shallow, hydrophobic major groove. Additionally, double methylation eliminated hydrogen bonds on recognition helix residues located at positions -1 and 1, which were essential for interaction with O6/N7 of G-bases. Bonding from linker residues Arg565, Lys595 and Lys596 were also reduced. Methylation of single or both CpGs significantly affected hydrogen bonding from all three Sp1 DNA binding domains, demonstrating that the consequences of cytosine modification extend beyond the neighboring nucleotides. The results indicate that cytosine methylation causes subtle structural alterations in Sp1 binding sites consequently resulting in inhibition of side chain interactions critical for specific base recognition and reduction of the binding affinity of Sp1. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Multiconfiguration Pair-Density Functional Theory.

PubMed

Li Manni, Giovanni; Carlson, Rebecca K; Luo, Sijie; Ma, Dongxia; Olsen, Jeppe; Truhlar, Donald G; Gagliardi, Laura

2014-09-09

We present a new theoretical framework, called Multiconfiguration Pair-Density Functional Theory (MC-PDFT), which combines multiconfigurational wave functions with a generalization of density functional theory (DFT). A multiconfigurational self-consistent-field (MCSCF) wave function with correct spin and space symmetry is used to compute the total electronic density, its gradient, the on-top pair density, and the kinetic and Coulomb contributions to the total electronic energy. We then use a functional of the total density, its gradient, and the on-top pair density to calculate the remaining part of the energy, which we call the on-top-density-functional energy in contrast to the exchange-correlation energy of Kohn-Sham DFT. Because the on-top pair density is an element of the two-particle density matrix, this goes beyond the Hohenberg-Kohn theorem that refers only to the one-particle density. To illustrate the theory, we obtain first approximations to the required new type of density functionals by translating conventional density functionals of the spin densities using a simple prescription, and we perform post-SCF density functional calculations using the total density, density gradient, and on-top pair density from the MCSCF calculations. Double counting of dynamic correlation or exchange does not occur because the MCSCF energy is not used. The theory is illustrated by applications to the bond energies and potential energy curves of H2, N2, F2, CaO, Cr2, and NiCl and the electronic excitation energies of Be, C, N, N(+), O, O(+), Sc(+), Mn, Co, Mo, Ru, N2, HCHO, C4H6, c-C5H6, and pyrazine. The method presented has a computational cost and scaling similar to MCSCF, but a quantitative accuracy, even with the present first approximations to the new types of density functionals, that is comparable to much more expensive multireference perturbation theory methods.

Reformulation of Density Functional Theory for N-Representable Densities and the Resolution of the v-Representability Problem

DOE PAGES

Gonis, A.; Zhang, X. G.; Stocks, G. M.; ...

2015-10-23

Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide a complete solution of the v-representability problem by establishing a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of themore » density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism.« less

Investigation on the individual contributions of N-H...O=C and C-H...O=C interactions to the binding energies of beta-sheet models.

PubMed

Wang, Chang-Sheng; Sun, Chang-Liang

2010-04-15

In this article, the binding energies of 16 antiparallel and parallel beta-sheet models are estimated using the analytic potential energy function we proposed recently and the results are compared with those obtained from MP2, AMBER99, OPLSAA/L, and CHARMM27 calculations. The comparisons indicate that the analytic potential energy function can produce reasonable binding energies for beta-sheet models. Further comparisons suggest that the binding energy of the beta-sheet models might come mainly from dipole-dipole attractive and repulsive interactions and VDW interactions between the two strands. The dipole-dipole attractive and repulsive interactions are further obtained in this article. The total of N-H...H-N and C=O...O=C dipole-dipole repulsive interaction (the secondary electrostatic repulsive interaction) in the small ring of the antiparallel beta-sheet models is estimated to be about 6.0 kcal/mol. The individual N-H...O=C dipole-dipole attractive interaction is predicted to be -6.2 +/- 0.2 kcal/mol in the antiparallel beta-sheet models and -5.2 +/- 0.6 kcal/mol in the parallel beta-sheet models. The individual C(alpha)-H...O=C attractive interaction is -1.2 +/- 0.2 kcal/mol in the antiparallel beta-sheet models and -1.5 +/- 0.2 kcal/mol in the parallel beta-sheet models. These values are important in understanding the interactions at protein-protein interfaces and developing a more accurate force field for peptides and proteins. 2009 Wiley Periodicals, Inc.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE PAGES

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

2017-11-20

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

NASA Astrophysics Data System (ADS)

Tao, Jianmin; Ye, Lin-Hui; Duan, Yuhua

2017-12-01

The primary goal of Kohn-Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao-Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE), Tao-Perdew-Staroverov-Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree-Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Finally, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Desiderata for Healthcare Integrated Data Repositories Based on Architectural Comparison of Three Public Repositories

PubMed Central

Huser, Vojtech; Cimino, James J.

2013-01-01

Integrated data repositories (IDRs) are indispensable tools for numerous biomedical research studies. We compare three large IDRs (Informatics for Integrating Biology and the Bedside (i2b2), HMO Research Network’s Virtual Data Warehouse (VDW) and Observational Medical Outcomes Partnership (OMOP) repository) in order to identify common architectural features that enable efficient storage and organization of large amounts of clinical data. We define three high-level classes of underlying data storage models and we analyze each repository using this classification. We look at how a set of sample facts is represented in each repository and conclude with a list of desiderata for IDRs that deal with the information storage model, terminology model, data integration and value-sets management. PMID:24551366

Desiderata for healthcare integrated data repositories based on architectural comparison of three public repositories.

PubMed

Huser, Vojtech; Cimino, James J

2013-01-01

Integrated data repositories (IDRs) are indispensable tools for numerous biomedical research studies. We compare three large IDRs (Informatics for Integrating Biology and the Bedside (i2b2), HMO Research Network's Virtual Data Warehouse (VDW) and Observational Medical Outcomes Partnership (OMOP) repository) in order to identify common architectural features that enable efficient storage and organization of large amounts of clinical data. We define three high-level classes of underlying data storage models and we analyze each repository using this classification. We look at how a set of sample facts is represented in each repository and conclude with a list of desiderata for IDRs that deal with the information storage model, terminology model, data integration and value-sets management.

Buckling analysis of carbon nanotube bundles under axial compressive, bending and torsional loadings via a structural mechanics model

NASA Astrophysics Data System (ADS)

Lashkari Zadeh, Ali; Shariati, Mahmoud; Torabi, Hamid

2012-11-01

A structural mechanics model is employed for the investigation of the buckling behavior of carbon nanotube bundles of three single-walled carbon nanotubes (SWCNTs) under axial compressive, bending and torsional loadings. The effects of van der Waals (vdW) forces are further modeled using a nonlinear spring element.The effects of different types of boundary conditions are studied for nanotubes with various aspect ratios. The results reveal that bundles comprising longer SWCNTs exhibit lower critical buckling load. Moreover, for the fixed-free boundary condition the rate of critical buckling load reduction is highest, while the lowest critical buckling load occurs. Simulations show good agreement between our model and molecular dynamics results.

A corrected model for static and dynamic electromechanical instability of narrow nanotweezers: Incorporation of size effect, surface layer and finite dimensions

NASA Astrophysics Data System (ADS)

Koochi, Ali; Hosseini-Toudeshky, Hossein; Abadyan, Mohamadreza

2018-03-01

Herein, a corrected theoretical model is proposed for modeling the static and dynamic behavior of electrostatically actuated narrow-width nanotweezers considering the correction due to finite dimensions, size dependency and surface energy. The Gurtin-Murdoch surface elasticity in conjunction with the modified couple stress theory is employed to consider the coupling effect of surface stresses and size phenomenon. In addition, the model accounts for the external force corrections by incorporating the impact of narrow width on the distribution of Casimir attraction, van der Waals (vdW) force and the fringing field effect. The proposed model is beneficial for the precise modeling of the narrow nanotweezers in nano-scale.

Self-Interaction Error in Density Functional Theory: An Appraisal.

PubMed

Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G

2018-05-03

Self-interaction error (SIE) is considered to be one of the major sources of error in most approximate exchange-correlation functionals for Kohn-Sham density-functional theory (KS-DFT), and it is large with all local exchange-correlation functionals and with some hybrid functionals. In this work, we consider systems conventionally considered to be dominated by SIE. For these systems, we demonstrate that by using multiconfiguration pair-density functional theory (MC-PDFT), the error of a translated local density-functional approximation is significantly reduced (by a factor of 3) when using an MCSCF density and on-top density, as compared to using KS-DFT with the parent functional; the error in MC-PDFT with local on-top functionals is even lower than the error in some popular KS-DFT hybrid functionals. Density-functional theory, either in MC-PDFT form with local on-top functionals or in KS-DFT form with some functionals having 50% or more nonlocal exchange, has smaller errors for SIE-prone systems than does CASSCF, which has no SIE.

Anisotropic nanocolloids: self-assembly, interfacial adsorption, and electrostatic screening

NASA Astrophysics Data System (ADS)

de Graaf, J.

2012-06-01

In this thesis we consider the influence of anisotropy on the behaviour of colloids using theory and simulations. The recent increase in the ability to synthesize anisotropic particles (cubes, caps, octapods, etc.) has led to samples of sufficient quality to perform self-assembly experiments. Our investigation is therefore particularly relevant to current and future experimental studies of colloids. We examine several topics for which shape anisotropy plays an important role: (1.) - Interfacial adsorption. We introduced the triangular-tessellation technique to approximate the surface areas and line length which are associated with a plane-particle intersection. Our method allowed us to determine the free energy of adsorption for a single irregular colloid with heterogeneous surface properties adsorbed at a flat liquid-liquid interface in the Pieranski approximation. Ellipsoids only adsorbed at the interface perpendicular to the interfacial normal. However, for cylinders we could find a metastable adsorption minimum corresponding to parallel adsorption. We also considered the possible time dependence of the adsorption process using simple dynamics. Finally, we studied the adsorption of truncated nanocubes with a contact-angle surface pattern and we observed that there are three prototypical equilibrium adsorption configurations for these particles. (2.) - Crystal-structure prediction. We extended an existing crystal-structure-prediction algorithm to predict structures for systems comprised of irregular hard particles. Using this technique we examined the high-density crystal structures for 17 irregular nonconvex shapes and we confirmed several mathematical conjectures for the packings of a large set of 142 convex polyhedra. We also proved that we have obtained the densest configurations for rhombicuboctahedra and rhombic enneacontrahedra, respectively. Moreover, we considered a family of truncated cubes, which interpolates between a cube and an octahedron, for which we obtained a fascinating richness in crystal structures. For the octahedron we determined the equation of state and we obtained a liquid, a (metastable) body-centred-cubic rotator phase, and a crystal phase. (3.) - Octapod hierarchical self-assembly. We analysed the recently observed hierarchical self-assembly of octapod-shaped nanocrystals (octapods) into three-dimensional (3D) superstructures. We constructed an empirical simulation model capable of reproducing the initial chain-formation step of the self-assembly. The van-der-Waals (vdW) interactions between octapods suspended in an (a)polar medium were obtained by means of a Hamaker-de-Boer-type integration and the nature of these interactions allowed us to justify elements of our empirical model. We used the theoretical vdW calculation, together with the experimental and simulation results, to formulate a mechanism which explained the observed self-assembly in terms of the solvent-dependence and directionality of the octapod-octapod interactions. (4.) - Ionic screening of charged Janus particles. We studied the screening of charged Janus particles in an electrolyte by primitive-model Monte Carlo (MC) simulations for a wide variety of parameters. We also introduced a method to compare these results to the predictions of nonlinear Poisson-Boltzmann (PB) theory. The comparison of MC and PB results allowed us to probe the range of validity of the PB approximation. This range of validity corresponds well to the range that was predicted by field-theoretical studies of homogeneously charged flat surfaces.

Molecular Modeling of Lipid Aggregates: Theory and Application

NASA Astrophysics Data System (ADS)

Fenner, Joel Stewart

The ability of cell membranes to perform a wide variety of biological functions stems from the organization and composition of its molecular constituents. There are many engineering applications, such as liposome drug delivery carriers, whose functionality takes advantage of the structure to function relationship of lipid membranes. The fundamental understanding of the relationship between the thermodynamic behavior and structure of lipid membranes and the molecular properties of their lipid constituents is crucial to the successful design of lipid related applications. However, information about how the local microscopic composition of lipid membranes responds to the presence of proteins and nanomaterials is challenging given the intrinsic experimental and theoretical difficulties of studying such small-scale systems. The present work generalizes a self consistent mean field theory for the study of the thermodynamic and structural behavior of lipid bilayers as a function of its molecular composition and physicochemical environments. This novel molecular theory provides with the ability of performing systematic thermodynamic calculations at relatively low computational costs while considering a detailed molecular description of the system under study. The competition of all relevant molecular interactions, such as electrostatics, vdW and chemical equilibria, in the membrane system is described. The developed molecular theory is applied to study how the protonation state of pH-sensitive amphiphiles in a membrane system affects the membrane's morphology. The molecular theory results demonstrate that the protonation state of ionizable groups within amphiphilic membranes shows a highly complex non-monotonic dependence on bulk salt concentration and pH strength. This result suggests that information about the pKa of the molecules is not sufficient to predict the protonation state of the ionizable groups in the membrane system. The molecular theory is also applied to study how the presence of proteins or functionalized nanoparticles near a multicomponent membrane surface leads to changes in its local membrane composition. The results support an electrostatic dependent recruitment mechanism of oncogenic RhoA proteins to the cell membrane. Finally, the molecular theory results describe how nanoparticle functionality and/or membrane molecular composition can be tuned to enhance or suppress nanoparticle adsorption on to phospholipid membranes.

Density-functional theory for internal magnetic fields

NASA Astrophysics Data System (ADS)

Tellgren, Erik I.

2018-01-01

A density-functional theory is developed based on the Maxwell-Schrödinger equation with an internal magnetic field in addition to the external electromagnetic potentials. The basic variables of this theory are the electron density and the total magnetic field, which can equivalently be represented as a physical current density. Hence, the theory can be regarded as a physical current density-functional theory and an alternative to the paramagnetic current density-functional theory due to Vignale and Rasolt. The energy functional has strong enough convexity properties to allow a formulation that generalizes Lieb's convex analysis formulation of standard density-functional theory. Several variational principles as well as a Hohenberg-Kohn-like mapping between potentials and ground-state densities follow from the underlying convex structure. Moreover, the energy functional can be regarded as the result of a standard approximation technique (Moreau-Yosida regularization) applied to the conventional Schrödinger ground-state energy, which imposes limits on the maximum curvature of the energy (with respect to the magnetic field) and enables construction of a (Fréchet) differentiable universal density functional.

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

PubMed

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

A note on the accuracy of KS-DFT densities

NASA Astrophysics Data System (ADS)

Ranasinghe, Duminda S.; Perera, Ajith; Bartlett, Rodney J.

2017-11-01

The accuracy of the density of wave function methods and Kohn-Sham (KS) density functionals is studied using moments of the density, ⟨rn ⟩ =∫ ρ (r )rnd τ =∫0∞4 π r2ρ (r ) rnd r ,where n =-1 ,-2,0,1,2 ,and 3 provides information about the short- and long-range behavior of the density. Coupled cluster (CC) singles, doubles, and perturbative triples (CCSD(T)) is considered as the reference density. Three test sets are considered: boron through neon neutral atoms, two and four electron cations, and 3d transition metals. The total density and valence only density are distinguished by dropping appropriate core orbitals. Among density functionals tested, CAMQTP00 and ωB97x show the least deviation for boron through neon neutral atoms. They also show accurate eigenvalues for the HOMO indicating that they should have a more correct long-range behavior for the density. For transition metals, some density functional approximations outperform some wave function methods, suggesting that the KS determinant could be a better starting point for some kinds of correlated calculations. By using generalized many-body perturbation theory (MBPT), the convergence of second-, third-, and fourth-order KS-MBPT for the density is addressed as it converges to the infinite-order coupled cluster result. For the transition metal test set, the deviations in the KS density functional theory methods depend on the amount of exact exchange the functional uses. Functionals with exact exchange close to 25% show smaller deviations from the CCSD(T) density.

Segmentation Algorithms for Detection of Targets in IR Imagery (Algorithmes de Segmentation pour la Detection de Cibles sur Images IR),

DTIC Science & Technology

1981-01-01

This fact being established, leptokurtic and platykurtic density functions are defined in terms of deviations from the normal density function. Thus...the usual definitions (Ref. 6) are: Leptokurtic - A density function that is peaked, K > 0, [18] and Platykurtic - A density function that is flat, K...has long Deen accepted that a symmetrical platykurtic density function, with K<O, is characterized by a flatter top and more abrupt terminals than the

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Rui; School of Mathematics and Information Science, North China University of Water Resources and Electric Power, Zhengzhou 450011; Zheng, Limin

Theoretical studies of the potential energy surface (PES) and bound states are performed for the N{sub 2}–N{sub 2}O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N{sub 2}O monomer is near the N{sub 2} monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency formore » intermolecular disrotation mode is 23.086 cm{sup −1}, which is in good agreement with the available experimental data of 22.334 cm{sup −1}. A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers {sup 14}N{sub 2}–N{sub 2}O and {sup 15}N{sub 2}–N{sub 2}O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters.« less

Predicting the impact of mutations on the specific activity of Bacillus thermocatenulatus lipase using a combined approach of docking and molecular dynamics.

PubMed

Yukselen, Onur; Timucin, Emel; Sezerman, Ugur

2016-10-01

Lipases are important biocatalysts owing to their ability to catalyze diverse reactions with exceptional substrate specificities. A combined docking and molecular dynamics (MD) approach was applied to study the chain-length selectivity of Bacillus thermocatenulatus lipase (BTL2) towards its natural substrates (triacylglycerols). A scoring function including electrostatic, van der Waals (vdW) and desolvation energies along with conformational entropy was developed to predict the impact of mutation. The native BTL2 and its 6 mutants (F17A, V175A, V175F, D176F, T178V and I320F) were experimentally analyzed to determine their specific activities towards tributyrin (C4) or tricaprylin (C8), which were used to test our approach. Our scoring methodology predicted the chain-length selectivity of BTL2 with 85.7% (6/7) accuracy with a positive correlation between the calculated scores and the experimental activity values (r = 0.82, p = 0.0004). Additionally, the impact of mutation on activity was predicted with 75% (9/12) accuracy. The described study represents a fast and reliable approach to accurately predict the effect of mutations on the activity and selectivity of lipases and also of other enzymes. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Dynamic Structure Factor: An Introduction

NASA Astrophysics Data System (ADS)

Sturm, K.

1993-02-01

The doubly differential cross-section for weak inelastic scattering of waves or particles by manybody systems is derived in Born approximation and expressed in terms of the dynamic structure factor according to van Hove. The application of this very general scheme to scattering of neutrons, x-rays and high-energy electrons is discussed briefly. The dynamic structure factor, which is the space and time Fourier transform of the density-density correlation function, is a property of the many-body system independent of the external probe and carries information on the excitation spectrum of the system. The relation of the electronic structure factor to the density-density response function defined in linear-response theory is shown using the fluctuation-dissipation theorem. This is important for calculations, since the response function can be calculated approximately from the independent-particle response function in self-consistent field approximations, such as the random-phase approximation or the local-density approximation of the density functional theory. Since the density-density response function also determines the dielectric function, the dynamic structure can be expressed by the dielectric function.

Comparing ab initio density-functional and wave function theories: the impact of correlation on the electronic density and the role of the correlation potential.

PubMed

Grabowski, Ireneusz; Teale, Andrew M; Śmiga, Szymon; Bartlett, Rodney J

2011-09-21

The framework of ab initio density-functional theory (DFT) has been introduced as a way to provide a seamless connection between the Kohn-Sham (KS) formulation of DFT and wave-function based ab initio approaches [R. J. Bartlett, I. Grabowski, S. Hirata, and S. Ivanov, J. Chem. Phys. 122, 034104 (2005)]. Recently, an analysis of the impact of dynamical correlation effects on the density of the neon atom was presented [K. Jankowski, K. Nowakowski, I. Grabowski, and J. Wasilewski, J. Chem. Phys. 130, 164102 (2009)], contrasting the behaviour for a variety of standard density functionals with that of ab initio approaches based on second-order Møller-Plesset (MP2) and coupled cluster theories at the singles-doubles (CCSD) and singles-doubles perturbative triples [CCSD(T)] levels. In the present work, we consider ab initio density functionals based on second-order many-body perturbation theory and coupled cluster perturbation theory in a similar manner, for a range of small atomic and molecular systems. For comparison, we also consider results obtained from MP2, CCSD, and CCSD(T) calculations. In addition to this density based analysis, we determine the KS correlation potentials corresponding to these densities and compare them with those obtained for a range of ab initio density functionals via the optimized effective potential method. The correlation energies, densities, and potentials calculated using ab initio DFT display a similar systematic behaviour to those derived from electronic densities calculated using ab initio wave function theories. In contrast, typical explicit density functionals for the correlation energy, such as VWN5 and LYP, do not show behaviour consistent with this picture of dynamical correlation, although they may provide some degree of correction for already erroneous explicitly density-dependent exchange-only functionals. The results presented here using orbital dependent ab initio density functionals show that they provide a treatment of exchange and correlation contributions within the KS framework that is more consistent with traditional ab initio wave function based methods.

Local and linear chemical reactivity response functions at finite temperature in density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franco-Pérez, Marco, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx; Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340; Ayers, Paul W., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx

2015-12-28

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dualmore » descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.« less

Local and linear chemical reactivity response functions at finite temperature in density functional theory.

PubMed

Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

2015-12-28

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

PubMed

Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

2015-01-13

Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

Structural stability and mechanical properties of technetium mononitride (TcN)

NASA Astrophysics Data System (ADS)

Soni, Shubhangi; Choudhary, K. K.; Kaurav, Netram

2018-05-01

Among the nitrides, 3d and 4d transition metal nitrides have been investigated both experimentally and theoretically due to their predominant performances and enormous applications. In the present paper, we have attempted to predict the structural stability and mechanical properties of technetium mononitride (TcN) using an effective interionic interaction potential, which includes the long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach. Our theoretical approach reveals the structural phase transition of the TcN B3 to B1 structure, wherein, the Gibbs' free energies of both the structures were minimized. The variations of elastic constants with pressure follow a systematic trend identical to that observed in other compounds of ZnS type structure family.

Pressure induced structural phase transition from NaCl-type (B1) to CsCl-type (B2) structure in sodium chloride

NASA Astrophysics Data System (ADS)

Jain, Aayushi; Dixit, R. C.

2018-05-01

Pressure induced structural phase transition of NaCl-type (B1) to CsCl-type (B2) structure in Sodium Chloride NaCl are presented. An effective interionic interaction potential (EIOP) with long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbor ions within the Hafemeister and Flygare approach with modified ionic charge is reported here. The reckon value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are compatible as compared with reported data. The variations of elastic constants and their combinations with pressure follow ordered behavior. The present approach has also succeeded in predicting the Born and relative stability criteria.

Magnetic-Field Density-Functional Theory (BDFT): Lessons from the Adiabatic Connection.

PubMed

Reimann, Sarah; Borgoo, Alex; Tellgren, Erik I; Teale, Andrew M; Helgaker, Trygve

2017-09-12

We study the effects of magnetic fields in the context of magnetic field density-functional theory (BDFT), where the energy is a functional of the electron density ρ and the magnetic field B. We show that this approach is a worthwhile alternative to current-density functional theory (CDFT) and may provide a viable route to the study of many magnetic phenomena using density-functional theory (DFT). The relationship between BDFT and CDFT is developed and clarified within the framework of the four-way correspondence of saddle functions and their convex and concave parents in convex analysis. By decomposing the energy into its Kohn-Sham components, we demonstrate that the magnetizability is mainly determined by those energy components that are related to the density. For existing density functional approximations, this implies that, for the magnetizability, improvements of the density will be more beneficial than introducing a magnetic-field dependence in the correlation functional. However, once a good charge density is achieved, we show that high accuracy is likely only obtainable by including magnetic-field dependence. We demonstrate that adiabatic-connection (AC) curves at different field strengths resemble one another closely provided each curve is calculated at the equilibrium geometry of that field strength. In contrast, if all AC curves are calculated at the equilibrium geometry of the field-free system, then the curves change strongly with increasing field strength due to the increasing importance of static correlation. This holds also for density functional approximations, for which we demonstrate that the main error encountered in the presence of a field is already present at zero field strength, indicating that density-functional approximations may be applied to systems in strong fields, without the need to treat additional static correlation.

Insights into the fold organization of TIM barrel from interaction energy based structure networks.

PubMed

Vijayabaskar, M S; Vishveshwara, Saraswathi

2012-01-01

There are many well-known examples of proteins with low sequence similarity, adopting the same structural fold. This aspect of sequence-structure relationship has been extensively studied both experimentally and theoretically, however with limited success. Most of the studies consider remote homology or "sequence conservation" as the basis for their understanding. Recently "interaction energy" based network formalism (Protein Energy Networks (PENs)) was developed to understand the determinants of protein structures. In this paper we have used these PENs to investigate the common non-covalent interactions and their collective features which stabilize the TIM barrel fold. We have also developed a method of aligning PENs in order to understand the spatial conservation of interactions in the fold. We have identified key common interactions responsible for the conservation of the TIM fold, despite high sequence dissimilarity. For instance, the central beta barrel of the TIM fold is stabilized by long-range high energy electrostatic interactions and low-energy contiguous vdW interactions in certain families. The other interfaces like the helix-sheet or the helix-helix seem to be devoid of any high energy conserved interactions. Conserved interactions in the loop regions around the catalytic site of the TIM fold have also been identified, pointing out their significance in both structural and functional evolution. Based on these investigations, we have developed a novel network based phylogenetic analysis for remote homologues, which can perform better than sequence based phylogeny. Such an analysis is more meaningful from both structural and functional evolutionary perspective. We believe that the information obtained through the "interaction conservation" viewpoint and the subsequently developed method of structure network alignment, can shed new light in the fields of fold organization and de novo computational protein design.

Multiconfiguration Pair-Density Functional Theory Is as Accurate as CASPT2 for Electronic Excitation.

PubMed

Hoyer, Chad E; Ghosh, Soumen; Truhlar, Donald G; Gagliardi, Laura

2016-02-04

A correct description of electronically excited states is critical to the interpretation of visible-ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory and a new kind of density functional called an on-top density functional. Here, we show that MC-PDFT with a first-generation on-top density functional performs as well as CASPT2 for an organic chemistry database including valence, Rydberg, and charge-transfer excitations. The results are very encouraging for practical applications.

On the use of the noncentral chi-square density function for the distribution of helicopter spectral estimates

NASA Technical Reports Server (NTRS)

Garber, Donald P.

1993-01-01

A probability density function for the variability of ensemble averaged spectral estimates from helicopter acoustic signals in Gaussian background noise was evaluated. Numerical methods for calculating the density function and for determining confidence limits were explored. Density functions were predicted for both synthesized and experimental data and compared with observed spectral estimate variability.

Stretched hydrogen molecule from a constrained-search density-functional perspective

DOE Office of Scientific and Technical Information (OSTI.GOV)

Valone, Steven M; Levy, Mel

2009-01-01

Constrained-search density functional theory gives valuable insights into the fundamentals of density functional theory. It provides exact results and bounds on the ground- and excited-state density functionals. An important advantage of the theory is that it gives guidance in the construction of functionals. Here they engage constrained search theory to explore issues associated with the functional behavior of 'stretched bonds' in molecular hydrogen. A constrained search is performed with familiar valence bond wavefunctions ordinarily used to describe molecular hydrogen. The effective, one-electron hamiltonian is computed and compared to the corresponding uncorrelated, Hartree-Fock effective hamiltonian. Analysis of the functional suggests themore » need to construct different functionals for the same density and to allow a competition among these functions. As a result the correlation energy functional is composed explicitly of energy gaps from the different functionals.« less

Active Space Dependence in Multiconfiguration Pair-Density Functional Theory.

PubMed

Sharma, Prachi; Truhlar, Donald G; Gagliardi, Laura

2018-02-13

In multiconfiguration pair-density functional theory (MC-PDFT), multiconfiguration self-consistent-field calculations and on-top density functionals are combined to describe both static and dynamic correlation. Here, we investigate how the MC-PDFT total energy and its components depend on the active space choice in the case of the H 2 and N 2 molecules. The active space dependence of the on-top pair density, the total density, the ratio of on-top pair density to half the square of the electron density, and the satisfaction of the virial theorem are also explored. We find that the density and on-top pair density do not change significantly with changes in the active space. However, the on-top ratio does change significantly with respect to active space change, and this affects the on-top energy. This study provides a foundation for designing on-top density functionals and automatizing the active space choice in MC-PDFT.

Multicomponent density functional theory embedding formulation.

PubMed

Culpitt, Tanner; Brorsen, Kurt R; Pak, Michael V; Hammes-Schiffer, Sharon

2016-07-28

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF(-) molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

Multicomponent density functional theory embedding formulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.

Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density ismore » separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.« less

The Visit-Data Warehouse: Enabling Novel Secondary Use of Health Information Exchange Data

PubMed Central

Fleischman, William; Lowry, Tina; Shapiro, Jason

2014-01-01

Introduction/Objectives: Health Information Exchange (HIE) efforts face challenges with data quality and performance, and this becomes especially problematic when data is leveraged for uses beyond primary clinical use. We describe a secondary data infrastructure focusing on patient-encounter, nonclinical data that was built on top of a functioning HIE platform to support novel secondary data uses and prevent potentially negative impacts these uses might have otherwise had on HIE system performance. Background: HIE efforts have generally formed for the primary clinical use of individual clinical providers searching for data on individual patients under their care, but many secondary uses have been proposed and are being piloted to support care management, quality improvement, and public health. Description of the HIE and Base Infrastructure: This infrastructure review describes a module built into the Healthix HIE. Healthix, based in the New York metropolitan region, comprises 107 participating organizations with 29,946 acute-care beds in 383 facilities, and includes more than 9.2 million unique patients. The primary infrastructure is based on the InterSystems proprietary Caché data model distributed across servers in multiple locations, and uses a master patient index to link individual patients’ records across multiple sites. We built a parallel platform, the “visit data warehouse,” of patient encounter data (demographics, date, time, and type of visit) using a relational database model to allow accessibility using standard database tools and flexibility for developing secondary data use cases. These four secondary use cases include the following: (1) tracking encounter-based metrics in a newly established geriatric emergency department (ED), (2) creating a dashboard to provide a visual display as well as a tabular output of near-real-time de-identified encounter data from the data warehouse, (3) tracking frequent ED users as part of a regional-approach to case management intervention, and (4) improving an existing quality improvement program that analyzes patients with return visits to EDs within 72 hours of discharge. Results/Lessons Learned: Setting up a separate, near-real-time, encounters-based relational database to complement an HIE built on a hierarchical database is feasible, and may be necessary to support many secondary uses of HIE data. As of November 2014, the visit-data warehouse (VDW) built by Healthix is undergoing technical validation testing and updates on an hourly basis. We had to address data integrity issues with both nonstandard and missing HL7 messages because of varied HL7 implementation across the HIE. Also, given our HIEs federated structure, some sites expressed concerns regarding data centralization for the VDW. An established and stable HIE governance structure was critical in overcoming this initial reluctance. Conclusions: As secondary use of HIE data becomes more prevalent, it may be increasingly necessary to build separate infrastructure to support secondary use without compromising performance. More research is needed to determine optimal ways of building such infrastructure and validating its use for secondary purposes. PMID:25848595

Combining Density Functional Theory and Green's Function Theory: Range-Separated, Nonlocal, Dynamic, and Orbital-Dependent Hybrid Functional.

PubMed

Kananenka, Alexei A; Zgid, Dominika

2017-11-14

We present a rigorous framework which combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short- and long-range components. Short-range contribution to the total energy and exchange-correlation potential is provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particular, we present a range-separated hybrid functional called srSVWN5-lrGF2 which combines the local-density approximation and the second-order Green's function theory. We illustrate that similarly to density functional approximations, the new functional is weakly basis-set dependent. Furthermore, it offers an improved description of the short-range dynamic correlation. The many-body contribution to the functional mitigates the many-electron self-interaction error present in many density functional approximations and provides a better description of molecular properties. Additionally, we illustrate that the new functional can be used to scale down the self-energy and, therefore, introduce an additional sparsity to the self-energy matrix that in the future can be exploited in calculations for large molecules or periodic systems.

Exact conditions on the temperature dependence of density functionals

DOE PAGES

Burke, K.; Smith, J. C.; Grabowski, P. E.; ...

2016-05-15

Universal exact conditions guided the construction of most ground-state density functional approximations in use today. Here, we derive the relation between the entropy and Mermin free energy density functionals for thermal density functional theory. Both the entropy and sum of kinetic and electron-electron repulsion functionals are shown to be monotonically increasing with temperature, while the Mermin functional is concave downwards. Analogous relations are found for both exchange and correlation. The importance of these conditions is illustrated in two extremes: the Hubbard dimer and the uniform gas.

Long-range corrected density functional through the density matrix expansion based semilocal exchange hole.

PubMed

Patra, Bikash; Jana, Subrata; Samal, Prasanjit

2018-03-28

The exchange hole, which is one of the principal constituents of the density functional formalism, can be used to design accurate range-separated hybrid functionals in association with appropriate correlation. In this regard, the exchange hole derived from the density matrix expansion has gained attention due to its fulfillment of some of the desired exact constraints. Thus, the new long-range corrected density functional proposed here combines the meta generalized gradient approximation level exchange functional designed from the density matrix expansion based exchange hole coupled with the ab initio Hartree-Fock exchange through the range separation of the Coulomb interaction operator using the standard error function technique. Then, in association with the Lee-Yang-Parr correlation functional, the assessment and benchmarking of the above newly constructed range-separated functional with various well-known test sets shows its reasonable performance for a broad range of molecular properties, such as thermochemistry, non-covalent interaction and barrier heights of the chemical reactions.

Beyond Kohn-Sham Approximation: Hybrid Multistate Wave Function and Density Functional Theory.

PubMed

Gao, Jiali; Grofe, Adam; Ren, Haisheng; Bao, Peng

2016-12-15

A multistate density functional theory (MSDFT) is presented in which the energies and densities for the ground and excited states are treated on the same footing using multiconfigurational approaches. The method can be applied to systems with strong correlation and to correctly describe the dimensionality of the conical intersections between strongly coupled dissociative potential energy surfaces. A dynamic-then-static framework for treating electron correlation is developed to first incorporate dynamic correlation into contracted state functions through block-localized Kohn-Sham density functional theory (KSDFT), followed by diagonalization of the effective Hamiltonian to include static correlation. MSDFT can be regarded as a hybrid of wave function and density functional theory. The method is built on and makes use of the current approximate density functional developed in KSDFT, yet it retains its computational efficiency to treat strongly correlated systems that are problematic for KSDFT but too large for accurate WFT. The results presented in this work show that MSDFT can be applied to photochemical processes involving conical intersections.

On extending Kohn-Sham density functionals to systems with fractional number of electrons.

PubMed

Li, Chen; Lu, Jianfeng; Yang, Weitao

2017-06-07

We analyze four ways of formulating the Kohn-Sham (KS) density functionals with a fractional number of electrons, through extending the constrained search space from the Kohn-Sham and the generalized Kohn-Sham (GKS) non-interacting v-representable density domain for integer systems to four different sets of densities for fractional systems. In particular, these density sets are (I) ensemble interacting N-representable densities, (II) ensemble non-interacting N-representable densities, (III) non-interacting densities by the Janak construction, and (IV) non-interacting densities whose composing orbitals satisfy the Aufbau occupation principle. By proving the equivalence of the underlying first order reduced density matrices associated with these densities, we show that sets (I), (II), and (III) are equivalent, and all reduce to the Janak construction. Moreover, for functionals with the ensemble v-representable assumption at the minimizer, (III) reduces to (IV) and thus justifies the previous use of the Aufbau protocol within the (G)KS framework in the study of the ground state of fractional electron systems, as defined in the grand canonical ensemble at zero temperature. By further analyzing the Aufbau solution for different density functional approximations (DFAs) in the (G)KS scheme, we rigorously prove that there can be one and only one fractional occupation for the Hartree Fock functional, while there can be multiple fractional occupations for general DFAs in the presence of degeneracy. This has been confirmed by numerical calculations using the local density approximation as a representative of general DFAs. This work thus clarifies important issues on density functional theory calculations for fractional electron systems.

Functional thermo-dynamics: a generalization of dynamic density functional theory to non-isothermal situations.

PubMed

Anero, Jesús G; Español, Pep; Tarazona, Pedro

2013-07-21

We present a generalization of Density Functional Theory (DFT) to non-equilibrium non-isothermal situations. By using the original approach set forth by Gibbs in his consideration of Macroscopic Thermodynamics (MT), we consider a Functional Thermo-Dynamics (FTD) description based on the density field and the energy density field. A crucial ingredient of the theory is an entropy functional, which is a concave functional. Therefore, there is a one to one connection between the density and energy fields with the conjugate thermodynamic fields. The connection between the three levels of description (MT, DFT, FTD) is clarified through a bridge theorem that relates the entropy of different levels of description and that constitutes a generalization of Mermin's theorem to arbitrary levels of description whose relevant variables are connected linearly. Although the FTD level of description does not provide any new information about averages and correlations at equilibrium, it is a crucial ingredient for the dynamics in non-equilibrium states. We obtain with the technique of projection operators the set of dynamic equations that describe the evolution of the density and energy density fields from an initial non-equilibrium state towards equilibrium. These equations generalize time dependent density functional theory to non-isothermal situations. We also present an explicit model for the entropy functional for hard spheres.

Universal functions of nuclear proximity potential for Skyrme nucleus-nucleus interaction in a semiclassical approach

NASA Astrophysics Data System (ADS)

Gupta, Raj K.; Singh, Dalip; Kumar, Raj; Greiner, Walter

2009-07-01

The universal function of the nuclear proximity potential is obtained for the Skyrme nucleus-nucleus interaction in the semiclassical extended Thomas-Fermi (ETF) approach. This is obtained as a sum of the spin-orbit-density-independent and spin-orbit-density-dependent parts of the Hamiltonian density, since the two terms behave differently, the spin-orbit-density-independent part mainly attractive and the spin-orbit-density-dependent part mainly repulsive. The semiclassical expansions of kinetic energy density and spin-orbit density are allowed up to second order, and the two-parameter Fermi density, with its parameters fitted to experiments, is used for the nuclear density. The universal functions or the resulting nuclear proximity potential reproduce the 'exact' Skyrme nucleus-nucleus interaction potential in the semiclassical approach, within less than ~1 MeV of difference, both at the maximum attraction and in the surface region. An application of the resulting interaction potential to fusion excitation functions shows clearly that the parameterized universal functions of nuclear proximity potential substitute completely the 'exact' potential in the Skyrme energy density formalism based on the semiclassical ETF method, including also the modifications of interaction barriers at sub-barrier energies in terms of modifying the constants of the universal functions.

Double-hybrid density-functional theory with meta-generalized-gradient approximations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Souvi, Sidi M. O., E-mail: sidi.souvi@irsn.fr; Sharkas, Kamal; Toulouse, Julien, E-mail: julien.toulouse@upmc.fr

2014-02-28

We extend the previously proposed one-parameter double-hybrid density-functional theory [K. Sharkas, J. Toulouse, and A. Savin, J. Chem. Phys. 134, 064113 (2011)] to meta-generalized-gradient-approximation (meta-GGA) exchange-correlation density functionals. We construct several variants of one-parameter double-hybrid approximations using the Tao-Perdew-Staroverov-Scuseria (TPSS) meta-GGA functional and test them on test sets of atomization energies and reaction barrier heights. The most accurate variant uses the uniform coordinate scaling of the density and of the kinetic energy density in the correlation functional, and improves over both standard Kohn-Sham TPSS and second-order Møller-Plesset calculations.

The force distribution probability function for simple fluids by density functional theory.

PubMed

Rickayzen, G; Heyes, D M

2013-02-28

Classical density functional theory (DFT) is used to derive a formula for the probability density distribution function, P(F), and probability distribution function, W(F), for simple fluids, where F is the net force on a particle. The final formula for P(F) ∝ exp(-AF(2)), where A depends on the fluid density, the temperature, and the Fourier transform of the pair potential. The form of the DFT theory used is only applicable to bounded potential fluids. When combined with the hypernetted chain closure of the Ornstein-Zernike equation, the DFT theory for W(F) agrees with molecular dynamics computer simulations for the Gaussian and bounded soft sphere at high density. The Gaussian form for P(F) is still accurate at lower densities (but not too low density) for the two potentials, but with a smaller value for the constant, A, than that predicted by the DFT theory.

Single-particle energies and density of states in density functional theory

NASA Astrophysics Data System (ADS)

van Aggelen, H.; Chan, G. K.-L.

2015-07-01

Time-dependent density functional theory (TD-DFT) is commonly used as the foundation to obtain neutral excited states and transition weights in DFT, but does not allow direct access to density of states and single-particle energies, i.e. ionisation energies and electron affinities. Here we show that by extending TD-DFT to a superfluid formulation, which involves operators that break particle-number symmetry, we can obtain the density of states and single-particle energies from the poles of an appropriate superfluid response function. The standard Kohn- Sham eigenvalues emerge as the adiabatic limit of the superfluid response under the assumption that the exchange- correlation functional has no dependence on the superfluid density. The Kohn- Sham eigenvalues can thus be interpreted as approximations to the ionisation energies and electron affinities. Beyond this approximation, the formalism provides an incentive for creating a new class of density functionals specifically targeted at accurate single-particle eigenvalues and bandgaps.

Trivial constraints on orbital-free kinetic energy density functionals

NASA Astrophysics Data System (ADS)

Luo, Kai; Trickey, S. B.

2018-03-01

Approximate kinetic energy density functionals (KEDFs) are central to orbital-free density functional theory. Limitations on the spatial derivative dependencies of KEDFs have been claimed from differential virial theorems. We identify a central defect in the argument: the relationships are not true for an arbitrary density but hold only for the minimizing density and corresponding chemical potential. Contrary to the claims therefore, the relationships are not constraints and provide no independent information about the spatial derivative dependencies of approximate KEDFs. A simple argument also shows that validity for arbitrary v-representable densities is not restored by appeal to the density-potential bijection.

Theoretical analysis of sound transmission loss through graphene sheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Natsuki, Toshiaki, E-mail: natsuki@shinshu-u.ac.jp; Institute of Carbon Science and Technology, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553; Ni, Qing-Qing

2014-11-17

We examine the potential of using graphene sheets (GSs) as sound insulating materials that can be used for nano-devices because of their small size, super electronic, and mechanical properties. In this study, a theoretical analysis is proposed to predict the sound transmission loss through multi-layered GSs, which are formed by stacks of GS and bound together by van der Waals (vdW) forces between individual layers. The result shows that the resonant frequencies of the sound transmission loss occur in the multi-layered GSs and the values are very high. Based on the present analytical solution, we predict the acoustic insulation propertymore » for various layers of sheets under both normal incident wave and acoustic field of random incidence source. The scheme could be useful in vibration absorption application of nano devices and materials.« less

Ensemble density variational methods with self- and ghost-interaction-corrected functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pastorczak, Ewa; Pernal, Katarzyna, E-mail: pernalk@gmail.com

2014-05-14

Ensemble density functional theory (DFT) offers a way of predicting excited-states energies of atomic and molecular systems without referring to a density response function. Despite a significant theoretical work, practical applications of the proposed approximations have been scarce and they do not allow for a fair judgement of the potential usefulness of ensemble DFT with available functionals. In the paper, we investigate two forms of ensemble density functionals formulated within ensemble DFT framework: the Gross, Oliveira, and Kohn (GOK) functional proposed by Gross et al. [Phys. Rev. A 37, 2809 (1988)] alongside the orbital-dependent eDFT form of the functional introducedmore » by Nagy [J. Phys. B 34, 2363 (2001)] (the acronym eDFT proposed in analogy to eHF – ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self- and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional.« less

Extension of many-body theory and approximate density functionals to fractional charges and fractional spins.

PubMed

Yang, Weitao; Mori-Sánchez, Paula; Cohen, Aron J

2013-09-14

The exact conditions for density functionals and density matrix functionals in terms of fractional charges and fractional spins are known, and their violation in commonly used functionals has been shown to be the root of many major failures in practical applications. However, approximate functionals are designed for physical systems with integer charges and spins, not in terms of the fractional variables. Here we develop a general framework for extending approximate density functionals and many-electron theory to fractional-charge and fractional-spin systems. Our development allows for the fractional extension of any approximate theory that is a functional of G(0), the one-electron Green's function of the non-interacting reference system. The extension to fractional charge and fractional spin systems is based on the ensemble average of the basic variable, G(0). We demonstrate the fractional extension for the following theories: (1) any explicit functional of the one-electron density, such as the local density approximation and generalized gradient approximations; (2) any explicit functional of the one-electron density matrix of the non-interacting reference system, such as the exact exchange functional (or Hartree-Fock theory) and hybrid functionals; (3) many-body perturbation theory; and (4) random-phase approximations. A general rule for such an extension has also been derived through scaling the orbitals and should be useful for functionals where the link to the Green's function is not obvious. The development thus enables the examination of approximate theories against known exact conditions on the fractional variables and the analysis of their failures in chemical and physical applications in terms of violations of exact conditions of the energy functionals. The present work should facilitate the calculation of chemical potentials and fundamental bandgaps with approximate functionals and many-electron theories through the energy derivatives with respect to the fractional charge. It should play an important role in developing accurate approximate density functionals and many-body theory.

Density-functional theory of spherical electric double layers and zeta potentials of colloidal particles in restricted-primitive-model electrolyte solutions.

PubMed

Yu, Yang-Xin; Wu, Jianzhong; Gao, Guang-Hua

2004-04-15

A density-functional theory is proposed to describe the density profiles of small ions around an isolated colloidal particle in the framework of the restricted primitive model where the small ions have uniform size and the solvent is represented by a dielectric continuum. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for the hard-sphere repulsion and a quadratic functional Taylor expansion for the electrostatic interactions. The theoretical predictions are in good agreement with the results from Monte Carlo simulations and from previous investigations using integral-equation theory for the ionic density profiles and the zeta potentials of spherical particles at a variety of solution conditions. Like the integral-equation approaches, the density-functional theory is able to capture the oscillatory density profiles of small ions and the charge inversion (overcharging) phenomena for particles with elevated charge density. In particular, our density-functional theory predicts the formation of a second counterion layer near the surface of highly charged spherical particle. Conversely, the nonlinear Poisson-Boltzmann theory and its variations are unable to represent the oscillatory behavior of small ion distributions and charge inversion. Finally, our density-functional theory predicts charge inversion even in a 1:1 electrolyte solution as long as the salt concentration is sufficiently high. (c) 2004 American Institute of Physics.

Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals.

PubMed

Śmiga, Szymon; Fabiano, Eduardo; Laricchia, Savio; Constantin, Lucian A; Della Sala, Fabio

2015-04-21

We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded molecular systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes this limitation and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method.

Locality of correlation in density functional theory.

PubMed

Burke, Kieron; Cancio, Antonio; Gould, Tim; Pittalis, Stefano

2016-08-07

The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that EC → -AC ZlnZ + BCZ as Z → ∞, where Z is the atomic number, AC is known, and we estimate BC to be about 37 mhartree. The local density approximation yields AC exactly, but a very incorrect value for BC, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with BC a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.

Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals [On the Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mardirossian, Narbe; Ruiz Pestana, Luis; Womack, James C.

The VV10 and rVV10 nonlocal correlation functionals are consistently implemented and assessed, with the goal of determining if the rVV10 nonlocal correlation functional can replace the VV10 nonlocal correlation functional in the recently developed B97M-V density functional, to give the B97M-rV density functional. Along the way, four density functionals are simultaneously tested: VV10, rVV10, B97M-V, and B97M-rV. An initial assessment is carried out across the S22 data set, and the short-range damping variable, b, is varied for all four density functionals in order to determine the sensitivity of the functionals to the empirical parameter. The results of this test indicatemore » that a value of b = 6 (fortuitously the same as that in B97M-V) is suitable for B97M-rV. The functionals are then compared across an extensive database of interaction energies, and it is demonstrated that B97M-rV either matches or outperforms B97M-V for all of the tests considered. Finally, the optimization of b across the S22 data set is extended to two range-separated hybrid density functionals, ωB97X-V and ωB97M-V, and a value of b = 6.2 is recommended for both ωB97X-rV and ωB97M-rV.« less

Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals [On the Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals

DOE PAGES

Mardirossian, Narbe; Ruiz Pestana, Luis; Womack, James C.; ...

2016-12-06

The VV10 and rVV10 nonlocal correlation functionals are consistently implemented and assessed, with the goal of determining if the rVV10 nonlocal correlation functional can replace the VV10 nonlocal correlation functional in the recently developed B97M-V density functional, to give the B97M-rV density functional. Along the way, four density functionals are simultaneously tested: VV10, rVV10, B97M-V, and B97M-rV. An initial assessment is carried out across the S22 data set, and the short-range damping variable, b, is varied for all four density functionals in order to determine the sensitivity of the functionals to the empirical parameter. The results of this test indicatemore » that a value of b = 6 (fortuitously the same as that in B97M-V) is suitable for B97M-rV. The functionals are then compared across an extensive database of interaction energies, and it is demonstrated that B97M-rV either matches or outperforms B97M-V for all of the tests considered. Finally, the optimization of b across the S22 data set is extended to two range-separated hybrid density functionals, ωB97X-V and ωB97M-V, and a value of b = 6.2 is recommended for both ωB97X-rV and ωB97M-rV.« less

Unstable density distribution associated with equatorial plasma bubble

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kherani, E. A., E-mail: esfhan.kherani@inpe.br; Meneses, F. Carlos de; Bharuthram, R.

2016-04-15

In this work, we present a simulation study of equatorial plasma bubble (EPB) in the evening time ionosphere. The fluid simulation is performed with a high grid resolution, enabling us to probe the steepened updrafting density structures inside EPB. Inside the density depletion that eventually evolves as EPB, both density and updraft are functions of space from which the density as implicit function of updraft velocity or the density distribution function is constructed. In the present study, this distribution function and the corresponding probability distribution function are found to evolve from Maxwellian to non-Maxwellian as the initial small depletion growsmore » to EPB. This non-Maxwellian distribution is of a gentle-bump type, in confirmation with the recently reported distribution within EPB from space-borne measurements that offer favorable condition for small scale kinetic instabilities.« less

Density Functionals of Chemical Bonding

PubMed Central

Putz, Mihai V.

2008-01-01

The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846

Bypassing the Kohn-Sham equations with machine learning.

PubMed

Brockherde, Felix; Vogt, Leslie; Li, Li; Tuckerman, Mark E; Burke, Kieron; Müller, Klaus-Robert

2017-10-11

Last year, at least 30,000 scientific papers used the Kohn-Sham scheme of density functional theory to solve electronic structure problems in a wide variety of scientific fields. Machine learning holds the promise of learning the energy functional via examples, bypassing the need to solve the Kohn-Sham equations. This should yield substantial savings in computer time, allowing larger systems and/or longer time-scales to be tackled, but attempts to machine-learn this functional have been limited by the need to find its derivative. The present work overcomes this difficulty by directly learning the density-potential and energy-density maps for test systems and various molecules. We perform the first molecular dynamics simulation with a machine-learned density functional on malonaldehyde and are able to capture the intramolecular proton transfer process. Learning density models now allows the construction of accurate density functionals for realistic molecular systems.Machine learning allows electronic structure calculations to access larger system sizes and, in dynamical simulations, longer time scales. Here, the authors perform such a simulation using a machine-learned density functional that avoids direct solution of the Kohn-Sham equations.

Multiple Point Dynamic Gas Density Measurements Using Molecular Rayleigh Scattering

NASA Technical Reports Server (NTRS)

Seasholtz, Richard; Panda, Jayanta

1999-01-01

A nonintrusive technique for measuring dynamic gas density properties is described. Molecular Rayleigh scattering is used to measure the time-history of gas density simultaneously at eight spatial locations at a 50 kHz sampling rate. The data are analyzed using the Welch method of modified periodograms to reduce measurement uncertainty. Cross-correlations, power spectral density functions, cross-spectral density functions, and coherence functions may be obtained from the data. The technique is demonstrated using low speed co-flowing jets with a heated inner jet.

Modeling solubility of CO2/hydrocarbon gas in ionic liquid ([emim][FAP]) using Aspen Plus simulations.

PubMed

Bagchi, Bishwadeep; Sati, Sushmita; Shilapuram, Vidyasagar

2017-08-01

The Peng-Robinson equation of state with quadratic van der Waals (vdW) mixing rule model was chosen to perform the thermodynamic calculations in Flash3 column of Aspen Plus to predict the solubility of CO 2 or any one of the hydrocarbons (HCs) among methane, ethane, propane, and butane in an ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([emim][FAP]). Bubble point pressure, solubility, bubble point temperature, fugacity, and partial molar volume at infinite dilution were obtained from the simulations, and enthalpy of absorption, Gibbs free energy of solvation, and entropy change of absorption were estimated by thermodynamic relations. Results show that carbon chain length has a significant effect on the bubble point pressure. Methane has the highest bubble point pressure among all the considered HCs and CO 2 . The bubble point pressure and fugacity variation with temperature is different for CO 2 as compared to HCs for mole fractions above 0.2. Two different profiles are noticed for enthalpy of absorption when plotted as a function of mole fraction of gas soluble in IL. Partial molar volume of CO 2 decreases with increase in temperature in [emim][FAP], while it is increased for HCs. Bubble point temperature decreases with increase in the mole fraction of the solute. Entropy of solvation increases with temperature till a particular value followed by a decrease with further increase in temperature. Gibbs free energy change of solvation showed that the process of solubility was spontaneous.

Knowledge-based grouping of modeled HLA peptide complexes.

PubMed

Kangueane, P; Sakharkar, M K; Lim, K S; Hao, H; Lin, K; Chee, R E; Kolatkar, P R

2000-05-01

Human leukocyte antigens are the most polymorphic of human genes and multiple sequence alignment shows that such polymorphisms are clustered in the functional peptide binding domains. Because of such polymorphism among the peptide binding residues, the prediction of peptides that bind to specific HLA molecules is very difficult. In recent years two different types of computer based prediction methods have been developed and both the methods have their own advantages and disadvantages. The nonavailability of allele specific binding data restricts the use of knowledge-based prediction methods for a wide range of HLA alleles. Alternatively, the modeling scheme appears to be a promising predictive tool for the selection of peptides that bind to specific HLA molecules. The scoring of the modeled HLA-peptide complexes is a major concern. The use of knowledge based rules (van der Waals clashes and solvent exposed hydrophobic residues) to distinguish binders from nonbinders is applied in the present study. The rules based on (1) number of observed atomic clashes between the modeled peptide and the HLA structure, and (2) number of solvent exposed hydrophobic residues on the modeled peptide effectively discriminate experimentally known binders from poor/nonbinders. Solved crystal complexes show no vdW Clash (vdWC) in 95% cases and no solvent exposed hydrophobic peptide residues (SEHPR) were seen in 86% cases. In our attempt to compare experimental binding data with the predicted scores by this scoring scheme, 77% of the peptides are correctly grouped as good binders with a sensitivity of 71%.

2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

NASA Astrophysics Data System (ADS)

Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

2017-09-01

Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

Statistics of primordial density perturbations from discrete seed masses

NASA Technical Reports Server (NTRS)

Scherrer, Robert J.; Bertschinger, Edmund

1991-01-01

The statistics of density perturbations for general distributions of seed masses with arbitrary matter accretion is examined. Formal expressions for the power spectrum, the N-point correlation functions, and the density distribution function are derived. These results are applied to the case of uncorrelated seed masses, and power spectra are derived for accretion of both hot and cold dark matter plus baryons. The reduced moments (cumulants) of the density distribution are computed and used to obtain a series expansion for the density distribution function. Analytic results are obtained for the density distribution function in the case of a distribution of seed masses with a spherical top-hat accretion pattern. More generally, the formalism makes it possible to give a complete characterization of the statistical properties of any random field generated from a discrete linear superposition of kernels. In particular, the results can be applied to density fields derived by smoothing a discrete set of points with a window function.

Two-Component Noncollinear Time-Dependent Spin Density Functional Theory for Excited State Calculations.

PubMed

Egidi, Franco; Sun, Shichao; Goings, Joshua J; Scalmani, Giovanni; Frisch, Michael J; Li, Xiaosong

2017-06-13

We present a linear response formalism for the description of the electronic excitations of a noncollinear reference defined via Kohn-Sham spin density functional methods. A set of auxiliary variables, defined using the density and noncollinear magnetization density vector, allows the generalization of spin density functional kernels commonly used in collinear DFT to noncollinear cases, including local density, GGA, meta-GGA and hybrid functionals. Working equations and derivations of functional second derivatives with respect to the noncollinear density, required in the linear response noncollinear TDDFT formalism, are presented in this work. This formalism takes all components of the spin magnetization into account independent of the type of reference state (open or closed shell). As a result, the method introduced here is able to afford a nonzero local xc torque on the spin magnetization while still satisfying the zero-torque theorem globally. The formalism is applied to a few test cases using the variational exact-two-component reference including spin-orbit coupling to illustrate the capabilities of the method.

Work-function calculations for a symmetrical total-charge-density profile at the metallic surface

NASA Astrophysics Data System (ADS)

Wojciechowski, K. F.; Sobańska-Nowotnik, M.

1983-07-01

It is shown that, if the total-charge-density profile nT(x) at the surface of jellium satisfies the Budd-Vannimenus constraint and also is a symmetrical function of x, relative to the ordinate axis, then the work-function variation versus the Wigner-Seitz radius rs does not depend on the form of nT(x). Also the simple linear-density profile is used to calculate the work function by application of the variational principle for the energy, including the first and second density-gradient corrections to the kinetic energy and the first gradient correction to the exchange and correlation energy. The results for the work function are in good agreement with the polycrystalline values for low-density metals.

Relativistic density functional theory with picture-change corrected electron density based on infinite-order Douglas-Kroll-Hess method

NASA Astrophysics Data System (ADS)

Oyama, Takuro; Ikabata, Yasuhiro; Seino, Junji; Nakai, Hiromi

2017-07-01

This Letter proposes a density functional treatment based on the two-component relativistic scheme at the infinite-order Douglas-Kroll-Hess (IODKH) level. The exchange-correlation energy and potential are calculated using the electron density based on the picture-change corrected density operator transformed by the IODKH method. Numerical assessments indicated that the picture-change uncorrected density functional terms generate significant errors, on the order of hartree for heavy atoms. The present scheme was found to reproduce the energetics in the four-component treatment with high accuracy.

Restoring the consistency with the contact density theorem of a classical density functional theory of ions at a planar electrical double layer.

PubMed

Gillespie, Dirk

2014-11-01

Classical density functional theory (DFT) of fluids is a fast and efficient theory to compute the structure of the electrical double layer in the primitive model of ions where ions are modeled as charged, hard spheres in a background dielectric. While the hard-core repulsive component of this ion-ion interaction can be accurately computed using well-established DFTs, the electrostatic component is less accurate. Moreover, many electrostatic functionals fail to satisfy a basic theorem, the contact density theorem, that relates the bulk pressure, surface charge, and ion densities at their distances of closest approach for ions in equilibrium at a smooth, hard, planar wall. One popular electrostatic functional that fails to satisfy the contact density theorem is a perturbation approach developed by Kierlik and Rosinberg [Phys. Rev. A 44, 5025 (1991)PLRAAN1050-294710.1103/PhysRevA.44.5025] and Rosenfeld [J. Chem. Phys. 98, 8126 (1993)JCPSA60021-960610.1063/1.464569], where the full free-energy functional is Taylor-expanded around a bulk (homogeneous) reference fluid. Here, it is shown that this functional fails to satisfy the contact density theorem because it also fails to satisfy the known low-density limit. When the functional is corrected to satisfy this limit, a corrected bulk pressure is derived and it is shown that with this pressure both the contact density theorem and the Gibbs adsorption theorem are satisfied.

Density functional with full exact exchange, balanced nonlocality of correlations, and constraint satisfaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Jianmin; Perdew, John P; Staroverov, Viktor N

2008-01-01

We construct a nonlocal density functional approximation with full exact exchange, while preserving the constraint-satisfaction approach and justified error cancellations of simpler semilocal functionals. This is achieved by interpolating between different approximations suitable for two extreme regions of the electron density. In a 'normal' region, the exact exchange-correlation hole density around an electron is semilocal because its spatial range is reduced by correlation and because it integrates over a narrow range to -1. These regions are well described by popular semilocal approximations (many of which have been constructed nonempirically), because of proper accuracy for a slowly-varying density or because ofmore » error cancellation between exchange and correlation. 'Abnormal' regions, where non locality is unveiled, include those in which exchange can dominate correlation (one-electron, nonuniform high-density, and rapidly-varying limits), and those open subsystems of fluctuating electron number over which the exact exchange-correlation hole integrates to a value greater than -1. Regions between these extremes are described by a hybrid functional mixing exact and semi local exchange energy densities locally (i.e., with a mixing fraction that is a function of position r and a functional of the density). Because our mixing fraction tends to 1 in the high-density limit, we employ full exact exchange according to the rigorous definition of the exchange component of any exchange-correlation energy functional. Use of full exact exchange permits the satisfaction of many exact constraints, but the nonlocality of exchange also requires balanced nonlocality of correlation. We find that this nonlocality can demand at least five empirical parameters (corresponding roughly to the four kinds of abnormal regions). Our local hybrid functional is perhaps the first accurate size-consistent density functional with full exact exchange. It satisfies other known exact constraints, including exactness for all one-electron densities, and provides an excellent, fit 1.0 the 223 molecular enthalpies of formation of the G3/99 set and the 42 reaction barrier heights of the BH42/03 set, improving both (but especially the latter) over most semilocal functionals and global hybrids. Exact constraints, physical insights, and paradigm examples hopefully suppress 'overfitting'.« less

Raman Optical Activity Spectra from Density Functional Perturbation Theory and Density-Functional-Theory-Based Molecular Dynamics.

PubMed

Luber, Sandra

2017-03-14

We describe the calculation of Raman optical activity (ROA) tensors from density functional perturbation theory, which has been implemented into the CP2K software package. Using the mixed Gaussian and plane waves method, ROA spectra are evaluated in the double-harmonic approximation. Moreover, an approach for the calculation of ROA spectra by means of density functional theory-based molecular dynamics is derived and used to obtain an ROA spectrum via time correlation functions, which paves the way for the calculation of ROA spectra taking into account anharmonicities and dynamic effects at ambient conditions.

Exact density functional theory for ideal polymer fluids with nearest neighbor bonding constraints.

PubMed

Woodward, Clifford E; Forsman, Jan

2008-08-07

We present a new density functional theory of ideal polymer fluids, assuming nearest-neighbor bonding constraints. The free energy functional is expressed in terms of end site densities of chain segments and thus has a simpler mathematical structure than previously used expressions using multipoint distributions. This work is based on a formalism proposed by Tripathi and Chapman [Phys. Rev. Lett. 94, 087801 (2005)]. Those authors obtain an approximate free energy functional for ideal polymers in terms of monomer site densities. Calculations on both repulsive and attractive surfaces show that their theory is reasonably accurate in some cases, but does differ significantly from the exact result for longer polymers with attractive surfaces. We suggest that segment end site densities, rather than monomer site densities, are the preferred choice of "site functions" for expressing the free energy functional of polymer fluids. We illustrate the application of our theory to derive an expression for the free energy of an ideal fluid of infinitely long polymers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Constantin, Lucian A.; Fabiano, Eduardo; Della Sala, Fabio

We introduce a novel non-local ingredient for the construction of exchange density functionals: the reduced Hartree parameter, which is invariant under the uniform scaling of the density and represents the exact exchange enhancement factor for one- and two-electron systems. The reduced Hartree parameter is used together with the conventional meta-generalized gradient approximation (meta-GGA) semilocal ingredients (i.e., the electron density, its gradient, and the kinetic energy density) to construct a new generation exchange functional, termed u-meta-GGA. This u-meta-GGA functional is exact for the exchange of any one- and two-electron systems, is size-consistent and non-empirical, satisfies the uniform density scaling relation, andmore » recovers the modified gradient expansion derived from the semiclassical atom theory. For atoms, ions, jellium spheres, and molecules, it shows a good accuracy, being often better than meta-GGA exchange functionals. Our construction validates the use of the reduced Hartree ingredient in exchange-correlation functional development, opening the way to an additional rung in the Jacob’s ladder classification of non-empirical density functionals.« less

Microscopically based energy density functionals for nuclei using the density matrix expansion: Implementation and pre-optimization

NASA Astrophysics Data System (ADS)

Stoitsov, M.; Kortelainen, M.; Bogner, S. K.; Duguet, T.; Furnstahl, R. J.; Gebremariam, B.; Schunck, N.

2010-11-01

In a recent series of articles, Gebremariam, Bogner, and Duguet derived a microscopically based nuclear energy density functional by applying the density matrix expansion (DME) to the Hartree-Fock energy obtained from chiral effective field theory two- and three-nucleon interactions. Owing to the structure of the chiral interactions, each coupling in the DME functional is given as the sum of a coupling constant arising from zero-range contact interactions and a coupling function of the density arising from the finite-range pion exchanges. Because the contact contributions have essentially the same structure as those entering empirical Skyrme functionals, a microscopically guided Skyrme phenomenology has been suggested in which the contact terms in the DME functional are released for optimization to finite-density observables to capture short-range correlation energy contributions from beyond Hartree-Fock. The present article is the first attempt to assess the ability of the newly suggested DME functional, which has a much richer set of density dependencies than traditional Skyrme functionals, to generate sensible and stable results for nuclear applications. The results of the first proof-of-principle calculations are given, and numerous practical issues related to the implementation of the new functional in existing Skyrme codes are discussed. Using a restricted singular value decomposition optimization procedure, it is found that the new DME functional gives numerically stable results and exhibits a small but systematic reduction of our test χ2 function compared to standard Skyrme functionals, thus justifying its suitability for future global optimizations and large-scale calculations.

A reference-modified density functional theory: An application to solvation free-energy calculations for a Lennard-Jones solution.

PubMed

Sumi, Tomonari; Maruyama, Yutaka; Mitsutake, Ayori; Koga, Kenichiro

2016-06-14

In the conventional classical density functional theory (DFT) for simple fluids, an ideal gas is usually chosen as the reference system because there is a one-to-one correspondence between the external field and the density distribution function, and the exact intrinsic free-energy functional is available for the ideal gas. In this case, the second-order density functional Taylor series expansion of the excess intrinsic free-energy functional provides the hypernetted-chain (HNC) approximation. Recently, it has been shown that the HNC approximation significantly overestimates the solvation free energy (SFE) for an infinitely dilute Lennard-Jones (LJ) solution, especially when the solute particles are several times larger than the solvent particles [T. Miyata and J. Thapa, Chem. Phys. Lett. 604, 122 (2014)]. In the present study, we propose a reference-modified density functional theory as a systematic approach to improve the SFE functional as well as the pair distribution functions. The second-order density functional Taylor series expansion for the excess part of the intrinsic free-energy functional in which a hard-sphere fluid is introduced as the reference system instead of an ideal gas is applied to the LJ pure and infinitely dilute solution systems and is proved to remarkably improve the drawbacks of the HNC approximation. Furthermore, the third-order density functional expansion approximation in which a factorization approximation is applied to the triplet direct correlation function is examined for the LJ systems. We also show that the third-order contribution can yield further refinements for both the pair distribution function and the excess chemical potential for the pure LJ liquids.

Basis convergence of range-separated density-functional theory.

PubMed

Franck, Odile; Mussard, Bastien; Luppi, Eleonora; Toulouse, Julien

2015-02-21

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with cardinal number X of the Dunning basis sets cc - p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

Use of selection indices to model the functional response of predators

USGS Publications Warehouse

Joly, D.O.; Patterson, B.R.

2003-01-01

The functional response of a predator to changing prey density is an important determinant of stability of predatora??prey systems. We show how Manly's selection indices can be used to distinguish between hyperbolic and sigmoidal models of a predator functional response to primary prey density in the presence of alternative prey. Specifically, an inverse relationship between prey density and preference for that prey results in a hyperbolic functional response while a positive relationship can yield either a hyperbolic or sigmoidal functional response, depending on the form and relative magnitudes of the density-dependent preference model, attack rate, and handling time. As an example, we examine wolf (Canis lupus) functional response to moose (Alces alces) density in the presence of caribou (Rangifer tarandus). The use of selection indices to evaluate the form of the functional response has significant advantages over previous attempts to fit Holling's functional response curves to killing-rate data directly, including increased sensitivity, use of relatively easily collected data, and consideration of other explanatory factors (e.g., weather, seasons, productivity).

Locality of correlation in density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, Kieron; Cancio, Antonio; Gould, Tim

The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that E{sub C} → −A{sub C} ZlnZ +more » B{sub C}Z as Z → ∞, where Z is the atomic number, A{sub C} is known, and we estimate B{sub C} to be about 37 mhartree. The local density approximation yields A{sub C} exactly, but a very incorrect value for B{sub C}, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with B{sub C} a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.« less

Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error.

PubMed

Bao, Junwei Lucas; Wang, Ying; He, Xiao; Gagliardi, Laura; Truhlar, Donald G

2017-11-16

Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.

Generalization of the Kohn-Sham system that can represent arbitrary one-electron density matrices

DOE PAGES

Hubertus J. J. van Dam

2016-04-27

Density functional theory is currently the most widely applied method in electronic structure theory. The Kohn-Sham method, based on a fictitious system of noninteracting particles, is the workhorse of the theory. The particular form of the Kohn-Sham wave function admits only idempotent one-electron density matrices whereas wave functions of correlated electrons in post-Hartree-Fock methods invariably have fractional occupation numbers. Here we show that by generalizing the orbital concept and introducing a suitable dot product as well as a probability density, a noninteracting system can be chosen that can represent the one-electron density matrix of any system, even one with fractionalmore » occupation numbers. This fictitious system ensures that the exact electron density is accessible within density functional theory. It can also serve as the basis for reduced density matrix functional theory. Moreover, to aid the analysis of the results the orbitals may be assigned energies from a mean-field Hamiltonian. This produces energy levels that are akin to Hartree-Fock orbital energies such that conventional analyses based on Koopmans' theorem are available. Lastly, this system is convenient in formalisms that depend on creation and annihilation operators as they are trivially applied to single-determinant wave functions.« less

Microscopically based energy density functionals for nuclei using the density matrix expansion. II. Full optimization and validation

NASA Astrophysics Data System (ADS)

Navarro Pérez, R.; Schunck, N.; Dyhdalo, A.; Furnstahl, R. J.; Bogner, S. K.

2018-05-01

Background: Energy density functional methods provide a generic framework to compute properties of atomic nuclei starting from models of nuclear potentials and the rules of quantum mechanics. Until now, the overwhelming majority of functionals have been constructed either from empirical nuclear potentials such as the Skyrme or Gogny forces, or from systematic gradient-like expansions in the spirit of the density functional theory for atoms. Purpose: We seek to obtain a usable form of the nuclear energy density functional that is rooted in the modern theory of nuclear forces. We thus consider a functional obtained from the density matrix expansion of local nuclear potentials from chiral effective field theory. We propose a parametrization of this functional carefully calibrated and validated on selected ground-state properties that is suitable for large-scale calculations of nuclear properties. Methods: Our energy functional comprises two main components. The first component is a non-local functional of the density and corresponds to the direct part (Hartree term) of the expectation value of local chiral potentials on a Slater determinant. Contributions to the mean field and the energy of this term are computed by expanding the spatial, finite-range components of the chiral potential onto Gaussian functions. The second component is a local functional of the density and is obtained by applying the density matrix expansion to the exchange part (Fock term) of the expectation value of the local chiral potential. We apply the UNEDF2 optimization protocol to determine the coupling constants of this energy functional. Results: We obtain a set of microscopically constrained functionals for local chiral potentials from leading order up to next-to-next-to-leading order with and without three-body forces and contributions from Δ excitations. These functionals are validated on the calculation of nuclear and neutron matter, nuclear mass tables, single-particle shell structure in closed-shell nuclei, and the fission barrier of 240Pu. Quantitatively, they perform noticeably better than the more phenomenological Skyrme functionals. Conclusions: The inclusion of higher-order terms in the chiral perturbation expansion seems to produce a systematic improvement in predicting nuclear binding energies while the impact on other observables is not really significant. This result is especially promising since all the fits have been performed at the single-reference level of the energy density functional approach, where important collective correlations such as center-of-mass correction, rotational correction, or zero-point vibrational energies have not been taken into account yet.

Influence of the volume and density functions within geometric models for estimating trunk inertial parameters.

PubMed

Wicke, Jason; Dumas, Genevieve A

2010-02-01

The geometric method combines a volume and a density function to estimate body segment parameters and has the best opportunity for developing the most accurate models. In the trunk, there are many different tissues that greatly differ in density (e.g., bone versus lung). Thus, the density function for the trunk must be particularly sensitive to capture this diversity, such that accurate inertial estimates are possible. Three different models were used to test this hypothesis by estimating trunk inertial parameters of 25 female and 24 male college-aged participants. The outcome of this study indicates that the inertial estimates for the upper and lower trunk are most sensitive to the volume function and not very sensitive to the density function. Although it appears that the uniform density function has a greater influence on inertial estimates in the lower trunk region than in the upper trunk region, this is likely due to the (overestimated) density value used. When geometric models are used to estimate body segment parameters, care must be taken in choosing a model that can accurately estimate segment volumes. Researchers wanting to develop accurate geometric models should focus on the volume function, especially in unique populations (e.g., pregnant or obese individuals).

Recent developments in LIBXC - A comprehensive library of functionals for density functional theory

NASA Astrophysics Data System (ADS)

Lehtola, Susi; Steigemann, Conrad; Oliveira, Micael J. T.; Marques, Miguel A. L.

2018-01-01

LIBXC is a library of exchange-correlation functionals for density-functional theory. We are concerned with semi-local functionals (or the semi-local part of hybrid functionals), namely local-density approximations, generalized-gradient approximations, and meta-generalized-gradient approximations. Currently we include around 400 functionals for the exchange, correlation, and the kinetic energy, spanning more than 50 years of research. Moreover, LIBXC is by now used by more than 20 codes, not only from the atomic, molecular, and solid-state physics, but also from the quantum chemistry communities.

A meta-GGA level screened range-separated hybrid functional by employing short range Hartree-Fock with a long range semilocal functional.

PubMed

Jana, Subrata; Samal, Prasanjit

2018-03-28

The range-separated hybrid density functionals are very successful in describing a wide range of molecular and solid-state properties accurately. In principle, such functionals are designed from spherically averaged or system averaged as well as reverse engineered exchange holes. In the present attempt, the screened range-separated hybrid functional scheme has been applied to the meta-GGA rung by using the density matrix expansion based semilocal exchange hole (or functional). The hybrid functional proposed here utilizes the spherically averaged density matrix expansion based exchange hole in the range separation scheme. For slowly varying density correction the range separation scheme is employed only through the local density approximation based exchange hole coupled with the corresponding fourth order gradient approximate Tao-Mo enhancement factor. The comprehensive testing and performance of the newly constructed functional indicates its applicability in describing several molecular properties. The most appealing feature of this present screened hybrid functional is that it will be practically very useful in describing solid-state properties at the meta-GGA level.

The large-scale correlations of multicell densities and profiles: implications for cosmic variance estimates

NASA Astrophysics Data System (ADS)

Codis, Sandrine; Bernardeau, Francis; Pichon, Christophe

2016-08-01

In order to quantify the error budget in the measured probability distribution functions of cell densities, the two-point statistics of cosmic densities in concentric spheres is investigated. Bias functions are introduced as the ratio of their two-point correlation function to the two-point correlation of the underlying dark matter distribution. They describe how cell densities are spatially correlated. They are computed here via the so-called large deviation principle in the quasi-linear regime. Their large-separation limit is presented and successfully compared to simulations for density and density slopes: this regime is shown to be rapidly reached allowing to get sub-percent precision for a wide range of densities and variances. The corresponding asymptotic limit provides an estimate of the cosmic variance of standard concentric cell statistics applied to finite surveys. More generally, no assumption on the separation is required for some specific moments of the two-point statistics, for instance when predicting the generating function of cumulants containing any powers of concentric densities in one location and one power of density at some arbitrary distance from the rest. This exact `one external leg' cumulant generating function is used in particular to probe the rate of convergence of the large-separation approximation.

A Density Functional for Liquid 3He Based on the Aziz Potential

NASA Astrophysics Data System (ADS)

Barranco, M.; Hernández, E. S.; Mayol, R.; Navarro, J.; Pi, M.; Szybisz, L.

2006-09-01

We propose a new class of density functionals for liquid 3He based on the Aziz helium-helium interaction screened at short distances by the microscopically calculated two-body distribution function g(r). Our aim is to reduce to a minumum the unavoidable phenomenological ingredients inherent to any density functional approach. Results for the homogeneous liquid and droplets are presented and discussed.

LSMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenbach, Markus; Li, Ying Wai; Liu, Xianglin

2017-12-01

LSMS is a first principles, Density Functional theory based, electronic structure code targeted mainly at materials applications. LSMS calculates the local spin density approximation to the diagonal part of the electron Green's function. The electron/spin density and energy are easily determined once the Green's function is known. Linear scaling with system size is achieved in the LSMS by using several unique properties of the real space multiple scattering approach to the Green's function.

The Naval Reserve Sea Air Mariner VOTECH (Vocational/Technical) Program: Qualified Civilian Schools for Ramp (Reserve Allied Medical Personnel Program)

DTIC Science & Technology

1985-09-15

l= C~tl Ffm R ~ s .8 isnMs?.y91 ed*% i ClassCap 116j 819= ia 2: 1.11.87 4 eed Vd.W1, AC.~aA I -ýS S 3601ŕ - __ =V3 EC=t8 I14 Ce’s Nee0’Rs-1 1987...8050551a 10106%8316- Ca’tilvtV-1-a2g-i- -,:! 2~ ~~ 55Br AV-S 3203 acca - C.-o- V V Klta MD $3Mcc14en R" C-n-VAr-M R’y’~oo M -ey r eca tt w 2 c-r *U. flgrD...A t62O24242100 E. Hcnrkt Rd. T- acca indumm Vocatonnal Technica Rochestr NY 14M2 State Te€]b- Inttt as Mmpbk A,• 4100 Co,ean Rd. 1I6) 424,-5M0 5993

Projections of Demand for Waterborne Transportation, Ohio River Basin, 1980, 1990, 2000, 2020, 2040. Volume 9. Group VII. Ores and Minerals.

DTIC Science & Technology

1980-12-01

U l 0 0 ) C 4140 c4 34jE 04 0)t 03.- In lo No ID 0ID 6)ID M). U 0 ( in cc m m m c m mm m a a) la.0u) 0r- 02d)20 C ’N C ~ 3 C -27- c -o 0 It14’ 0 14 tn...N 1.D/ c4 0)00E w.~ 0 V-- -"- -- V04 M1)4VdW -4I -..- 1. 0001M.-40 00 4D4J.’ ::l c:; Q o u00 0 0.0 a 0~~ ~ m𔃺 w , 0-0m.-Q)uH 1.4 0 : . 0 4140 .0 ZZl...Statistical Report. 1969-78 eds. Washington, D.C.: AISI , 1970-79. American Metal Market. Metal Statistics. 1970 -d. New York: Fairchild, 1976. "Facts and

Spin-Flavor van der Waals Forces and NN interaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alvaro Calle Cordon, Enrique Ruiz Arriola

A major goal in Nuclear Physics is the derivation of the Nucleon-Nucleon (NN) interaction from Quantum Chromodynamics (QCD). In QCD the fundamental degrees of freedom are colored quarks and gluons which are confined to form colorless strongly interacting hadrons. Because of this the resulting nuclear forces at sufficiently large distances correspond to spin-flavor excitations, very much like the dipole excitations generating the van der Waals (vdW) forces acting between atoms. We study the Nucleon-Nucleon interaction in the Born-Oppenheimer approximation at second order in perturbation theory including the Delta resonance as an intermediate state. The potential resembles strongly chiral potentials computedmore » either via soliton models or chiral perturbation theory and has a van der Waals like singularity at short distances which is handled by means of renormalization techniques. Results for the deuteron are discussed.« less

Force Density Function Relationships in 2-D Granular Media

NASA Technical Reports Server (NTRS)

Youngquist, Robert C.; Metzger, Philip T.; Kilts, Kelly N.

2004-01-01

An integral transform relationship is developed to convert between two important probability density functions (distributions) used in the study of contact forces in granular physics. Developing this transform has now made it possible to compare and relate various theoretical approaches with one another and with the experimental data despite the fact that one may predict the Cartesian probability density and another the force magnitude probability density. Also, the transforms identify which functional forms are relevant to describe the probability density observed in nature, and so the modified Bessel function of the second kind has been identified as the relevant form for the Cartesian probability density corresponding to exponential forms in the force magnitude distribution. Furthermore, it is shown that this transform pair supplies a sufficient mathematical framework to describe the evolution of the force magnitude distribution under shearing. Apart from the choice of several coefficients, whose evolution of values must be explained in the physics, this framework successfully reproduces the features of the distribution that are taken to be an indicator of jamming and unjamming in a granular packing. Key words. Granular Physics, Probability Density Functions, Fourier Transforms

Bluegill growth as modified by plant density: an exploration of underlying mechanisms

USGS Publications Warehouse

Savino, Jacqueline F.; Marschall, Elizabeth A.; Stein, Roy A.

1992-01-01

Bluegill (Lepomis macrochira) growth varies inconsistently with plant density. In laboratory and field experiments, we explored mechanisms underlying bluegill growth as a function of plant and invertebrate density. In the laboratory, bluegills captured more chironomids (Chironomus riparius) than damselflies (Enallagma spp. and Ischnura spp.), but energy intake per time spent searching did not differ between damselfly and chironomid treatments. From laboratory data, we described prey encounter rates as functions of plant and invertebrate density. In Clark Lake, Ohio, we created 0.05-ha mesocosms of inshore vegetation to generate macrophyte densities of 125, 270, and 385 stems/m2 of Potamogeton and Ceratophyllum and added 46-mm bluegill (1/m2). In these mesocosms, invertebrate density increased as a function of macrophyte density. Combining this function with encounter rate functions derived from laboratory data, we predicted that bluegill growth should peak at a high macrophyte density, greater than 1000 stems/m2, even though growth should change only slightly beyond 100 stems/m2. Consistent with our predictions, bluegills did not grow differentially, nor did their use of different prey taxa differ, across macrophyte densities in the field. Bluegills preferred chironomid pupae, which were relatively few in numbers but vulnerable to predation, whereas more cryptic, chironomid larvae, which were associated with vegetation but were relatively abundant, were eaten as encountered. Bluegill avoided physid snails. Contrary to previous work, vegetation did not influence growth or diet of bluegill beyond relatively low densities owing to the interaction between capture probabilities and macroinvertebrate densities.

Assessing Density Functionals Using Many Body Theory for Hybrid Perovskites

NASA Astrophysics Data System (ADS)

Bokdam, Menno; Lahnsteiner, Jonathan; Ramberger, Benjamin; Schäfer, Tobias; Kresse, Georg

2017-10-01

Which density functional is the "best" for structure simulations of a particular material? A concise, first principles, approach to answer this question is presented. The random phase approximation (RPA)—an accurate many body theory—is used to evaluate various density functionals. To demonstrate and verify the method, we apply it to the hybrid perovskite MAPbI3 , a promising new solar cell material. The evaluation is done by first creating finite temperature ensembles for small supercells using RPA molecular dynamics, and then evaluating the variance between the RPA and various approximate density functionals for these ensembles. We find that, contrary to recent suggestions, van der Waals functionals do not improve the description of the material, whereas hybrid functionals and the strongly constrained appropriately normed (SCAN) density functional yield very good agreement with the RPA. Finally, our study shows that in the room temperature tetragonal phase of MAPbI3 , the molecules are preferentially parallel to the shorter lattice vectors but reorientation on ps time scales is still possible.

Analytical gradients for subsystem density functional theory within the slater-function-based amsterdam density functional program.

PubMed

Schlüns, Danny; Franchini, Mirko; Götz, Andreas W; Neugebauer, Johannes; Jacob, Christoph R; Visscher, Lucas

2017-02-05

We present a new implementation of analytical gradients for subsystem density-functional theory (sDFT) and frozen-density embedding (FDE) into the Amsterdam Density Functional program (ADF). The underlying theory and necessary expressions for the implementation are derived and discussed in detail for various FDE and sDFT setups. The parallel implementation is numerically verified and geometry optimizations with different functional combinations (LDA/TF and PW91/PW91K) are conducted and compared to reference data. Our results confirm that sDFT-LDA/TF yields good equilibrium distances for the systems studied here (mean absolute deviation: 0.09 Å) compared to reference wave-function theory results. However, sDFT-PW91/PW91k quite consistently yields smaller equilibrium distances (mean absolute deviation: 0.23 Å). The flexibility of our new implementation is demonstrated for an HCN-trimer test system, for which several different setups are applied. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.

PubMed

Chen, Zehua; Zhang, Du; Jin, Ye; Yang, Yang; Su, Neil Qiang; Yang, Weitao

2017-09-21

To describe static correlation, we develop a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We show that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn-Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle-particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical results show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

Basis convergence of range-separated density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Franck, Odile, E-mail: odile.franck@etu.upmc.fr; Mussard, Bastien, E-mail: bastien.mussard@upmc.fr; CNRS, UMR 7616, Laboratoire de Chimie Théorique, F-75005 Paris

2015-02-21

Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. Wemore » study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N{sub 2}, and H{sub 2}O) with cardinal number X of the Dunning basis sets cc − p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.« less

Functional renormalization group and Kohn-Sham scheme in density functional theory

NASA Astrophysics Data System (ADS)

Liang, Haozhao; Niu, Yifei; Hatsuda, Tetsuo

2018-04-01

Deriving accurate energy density functional is one of the central problems in condensed matter physics, nuclear physics, and quantum chemistry. We propose a novel method to deduce the energy density functional by combining the idea of the functional renormalization group and the Kohn-Sham scheme in density functional theory. The key idea is to solve the renormalization group flow for the effective action decomposed into the mean-field part and the correlation part. Also, we propose a simple practical method to quantify the uncertainty associated with the truncation of the correlation part. By taking the φ4 theory in zero dimension as a benchmark, we demonstrate that our method shows extremely fast convergence to the exact result even for the highly strong coupling regime.

Rational Density Functional Selection Using Game Theory.

PubMed

McAnanama-Brereton, Suzanne; Waller, Mark P

2018-01-22

Theoretical chemistry has a paradox of choice due to the availability of a myriad of density functionals and basis sets. Traditionally, a particular density functional is chosen on the basis of the level of user expertise (i.e., subjective experiences). Herein we circumvent the user-centric selection procedure by describing a novel approach for objectively selecting a particular functional for a given application. We achieve this by employing game theory to identify optimal functional/basis set combinations. A three-player (accuracy, complexity, and similarity) game is devised, through which Nash equilibrium solutions can be obtained. This approach has the advantage that results can be systematically improved by enlarging the underlying knowledge base, and the deterministic selection procedure mathematically justifies the density functional and basis set selections.

The maximal-density mass function for primordial black hole dark matter

NASA Astrophysics Data System (ADS)

Lehmann, Benjamin V.; Profumo, Stefano; Yant, Jackson

2018-04-01

The advent of gravitational wave astronomy has rekindled interest in primordial black holes (PBH) as a dark matter candidate. As there are many different observational probes of the PBH density across different masses, constraints on PBH models are dependent on the functional form of the PBH mass function. This complicates general statements about the mass functions allowed by current data, and, in particular, about the maximum total density of PBH. Numerical studies suggest that some forms of extended mass functions face tighter constraints than monochromatic mass functions, but they do not preclude the existence of a functional form for which constraints are relaxed. We use analytical arguments to show that the mass function which maximizes the fraction of the matter density in PBH subject to all constraints is a finite linear combination of monochromatic mass functions. We explicitly compute the maximum fraction of dark matter in PBH for different combinations of current constraints, allowing for total freedom of the mass function. Our framework elucidates the dependence of the maximum PBH density on the form of observational constraints, and we discuss the implications of current and future constraints for the viability of the PBH dark matter paradigm.

Derivative discontinuity and exchange-correlation potential of meta-GGAs in density-functional theory.

PubMed

Eich, F G; Hellgren, Maria

2014-12-14

We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state and exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative.

Derivative discontinuity and exchange-correlation potential of meta-GGAs in density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eich, F. G., E-mail: eichf@missouri.edu; Hellgren, Maria

2014-12-14

We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state andmore » exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative.« less

Spectral function from Reduced Density Matrix Functional Theory

NASA Astrophysics Data System (ADS)

Romaniello, Pina; di Sabatino, Stefano; Berger, Jan A.; Reining, Lucia

2015-03-01

In this work we focus on the calculation of the spectral function, which determines, for example, photoemission spectra, from reduced density matrix functional theory. Starting from its definition in terms of the one-body Green's function we derive an expression for the spectral function that depends on the natural occupation numbers and on an effective energy which accounts for all the charged excitations. This effective energy depends on the two-body as well as higher-order density matrices. Various approximations to this expression are explored by using the exactly solvable Hubbard chains.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

DOE PAGES

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

2018-03-13

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

Understanding PGM-free Catalysts by Linking Density Functional Theory Calculations and Structural Analysis: Perspectives and Challenges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonzales, Ivana; Artyushkova, Kateryna; Atanassov, Plamen

Here, we discuss perspectives and challenges in applying density functional theory for the calculation of spectroscopic properties of platinum group metal (PGM)-free electrocatalysts for oxygen reduction. More specifically, we discuss recent advances in the density functional theory calculations of core-level shifts in binding energies of N 1s electrons as measured by X-ray photoelectron spectroscopy. The link between the density functional theory calculations, the electrocatalytic performance of the catalysts, and structural analysis using modern spectroscopic techniques is expected to significantly increase our understanding of PGM-free catalysts at the molecular level.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burke, K.; Smith, J. C.; Grabowski, P. E.

Universal exact conditions guided the construction of most ground-state density functional approximations in use today. Here, we derive the relation between the entropy and Mermin free energy density functionals for thermal density functional theory. Both the entropy and sum of kinetic and electron-electron repulsion functionals are shown to be monotonically increasing with temperature, while the Mermin functional is concave downwards. Analogous relations are found for both exchange and correlation. The importance of these conditions is illustrated in two extremes: the Hubbard dimer and the uniform gas.

Linear-response time-dependent density-functional theory with pairing fields.

PubMed

Peng, Degao; van Aggelen, Helen; Yang, Yang; Yang, Weitao

2014-05-14

Recent development in particle-particle random phase approximation (pp-RPA) broadens the perspective on ground state correlation energies [H. van Aggelen, Y. Yang, and W. Yang, Phys. Rev. A 88, 030501 (2013), Y. Yang, H. van Aggelen, S. N. Steinmann, D. Peng, and W. Yang, J. Chem. Phys. 139, 174110 (2013); D. Peng, S. N. Steinmann, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 104112 (2013)] and N ± 2 excitation energies [Y. Yang, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 224105 (2013)]. So far Hartree-Fock and approximated density-functional orbitals have been utilized to evaluate the pp-RPA equation. In this paper, to further explore the fundamentals and the potential use of pairing matrix dependent functionals, we present the linear-response time-dependent density-functional theory with pairing fields with both adiabatic and frequency-dependent kernels. This theory is related to the density-functional theory and time-dependent density-functional theory for superconductors, but is applied to normal non-superconducting systems for our purpose. Due to the lack of the proof of the one-to-one mapping between the pairing matrix and the pairing field for time-dependent systems, the linear-response theory is established based on the representability assumption of the pairing matrix. The linear response theory justifies the use of approximated density-functionals in the pp-RPA equation. This work sets the fundamentals for future density-functional development to enhance the description of ground state correlation energies and N ± 2 excitation energies.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Handling times and saturating transmission functions in a snail-worm symbiosis.

PubMed

Hopkins, Skylar R; McGregor, Cari M; Belden, Lisa K; Wojdak, Jeremy M

2018-06-16

All dynamic species interaction models contain an assumption that describes how contact rates scale with population density. Choosing an appropriate contact-density function is important, because different functions have different implications for population dynamics and stability. However, this choice can be challenging, because there are many possible functions, and most are phenomenological and thus difficult to relate to underlying ecological processes. Using one such phenomenological function, we described a nonlinear relationship between field transmission rates and host density in a common snail-oligochaete symbiosis. We then used a well-known contact function from predator-prey models, the Holling Type II functional response, to describe and predict host snail contact rates in the laboratory. The Holling Type II functional response accurately described both the nonlinear contact-density relationship and the average contact duration that we observed. Therefore, we suggest that contact rates saturate with host density in this system because each snail contact requires a non-instantaneous handling time, and additional possible contacts do not occur during that handling time. Handling times and nonlinear contact rates might also explain the nonlinear relationship between symbiont transmission and snail density that we observed in the field, which could be confirmed by future work that controls for other potential sources of seasonal variation in transmission rates. Because most animal contacts are not instantaneous, the Holling Type II functional response might be broadly relevant to diverse host-symbiont systems.

Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Constantin, Lucian A; Sun, Jianwei; Csonka, Gábor I

2009-04-14

Some fundamental issues in ground-state density functional theory are discussed without equations: (1) The standard Hohenberg-Kohn and Kohn-Sham theorems were proven for a Hamiltonian that is not quite exact for real atoms, molecules, and solids. (2) The density functional for the exchange-correlation energy, which must be approximated, arises from the tendency of electrons to avoid one another as they move through the electron density. (3) In the absence of a magnetic field, either spin densities or total electron density can be used, although the former choice is better for approximations. (4) "Spin contamination" of the determinant of Kohn-Sham orbitals for an open-shell system is not wrong but right. (5) Only to the extent that symmetries of the interacting wave function are reflected in the spin densities should those symmetries be respected by the Kohn-Sham noninteracting or determinantal wave function. Functionals below the highest level of approximations should however sometimes break even those symmetries, for good physical reasons. (6) Simple and commonly used semilocal (lower-level) approximations for the exchange-correlation energy as a functional of the density can be accurate for closed systems near equilibrium and yet fail for open systems of fluctuating electron number. (7) The exact Kohn-Sham noninteracting state need not be a single determinant, but common approximations can fail when it is not. (8) Over an open system of fluctuating electron number, connected to another such system by stretched bonds, semilocal approximations make the exchange-correlation energy and hole-density sum rule too negative. (9) The gap in the exact Kohn-Sham band structure of a crystal underestimates the real fundamental gap but may approximate the first exciton energy in the large-gap limit. (10) Density functional theory is not really a mean-field theory, although it looks like one. The exact functional includes strong correlation, and semilocal approximations often overestimate the strength of static correlation through their semilocal exchange contributions. (11) Only under rare conditions can excited states arise directly from a ground-state theory.

A real-space stochastic density matrix approach for density functional electronic structure.

PubMed

Beck, Thomas L

2015-12-21

The recent development of real-space grid methods has led to more efficient, accurate, and adaptable approaches for large-scale electrostatics and density functional electronic structure modeling. With the incorporation of multiscale techniques, linear-scaling real-space solvers are possible for density functional problems if localized orbitals are used to represent the Kohn-Sham energy functional. These methods still suffer from high computational and storage overheads, however, due to extensive matrix operations related to the underlying wave function grid representation. In this paper, an alternative stochastic method is outlined that aims to solve directly for the one-electron density matrix in real space. In order to illustrate aspects of the method, model calculations are performed for simple one-dimensional problems that display some features of the more general problem, such as spatial nodes in the density matrix. This orbital-free approach may prove helpful considering a future involving increasingly parallel computing architectures. Its primary advantage is the near-locality of the random walks, allowing for simultaneous updates of the density matrix in different regions of space partitioned across the processors. In addition, it allows for testing and enforcement of the particle number and idempotency constraints through stabilization of a Feynman-Kac functional integral as opposed to the extensive matrix operations in traditional approaches.

Density functional theory and an experimentally-designed energy functional of electron density.

PubMed

Miranda, David A; Bueno, Paulo R

2016-09-21

We herein demonstrate that capacitance spectroscopy (CS) experimentally allows access to the energy associated with the quantum mechanical ground state of many-electron systems. Priorly, electrochemical capacitance, C [small mu, Greek, macron] [ρ], was previously understood from conceptual and computational density functional theory (DFT) calculations. Thus, we herein propose a quantum mechanical experiment-based variational method for electron charging processes based on an experimentally-designed functional of the ground state electron density. In this methodology, the electron state density, ρ, and an energy functional of the electron density, E [small mu, Greek, macron] [ρ], can be obtained from CS data. CS allows the derivative of the electrochemical potential with respect to the electron density, (δ[small mu, Greek, macron][ρ]/δρ), to be obtained as a unique functional of the energetically minimised system, i.e., β/C [small mu, Greek, macron] [ρ], where β is a constant (associated with the size of the system) and C [small mu, Greek, macron] [ρ] is an experimentally observable quantity. Thus the ground state energy (at a given fixed external potential) can be obtained simply as E [small mu, Greek, macron] [ρ], from the experimental measurement of C [small mu, Greek, macron] [ρ]. An experimental data-set was interpreted to demonstrate the potential of this quantum mechanical experiment-based variational principle.

Introduction to Classical Density Functional Theory by a Computational Experiment

ERIC Educational Resources Information Center

Jeanmairet, Guillaume; Levy, Nicolas; Levesque, Maximilien; Borgis, Daniel

2014-01-01

We propose an in silico experiment to introduce the classical density functional theory (cDFT). Density functional theories, whether quantum or classical, rely on abstract concepts that are nonintuitive; however, they are at the heart of powerful tools and active fields of research in both physics and chemistry. They led to the 1998 Nobel Prize in…

4-Arylflavan-3-ols as Proanthocyanidin Models: Absolute Configuration via Density Functional Calculation of Electronic Circular Dichroism

USDA-ARS?s Scientific Manuscript database

Density functional theory/B3LYP has been employed to optimize the conformations of selected 4-arylflavan-3-ols and their phenolic methyl ether 3-O-acetates. The electronic circular dichroism spectra of the major conformers have been calculated using time-dependent density functional theory to valida...

Nonlocal kinetic energy functionals by functional integration.

PubMed

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-14

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, T s [ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δT s [ρ]δρ(r), yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for T s [ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

Nonlocal kinetic energy functionals by functional integration

NASA Astrophysics Data System (ADS)

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-01

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, Ts[ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δ/Ts[ρ ] δ ρ (r ) , yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for Ts[ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

DOE PAGES

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; ...

2017-11-27

Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VOmore » $$_2$$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.« less

Time-dependent density-functional tight-binding method with the third-order expansion of electron density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishimoto, Yoshio, E-mail: nishimoto.yoshio@fukui.kyoto-u.ac.jp

2015-09-07

We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of themore » third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.« less

Time-dependent density-functional tight-binding method with the third-order expansion of electron density.

PubMed

Nishimoto, Yoshio

2015-09-07

We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan

Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VOmore » $$_2$$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.« less

Electron correlation and the self-interaction error of density functional theory

NASA Astrophysics Data System (ADS)

Polo, Victor; Kraka, Elfi; Cremer, Dieter

The self-interaction error (SIE) of commonly used DFT functionals has been systematically investigated by comparing the electron density distribution ρ( r ) generated by self-interaction corrected DFT (SIC-DFT) with a series of reference densities obtained by DFT or wavefunction theory (WFT) methods that cover typical electron correlation effects. Although the SIE of GGA functionals is considerably smaller than that of LDA functionals, it has significant consequences for the coverage of electron correlation effects at the DFT level of theory. The exchange SIE mimics long range (non-dynamic) pair correlation effects, and is responsible for the fact that the electron density of DFT exchange-only calculations resembles often that of MP4, MP2 or even CCSD(T) calculations. Changes in the electron density caused by SICDFT exchange are comparable with those that are associated with HF exchange. Correlation functionals contract the density towards the bond and the valence region, thus taking negative charge out of the van der Waals region where these effects are exaggerated by the influence of the SIE of the correlation functional. Hence, SIC-DFT leads in total to a relatively strong redistribution of negative charge from van der Waals, non-bonding, and valence regions of heavy atoms to the bond regions. These changes, although much stronger, resemble those obtained when comparing the densities of hybrid functionals such as B3LYP with the corresponding GGA functional BLYP. Hence, the balanced mixing of local and non-local exchange and correlation effects as it is achieved by hybrid functionals mimics SIC-DFT and can be considered as an economic way to include some SIC into standard DFT. However, the investigation shows also that the SIC-DFT description of molecules is unreliable because the standard functionals used were optimized for DFT including the SIE.

Source-Free Exchange-Correlation Magnetic Fields in Density Functional Theory.

PubMed

Sharma, S; Gross, E K U; Sanna, A; Dewhurst, J K

2018-03-13

Spin-dependent exchange-correlation energy functionals in use today depend on the charge density and the magnetization density: E xc [ρ, m]. However, it is also correct to define the functional in terms of the curl of m for physical external fields: E xc [ρ,∇ × m]. The exchange-correlation magnetic field, B xc , then becomes source-free. We study this variation of the theory by uniquely removing the source term from local and generalized gradient approximations to the functional. By doing so, the total Kohn-Sham moments are improved for a wide range of materials for both functionals. Significantly, the moments for the pnictides are now in good agreement with experiment. This source-free method is simple to implement in all existing density functional theory codes.

Density-Decomposed Orbital-Free Density Functional Theory for Covalent Systems and Application to Li-Si alloys

NASA Astrophysics Data System (ADS)

Xia, Junchao; Carter, Emily

2014-03-01

We propose a density decomposition scheme using a Wang-Govind-Carter (WGC)-based kinetic energy density functional (KEDF) to accurately and efficiently simulate covalent systems within orbital-free (OF) density functional theory (DFT). By using a local, density-dependent scale function, the total density is decomposed into a localized density within covalent bond regions and a flattened delocalized density, with the former described by semilocal KEDFs and the latter treated by the WGC KEDF. The new model predicts reasonable equilibrium volumes, bulk moduli, and phase ordering energies for various semiconductors compared to Kohn-Sham (KS) DFT benchmarks. The surface energy of Si(100) also agrees well with KSDFT. We further apply the model to study mechanical properties of Li-Si alloys, which have been recently recognized as a promising candidate for next-generation anodes of Li-ion batteries with outstanding capacity. We study multiple crystalline Li-Si alloys. The WGCD KEDF predicts accurate cell lattice vectors, equilibrium volumes, elastic moduli, electron densities, alloy formation and Li adsorption energies. Because of its quasilinear scaling, coupled with the level of accuracy shown here, OFDFT appears quite promising for large-scale simulation of such materials phenomena. Office of Naval Research, National Science Foundation, Tigress High Performance Computing Center.

Interconfigurational energies in transition-metal atoms using gradient-corrected density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kutzler, F.W.; Painter, G.S.

1991-03-15

The rapid variation of charge and spin densities in atoms and molecules provides a severe test for local-density-functional theory and for the use of gradient corrections. In the study reported in this paper, we use the Langreth, Mehl, and Hu (LMH) functional and the generalized gradient approximation (GGA) of Perdew and Yue to calculate {ital s}-{ital d} transition energies, 4{ital s} ionization energies, and 3{ital d} ionization energies for the 3{ital d} transition-metal atoms. These calculations are compared with results from the local-density functional of Vosko, Wilk, and Nusair. By comparison with experimental energies, we find that the gradient functionalsmore » are only marginally more successful than the local-density approximation in calculating energy differences between states in transition-metal atoms. The GGA approximation is somewhat better than the LMH functional for most of the atoms studied, although there are several exceptions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smallwood, D.O.

In a previous paper Smallwood and Paez (1991) showed how to generate realizations of partially coherent stationary normal time histories with a specified cross-spectral density matrix. This procedure is generalized for the case of multiple inputs with a specified cross-spectral density function and a specified marginal probability density function (pdf) for each of the inputs. The specified pdfs are not required to be Gaussian. A zero memory nonlinear (ZMNL) function is developed for each input to transform a Gaussian or normal time history into a time history with a specified non-Gaussian distribution. The transformation functions have the property that amore » transformed time history will have nearly the same auto spectral density as the original time history. A vector of Gaussian time histories are then generated with the specified cross-spectral density matrix. These waveforms are then transformed into the required time history realizations using the ZMNL function.« less

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

NASA Astrophysics Data System (ADS)

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; Heinonen, Olle; Kent, Paul R. C.; Krogel, Jaron T.

2017-11-01

Diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3 d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et al. [Science 355, 371 (2017), 10.1126/science.aag0410] in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO2, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development. With our reference data, the accuracy of both the energy and the electron density can be monitored simultaneously, which is useful for functional development. So far, this kind of detailed high accuracy reference data for correlated materials has been absent from the literature.

Invited Paper - Density functional theory: coverage of dynamic and non-dynamic electron correlation effects

NASA Astrophysics Data System (ADS)

Cremer, Dieter

The electron correlation effects covered by density functional theory (DFT) can be assessed qualitatively by comparing DFT densities ρ(r) with suitable reference densities obtained with wavefunction theory (WFT) methods that cover typical electron correlation effects. The analysis of difference densities ρ(DFT)-ρ(WFT) reveals that LDA and GGA exchange (X) functionals mimic non-dynamic correlation effects in an unspecified way. It is shown that these long range correlation effects are caused by the self-interaction error (SIE) of standard X functionals. Self-interaction corrected (SIC) DFT exchange gives, similar to exact exchange, for the bonding region a delocalized exchange hole, and does not cover any correlation effects. Hence, the exchange SIE is responsible for the fact that DFT densities often resemble MP4 or MP2 densities. The correlation functional changes X-only DFT densities in a manner observed when higher order coupling effects between lower order N-electron correlation effects are included. Hybrid functionals lead to changes in the density similar to those caused by SICDFT, which simply reflects the fact that hybrid functionals have been developed to cover part of the SIE and its long range correlation effects in a balanced manner. In the case of spin-unrestricted DFT (UDFT), non-dynamic electron correlation effects enter the calculation both via the X functional and via the wavefunction, which may cause a double-counting of correlation effects. The use of UDFT in the form of permuted orbital and broken-symmetry DFT (PO-UDFT, BS-UDFT) can lead to reasonable descriptions of multireference systems provided certain conditions are fulfilled. More reliable, however, is a combination of DFT and WFT methods, which makes the routine description of multireference systems possible. The development of such methods implies a separation of dynamic and non-dynamic correlation effects. Strategies for accomplishing this goal are discussed in general and tested in practice for CAS (complete active space)-DFT.

Pseudolocal tomography

DOEpatents

Katsevich, Alexander J.; Ramm, Alexander G.

1996-01-01

Local tomographic data is used to determine the location and value of a discontinuity between a first internal density of an object and a second density of a region within the object. A beam of radiation is directed in a predetermined pattern through the region of the object containing the discontinuity. Relative attenuation data of the beam is determined within the predetermined pattern having a first data component that includes attenuation data through the region. The relative attenuation data is input to a pseudo-local tomography function, where the difference between the internal density and the pseudo-local tomography function is computed across the discontinuity. The pseudo-local tomography function outputs the location of the discontinuity and the difference in density between the first density and the second density.

Pseudolocal tomography

DOEpatents

Katsevich, A.J.; Ramm, A.G.

1996-07-23

Local tomographic data is used to determine the location and value of a discontinuity between a first internal density of an object and a second density of a region within the object. A beam of radiation is directed in a predetermined pattern through the region of the object containing the discontinuity. Relative attenuation data of the beam is determined within the predetermined pattern having a first data component that includes attenuation data through the region. The relative attenuation data is input to a pseudo-local tomography function, where the difference between the internal density and the pseudo-local tomography function is computed across the discontinuity. The pseudo-local tomography function outputs the location of the discontinuity and the difference in density between the first density and the second density. 7 figs.

Uniform magnetic fields in density-functional theory

NASA Astrophysics Data System (ADS)

Tellgren, Erik I.; Laestadius, Andre; Helgaker, Trygve; Kvaal, Simen; Teale, Andrew M.

2018-01-01

We construct a density-functional formalism adapted to uniform external magnetic fields that is intermediate between conventional density functional theory and Current-Density Functional Theory (CDFT). In the intermediate theory, which we term linear vector potential-DFT (LDFT), the basic variables are the density, the canonical momentum, and the paramagnetic contribution to the magnetic moment. Both a constrained-search formulation and a convex formulation in terms of Legendre-Fenchel transformations are constructed. Many theoretical issues in CDFT find simplified analogs in LDFT. We prove results concerning N-representability, Hohenberg-Kohn-like mappings, existence of minimizers in the constrained-search expression, and a restricted analog to gauge invariance. The issue of additivity of the energy over non-interacting subsystems, which is qualitatively different in LDFT and CDFT, is also discussed.

Uniform magnetic fields in density-functional theory.

PubMed

Tellgren, Erik I; Laestadius, Andre; Helgaker, Trygve; Kvaal, Simen; Teale, Andrew M

2018-01-14

We construct a density-functional formalism adapted to uniform external magnetic fields that is intermediate between conventional density functional theory and Current-Density Functional Theory (CDFT). In the intermediate theory, which we term linear vector potential-DFT (LDFT), the basic variables are the density, the canonical momentum, and the paramagnetic contribution to the magnetic moment. Both a constrained-search formulation and a convex formulation in terms of Legendre-Fenchel transformations are constructed. Many theoretical issues in CDFT find simplified analogs in LDFT. We prove results concerning N-representability, Hohenberg-Kohn-like mappings, existence of minimizers in the constrained-search expression, and a restricted analog to gauge invariance. The issue of additivity of the energy over non-interacting subsystems, which is qualitatively different in LDFT and CDFT, is also discussed.

Communication: A new class of non-empirical explicit density functionals on the third rung of Jacob's ladder

NASA Astrophysics Data System (ADS)

de Silva, Piotr; Corminboeuf, Clémence

2015-09-01

We construct an orbital-free non-empirical meta-generalized gradient approximation (GGA) functional, which depends explicitly on density through the density overlap regions indicator [P. de Silva and C. Corminboeuf, J. Chem. Theory Comput. 10, 3745 (2014)]. The functional does not depend on either the kinetic energy density or the density Laplacian; therefore, it opens a new class of meta-GGA functionals. By construction, our meta-GGA yields exact exchange and correlation energy for the hydrogen atom and recovers the second order gradient expansion for exchange in the slowly varying limit. We show that for molecular systems, overall performance is better than non-empirical GGAs. For atomization energies, performance is on par with revTPSS, without any dependence on Kohn-Sham orbitals.

General dynamical density functional theory for classical fluids.

PubMed

Goddard, Benjamin D; Nold, Andreas; Savva, Nikos; Pavliotis, Grigorios A; Kalliadasis, Serafim

2012-09-21

We study the dynamics of a colloidal fluid including inertia and hydrodynamic interactions, two effects which strongly influence the nonequilibrium properties of the system. We derive a general dynamical density functional theory which shows very good agreement with full Langevin dynamics. In suitable limits, we recover existing dynamical density functional theories and a Navier-Stokes-like equation with additional nonlocal terms.

On the v-representabilty problem in density functional theory: Application to non-interacting systems

DOE PAGES

Dane, Markus; Gonis, Antonios

2016-07-05

Based on a computational procedure for determining the functional derivative with respect to the density of any antisymmetric N-particle wave function for a non-interacting system that leads to the density, we devise a test as to whether or not a wave function known to lead to a given density corresponds to a solution of a Schrödinger equation for some potential. We examine explicitly the case of non-interacting systems described by Slater determinants. Here, numerical examples for the cases of a one-dimensional square-well potential with infinite walls and the harmonic oscillator potential illustrate the formalism.

Excitation energies of molecules within time-independent density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hemanadhan, M., E-mail: hemanadh@iitk.ac.in; Harbola, Manoj K., E-mail: hemanadh@iitk.ac.in

2014-04-24

Recently proposed exchange energy functional for excited-states is tested for obtaining excitation energies of diatomic molecules. The functional is the ground-state counterpart of the local-density approximation, the modified local spin density (MLSD). The MLSD functional is tested for the N{sub 2} and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N{sub 2} molecule is in close vicinity to that obtained from the exact exchange orbital functional, Krieger, Li and Iafrate (KLI). For the CO molecule, the departure in excitation energy is observed and is due to the overcorrection of self-interaction.

Excitation energies of molecules within time-independent density functional theory

NASA Astrophysics Data System (ADS)

Hemanadhan, M.; Harbola, Manoj K.

2014-04-01

Recently proposed exchange energy functional for excited-states is tested for obtaining excitation energies of diatomic molecules. The functional is the ground-state counterpart of the local-density approximation, the modified local spin density (MLSD). The MLSD functional is tested for the N2 and CO diatomic molecules. The excitation energy obtained with the MLSD functional for the N2 molecule is in close vicinity to that obtained from the exact exchange orbital functional, Krieger, Li and Iafrate (KLI). For the CO molecule, the departure in excitation energy is observed and is due to the overcorrection of self-interaction.

Kinetic Energy of Hydrocarbons as a Function of Electron Density and Convolutional Neural Networks.

PubMed

Yao, Kun; Parkhill, John

2016-03-08

We demonstrate a convolutional neural network trained to reproduce the Kohn-Sham kinetic energy of hydrocarbons from an input electron density. The output of the network is used as a nonlocal correction to conventional local and semilocal kinetic functionals. We show that this approximation qualitatively reproduces Kohn-Sham potential energy surfaces when used with conventional exchange correlation functionals. The density which minimizes the total energy given by the functional is examined in detail. We identify several avenues to improve on this exploratory work, by reducing numerical noise and changing the structure of our functional. Finally we examine the features in the density learned by the neural network to anticipate the prospects of generalizing these models.

Effective model hierarchies for dynamic and static classical density functional theories

NASA Astrophysics Data System (ADS)

Majaniemi, S.; Provatas, N.; Nonomura, M.

2010-09-01

The origin and methodology of deriving effective model hierarchies are presented with applications to solidification of crystalline solids. In particular, it is discussed how the form of the equations of motion and the effective parameters on larger scales can be obtained from the more microscopic models. It will be shown that tying together the dynamic structure of the projection operator formalism with static classical density functional theories can lead to incomplete (mass) transport properties even though the linearized hydrodynamics on large scales is correctly reproduced. To facilitate a more natural way of binding together the dynamics of the macrovariables and classical density functional theory, a dynamic generalization of density functional theory based on the nonequilibrium generating functional is suggested.

Quest for a universal density functional: the accuracy of density functionals across a broad spectrum of databases in chemistry and physics.

PubMed

Peverati, Roberto; Truhlar, Donald G

2014-03-13

Kohn-Sham density functional theory is in principle an exact formulation of quantum mechanical electronic structure theory, but in practice we have to rely on approximate exchange-correlation (xc) functionals. The objective of our work has been to design an xc functional with broad accuracy across as wide an expanse of chemistry and physics as possible, leading--as a long-range goal--to a functional with good accuracy for all problems, i.e. a universal functional. To guide our path towards that goal and to measure our progress, we have developed-building on earlier work of our group-a set of databases of reference data for a variety of energetic and structural properties in chemistry and physics. These databases include energies of molecular processes, such as atomization, complexation, proton addition and ionization; they also include molecular geometries and solid-state lattice constants, chemical reaction barrier heights, and cohesive energies and band gaps of solids. For this paper, we gather many of these databases into four comprehensive databases, two with 384 energetic data for chemistry and solid-state physics and another two with 68 structural data for chemistry and solid-state physics, and we test two wave function methods and 77 density functionals (12 Minnesota meta functionals and 65 others) in a consistent way across this same broad set of data. We especially highlight the Minnesota density functionals, but the results have broader implications in that one may see the successes and failures of many kinds of density functionals when they are all applied to the same data. Therefore, the results provide a status report on the quest for a universal functional.

Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry.

PubMed

Tao, Jianmin; Mo, Yuxiang

2016-08-12

Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals.