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Sample records for der waals liquids

  1. Multiple critical points and liquid liquid equilibria from the van der Waals like equations of state

    NASA Astrophysics Data System (ADS)

    Artemenko, Sergey; Lozovsky, Taras; Mazur, Victor

    2008-06-01

    The principal aim of this work is a comprehensive analysis of the phase diagram of water via the van der Waals like equations of state (EoSs) which are considered as superpositions of repulsive and attractive forces. We test more extensively the modified van der Waals EoS (MVDW) proposed by Skibinski et al (2004 Phys. Rev. E 69 061206) and refine this model by introducing instead of the classical van der Waals repulsive term a very accurate hard sphere EoS over the entire stable and metastable regions (Liu 2006 Preprint cond-mat/0605392). It was detected that the simplest form of MVDW EoS displays a complex phase behavior, including three critical points, and identifies four fluid phases (gas, low density liquid (LDL), high density liquid (HDL), and very high density liquid (VHDL)). Moreover the experimentally observed (Mallamace et al 2007 Proc. Natl Acad. Sci. USA 104 18387) anomalous behavior of the density of water in the deeply supercooled region (a density minimum) is reproduced by the MWDW EoS. An improvement of the repulsive part does not change the topological picture of the phase behavior of water in the wide range of thermodynamic variables. The new parameters set for second and third critical points are recognized by thorough analysis of experimental data for the loci of thermodynamic response function extrema.

  2. Diffuse-interface modeling of liquid-vapor phase separation in a van der Waals fluid

    NASA Astrophysics Data System (ADS)

    Lamorgese, A. G.; Mauri, R.

    2009-04-01

    We simulate liquid-vapor phase separation in a van der Waals fluid that is deeply quenched into the unstable range of its phase diagram. Our theoretical approach follows the diffuse-interface model, where convection induced by phase change is accounted for via a nonequilibrium (Korteweg) force expressing the tendency of the liquid-vapor system to minimize its free energy. Spinodal decomposition patterns for critical and off-critical van der Waals fluids are studied numerically, revealing the scaling laws of the characteristic length scale and composition of single-phase microdomains, together with their dependence on the Reynolds number. Unlike phase separation of viscous binary mixtures, here local equilibrium is reached almost immediately after single-phase domains start to form. In addition, as predicted by scaling laws, such domains grow in time like t2/3. Comparison between 2D and 3D results reveals that 2D simulations capture, even quantitatively, the main features of the phenomenon.

  3. Influence of dielectric properties on van der Waals/Casimir forces in solid-liquid systems

    SciTech Connect

    Zwol, P. J. van; Palasantzas, G.; De Hosson, J. Th. M.

    2009-05-15

    In this paper, we present calculations of van der Waals/Casimir forces, described by Lifshitz theory, for the solid-liquid-solid system using measured dielectric functions of all involved materials for the wavelength range from millimeters down to subnanometers. It is shown that even if the dielectric function is known over all relevant frequency ranges, the scatter in the dielectric data can lead to very large scatter in the calculated van der Waals/Casimir forces. Especially when the liquid dielectric function becomes comparable in magnitude to the dielectric function of one of the interacting solids, the associated variation in the force can be up to a factor of 2 for plate-plate separations 5-500 nm. This corresponds to an uncertainty up to 100% in the theory prediction for a specific system. As a result accuracy testing of the Lifshitz theory under these circumstances is rather questionable. Finally we discuss predictions of Lifshitz theory regarding multiple repulsive-attractive transitions with separation distance, as well as nontrivial scaling of the van der Waals/Casimir force with distance.

  4. Van der Waals Forces

    NASA Astrophysics Data System (ADS)

    Parsegian, V. Adrian

    2006-03-01

    This should prove to be the definitive work explaining van der Waals forces, how to calculate them and take account of their impact under any circumstances and conditions. These weak intermolecular forces are of truly pervasive impact, and biologists, chemists, physicists and engineers will profit greatly from the thorough grounding in these fundamental forces that this book offers. Parsegian has organized his book at three successive levels of mathematical sophistication, to satisfy the needs and interests of readers at all levels of preparation. The Prelude and Level 1 are intended to give everyone an overview in words and pictures of the modern theory of van der Waals forces. Level 2 gives the formulae and a wide range of algorithms to let readers compute the van der Waals forces under virtually any physical or physiological conditions. Level 3 offers a rigorous basic formulation of the theory. Author is among the most highly respected biophysicists Van der Waals forces are significant for a wide range of questions and problems in the life sciences, chemistry, physics, and engineering, ranging up to the macro level No other book that develops the subject vigorously, and this book also makes the subject intuitively accessible to students who had not previously been mathematically sophisticated enough to calculate them

  5. Hidden scale invariance in molecular van der Waals liquids: A simulation study

    NASA Astrophysics Data System (ADS)

    Schrøder, Thomas B.; Pedersen, Ulf R.; Bailey, Nicholas P.; Toxvaerd, Søren; Dyre, Jeppe C.

    2009-10-01

    Results from molecular dynamics simulations of two viscous molecular model liquids—the Lewis-Wahnström model of orthoterphenyl and an asymmetric dumbbell model—are reported. We demonstrate that the liquids have a “hidden” approximate scale invariance: equilibrium potential energy fluctuations are accurately described by inverse power-law (IPL) potentials, the radial distribution functions are accurately reproduced by the IPL’s, and the radial distribution functions obey the IPL predicted scaling properties to a good approximation. IPL scaling of the dynamics also applies—with the scaling exponent predicted by the equilibrium fluctuations. In contrast, the equation of state does not obey the IPL scaling. We argue that our results are general for van der Waals liquids, but do not apply, e.g., for hydrogen-bonded liquids.

  6. van der Waals torque

    NASA Astrophysics Data System (ADS)

    Esquivel-Sirvent, Raul; Schatz, George

    2014-03-01

    The theory of generalized van der Waals forces by Lifshtz when applied to optically anisotropic media predicts the existence of a torque. In this work we present a theoretical calculation of the van der Waals torque for two systems. First we consider two isotropic parallel plates where the anisotropy is induced using an external magnetic field. The anisotropy will in turn induce a torque. As a case study we consider III-IV semiconductors such as InSb that can support magneto plasmons. The calculations of the torque are done in the Voigt configuration, that occurs when the magnetic field is parallel to the surface of the slabs. The change in the dielectric function as the magnetic field increases has the effect of decreasing the van der Waals force and increasing the torque. Thus, the external magnetic field is used to tune both the force and torque. The second example we present is the use of the torque in the non retarded regime to align arrays of nano particle slabs. The torque is calculated within Barash and Ginzburg formalism in the nonretarded limit, and is quantified by the introduction of a Hamaker torque constant. Calculations are conducted between anisotropic slabs of materials including BaTiO3 and arrays of Ag nano particles. Depending on the shape and arrangement of the Ag nano particles the effective dielectric function of the array can be tuned as to make it more or less anisotropic. We show how this torque can be used in self assembly of arrays of nano particles. ref. R. Esquivel-Sirvent, G. C. Schatz, Phys. Chem C, 117, 5492 (2013). partial support from DGAPA-UNAM.

  7. Nuclear liquid-gas phase transition at large N{sub c} in the van der Waals approximation

    SciTech Connect

    Torrieri, Giorgio; Mishustin, Igor

    2010-11-15

    We examine the nuclear liquid-gas phase transition at a large number of colors (N{sub c}) within the framework of the van der Waals (VdW) We argue that the VdW equation is appropriate for describing internucleon forces, and discuss how each parameter scales with N{sub c}. We demonstrate that N{sub c}=3 (our world) is not large with respect to the other dimensionless scale relevant to baryonic matter, the number of neighbors in a dense system N{sub N}. Consequently, we show that the liquid-gas phase transition looks dramatically different at N{sub c{yields}{infinity}} with respect to our world: The critical-point temperature becomes of the order of {Lambda}{sub QCD} rather than below it. The critical-point density becomes of the order of the baryonic density, rather than an order of magnitude below it. These are precisely the characteristics usually associated with the ''quarkyonic phase.'' We therefore conjecture that quarkyonic matter is simply the large-N{sub c} limit of the nuclear liquid, and the interplay between N{sub c} and N{sub N} is the reason that the nuclear liquid in our world is so different from quarkyonic matter. We conclude by suggesting ways in which our conjecture can be tested in future lattice measurements.

  8. ARPES studies of van der Waals heterostructure

    NASA Astrophysics Data System (ADS)

    Wang, Eryin; Lu, Xiaobo; Chen, Guorui; Fedorov, Alexei V.; Zhang, Yuanbo; Zhang, Guangyu; Zhou, Shuyun

    Van der Waals heterostructures are a novel class of ``materials by design'' which are formed by stacking different two-dimensional crystals together via van der Waals interaction. The periodic potential by the Moir é superlattice can be used as a control knob for tuning the electronic properties of two dimensional materials and can induce various novel quantum phenomena. Here we report direct electronic structure studies the of a model van der Waals heterostructure using angle-resolved photoemission spectroscopy (ARPES). This work is supported by the National Natural Science Foundation of China and Ministry of Education of China.

  9. Van der Waals interaction in uniaxial anisotropic media

    NASA Astrophysics Data System (ADS)

    Kornilovitch, Pavel E.

    2013-01-01

    Van der Waals interactions between flat surfaces in uniaxial anisotropic media are investigated in the nonretarded limit. The main focus is the effect of nonzero tilt between the optical axis and the surface normal on the strength of the van der Waals attraction. General expressions for the van der Waals free energy are derived using the surface mode method and the transfer-matrix formalism. To facilitate numerical calculations a temperature-dependent three-band parameterization of the dielectric tensor of the liquid crystal 5CB is developed. A solid slab immersed in a liquid crystal experiences a van der Waals torque that aligns the surface normal relative to the optical axis of the medium. The preferred orientation is different for different materials. Two solid slabs in close proximity experience a van der Waals attraction that is strongest for homeotropic alignment of the intervening liquid crystal for all the materials studied. The results have implications for the stability of plate-like colloids in liquid crystal hosts.

  10. Van der Waals interaction in uniaxial anisotropic media.

    PubMed

    Kornilovitch, Pavel E

    2013-01-23

    Van der Waals interactions between flat surfaces in uniaxial anisotropic media are investigated in the nonretarded limit. The main focus is the effect of nonzero tilt between the optical axis and the surface normal on the strength of the van der Waals attraction. General expressions for the van der Waals free energy are derived using the surface mode method and the transfer-matrix formalism. To facilitate numerical calculations a temperature-dependent three-band parameterization of the dielectric tensor of the liquid crystal 5CB is developed. A solid slab immersed in a liquid crystal experiences a van der Waals torque that aligns the surface normal relative to the optical axis of the medium. The preferred orientation is different for different materials. Two solid slabs in close proximity experience a van der Waals attraction that is strongest for homeotropic alignment of the intervening liquid crystal for all the materials studied. The results have implications for the stability of plate-like colloids in liquid crystal hosts. PMID:23234868

  11. Role of Van der Waals interactions in determining the structure of liquid tellurides

    NASA Astrophysics Data System (ADS)

    Micoulaut, Matthieu; Flores-Ruiz, Hugo; Coulet, Vanessa; Piarristeguy, Andrea; Johnson, Mark; Cuello, Gabriel; Pradel, Annie

    The simulation of tellurides using standard density functional (DFT) theory based molecular dynamics usually leads to an overestimation of the bond distances and a noticeable mismatch between theory and experiments when e.g. structure functions are being directly compared. Here, the structural properties of several compositions of Ge-Te and Ge-Sb-Te liquids are studied from a combination of neutron diffraction and DFT-based molecular dynamics. Importantly, we find an excellent agreement in the reproduction of the structure in real and reciprocal spaces, resulting from the incorporation of dispersion forces in the simulation. We then investigate structural properties including structure factors, pair distribution functions, angular distributions, coordination numbers, neighbor distributions, and compare our results with experimental findings. References:Physical Review B 92, 134205 (2015)Physical Review B 89, 174205 (2014)Physical Review B 90, 094207 (2014) Support from Agence Nationale de la Recherche (ANR) (Grant No. ANR-11-BS08-0012) is gratefully acknowledged.

  12. Resonance broadening and van der waals broadening

    NASA Astrophysics Data System (ADS)

    Mashonkina, L.

    2010-11-01

    Resonance broadening is important for the hydrogen lines in the spectra of F-type and later stars. In the corresponding temperature regime, the extended wings of the Balmer lines are used as a stellar effective temperature indicator. We show the effect of the use of two broadening theories, Ali & Griem (1965, 1966) and Barklem et al. (2000a, 2000b), on the effective temperature derived in non-LTE from Hα and Hβ in the Sun and the metal-poor star HD19445. Van der Waals broadening is important for strong spectral lines in the atmospheres of F-type and later stars. For the selected transitions in Ca I and Ca II, line profile comparisons are made between applying the van der Waals damping constants from laboratory measurements, the ABO perturbation theory, and the classic Unsöld approximation.

  13. van der Waals Forces between Cylinders

    PubMed Central

    Mitchell, D. J.; Ninham, B. W.; Richmond, P.

    1973-01-01

    We derive the retarded van der Waals interaction between two long thin parallel dielectric cylinders immersed in a solvent. The result shows that the ultraviolet interactions which may be responsible for the specificity of macromolecular interactions do not operate strongly over distances R ≥ 50 Å. For greater distances the contribution of these frequencies ξ is damped by a factor ∞ e-ξR/c. PMID:4696763

  14. Generalized van der Waals density functional theory for nonuniform polymers

    SciTech Connect

    Patra, Chandra N.; Yethiraj, Arun

    2000-01-15

    A density functional theory is presented for the effect of attractions on the structure of polymers at surfaces. The theory treats the ideal gas functional exactly, and uses a weighted density approximation for the hard chain contribution to the excess free energy functional. The attractive interactions are treated using a van der Waals approximation. The theory is in good agreement with computer simulations for the density profiles at surfaces for a wide range of densities and temperatures, except for low polymer densities at low temperatures where it overestimates the depletion of chains from the surface. This deficiency is attributed to the neglect of liquid state correlations in the van der Waals term of the free energy functional. (c) 2000 American Institute of Physics.

  15. van der Waals Heterostructures Grown by MBE

    NASA Astrophysics Data System (ADS)

    Hinkle, Christopher

    In this work, we demonstrate the high-quality MBE heterostructure growth of various layered 2D materials by van der Waals epitaxy (VDWE). The coupling of different types of van der Waals materials including transition metal dichalcogenide thin films (e.g., WSe2, WTe2, HfSe2) , insulating hexagonal boron nitride (h-BN), and topological insulators (e.g., Bi2Se3) allows for the fabrication of novel electronic devices that take advantage of unique quantum confinement and spin-based characteristics. The relaxed lattice-matching criteria of van der Waals epitaxy has allowed for high-quality heterostructure growth with atomically abrupt interfaces, allowing us to couple these materials based primarily on their band alignment and electronic properties. We will discuss the impact of sample preparation, surface reactivity, and lattice mismatch of various substrates (sapphire, graphene, TMDs, Bi2Se3) on the growth mode and quality of the films and will discuss our studies of substrate temperature and flux rates on the resultant growth and grain size. Structural and chemical characterization was conducted via reflection high energy electron diffraction (RHEED, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning tunneling microscopy/spectroscopy (STM/S), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Experimentally determined band alignments have been determined and compared with first-principles calculations allowing the design of novel low-power logic and magnetic memory devices. Initial results from the electrical characterization of these grown thin films and some simple devices will also be presented. These VDWE grown layered 2D materials show significant potential for fabricating novel heterostructures with tunable band alignments and magnetic properties for a variety of nanoelectronic and optoelectronic applications.

  16. Supramolecular liquid crystalline π-conjugates: the role of aromatic π-stacking and van der Waals forces on the molecular self-assembly of oligophenylenevinylenes.

    PubMed

    Goel, Mahima; Jayakannan, M

    2010-10-01

    Here, we report a unique design strategy to trace the role of aromatic π-stacking and van der Waals interactions on the molecular self-organization of π-conjugated building blocks in a single system. A new series of bulky oligophenylenevinylenes (OPVs) bearing a tricyclodecanemethylene (TCD) unit in the aromatic π-core with flexible long methylene chains (n = 0-12 and 16) in the longitudinal position were designed and synthesized. The OPVs were found to be liquid crystalline, and their enthalpies of phase transitions (also entropies) showed odd-even oscillation with respect to the number of carbon atoms in alkyl chains. OPVs with an even number of methylene units in the side chains showed higher enthalpies with respect to their highly packed solid structures compared to odd-numbered ones. Polarized light microscopic analysis confirmed the formation of cholesteric liquid crystalline (LC) phases of fan shaped textures with focal conics in OPVs with 5 ≤ n ≤ 9. OPVs with longer alkyl chains (OPV-10 to OPV-12) produced a birefringence pattern consisting of dark and bright ring-banded suprastructures. The melting temperature followed a sigmoidal trend, indicating the transformation of molecular self-organization in OPVs from solid to ring-banded suprastructures via cholesteric LC intermediates. At longer alkyl chain lengths, the van der Waals interactions among the alkyl chains became predominant and translated the mesogenic effect across the lamellae; as a consequence, the lamellae underwent twisted self-organization along the radial growth direction of the spherulites to produce bright and dark bands. Scanning electron microscope (SEM) analysis of cholesteric LC and ring-banded textures strongly supported the existence of twisted lamellae in the OPVs with ring-banded textures. Variable temperature X-ray diffraction analysis confirmed the reversibility of the molecular self-organization in the solid state and also showed the existence of the higher ordered

  17. Using instability of nanometric liquid Cu films on SiO2 substrates to determine the underlying van der Waals potential

    NASA Astrophysics Data System (ADS)

    González, Alejandro G.; Diez, Javier A.; Wu, Yueying; Fowlkes, Jason D.; Rack, Philip D.; Kondic, Lou

    2013-11-01

    We study the instability of nanometric Cu thin films on a SiO2 substrate. The metal is melted by means of laser pulses for some tens of nanoseconds. The free surface destabilizes during the liquid lifetime, leading to the formation of holes at first and to metal drops on the substrate in later stages. By analyzing the Fourier transforms of the SEM images obtained during the metal film evolution, we determine the emerging length scales for both early and late stages of the instability development. The results are analyzed within the framework of a long-wave hydrodynamic model, which introduces van der Waals forces by means of disjoining and conjoining pressures. These forces are characterized by a pair of exponents for the ratio h / h * , where h is the liquid thickness and h* is a residual one. We find that the pair (3 , 2) provides a good agreement for the relationship of the wavelength with maximum growth rate, λm, while other typical pairs, such as (4 , 3) and (9 , 3) do not provide accurate description of the experimental data. Supported by CONICET-Argentina grant PIP 844/2011 (AGG, JAD), and by NSF grants CBET-1235651 (PDR) and CBET-1235710 (LK).

  18. Tunnelling in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Mishchenko, Artem; Novoselov, Kostya; Geim, Andre; Eaves, Laurence; Falko, Vladimir

    When graphene and other conductive two-dimensional (2D) materials are separated by an atomically thin insulating 2D crystal, quantum mechanical tunnelling leads to appreciable current between two 2D conductors due to the overlap of their wavefunctions. These tunnel devices demonstrate interesting physics and potential for applications: such effects as resonant tunnelling, negative differential conductance, light emission and detection have already been demonstrated. In this presentation we will outline the current status and perspectives of tunnelling transistors based on 2D materials assembled into van der Waals heterostructures. Particularly, we will present results on mono- and bilayer graphene tunnelling, tunnelling in 2D crystal-based quantum wells, and tunnelling in superconducting 2D materials. Such effects as momentum and chirality conservation, phonon- and impurity-assisted tunnelling will also be discussed. Finally, we will ponder the implications of discovered effects for practical applications.

  19. Free volume from positron lifetime and pressure-volume-temperature experiments in relation to structural relaxation of van der Waals molecular glass-forming liquids.

    PubMed

    Dlubek, G; Shaikh, M Q; Rätzke, K; Paluch, M; Faupel, F

    2010-06-16

    Positron annihilation lifetime spectroscopy (PALS) is employed to characterize the temperature dependence of the free volume in two van der Waals liquids: 1, 1'-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1, 1'-di(4-methoxy-5-methylphenyl)cyclohexane (BMMPC). From the PALS spectra analysed with the routine LifeTime9.0, the size (volume) distribution of local free volumes (subnanometer size holes), its mean, [v(h)], and mean dispersion, σ(h), were calculated. A comparison with the macroscopic volume from pressure-volume-temperature (PV T) experiments delivered the hole density and the specific hole free volume and a complete characterization of the free volume microstructure in that sense. These data are used in correlation with structural (α) relaxation data from broad-band dielectric spectroscopy (BDS) in terms of the Cohen-Grest and Cohen-Turnbull free volume models. An extension of the latter model allows us to quantify deviations between experiments and theory and an attempt to systematize these in terms of T(g) or of the fragility. The experimental data for several fragile and less fragile glass formers are involved in the final discussion. It was concluded that, for large differences in the fragility of different glass formers, the positron lifetime mirrors clearly the different character of these materials. For small differences in the fragility, additional properties like the character of bonds and chemical structure of the material may affect size, distribution and thermal behaviour of the free volume. PMID:21393763

  20. Isotope separation by photodissociation of Van der Waal's molecules

    DOEpatents

    Lee, Yuan T.

    1977-01-01

    A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

  1. Supercurrent in van der Waals Josephson junction.

    PubMed

    Yabuki, Naoto; Moriya, Rai; Arai, Miho; Sata, Yohta; Morikawa, Sei; Masubuchi, Satoru; Machida, Tomoki

    2016-01-01

    Supercurrent flow between two superconductors with different order parameters, a phenomenon known as the Josephson effect, can be achieved by inserting a non-superconducting material between two superconductors to decouple their wavefunctions. These Josephson junctions have been employed in fields ranging from digital to quantum electronics, yet their functionality is limited by the interface quality and use of non-superconducting material. Here we show that by exfoliating a layered dichalcogenide (NbSe2) superconductor, the van der Waals (vdW) contact between the cleaved surfaces can instead be used to construct a Josephson junction. This is made possible by recent advances in vdW heterostructure technology, with an atomically flat vdW interface free of oxidation and inter-diffusion achieved by eliminating all heat treatment during junction preparation. Here we demonstrate that this artificially created vdW interface provides sufficient decoupling of the wavefunctions of the two NbSe2 crystals, with the vdW Josephson junction exhibiting a high supercurrent transparency. PMID:26830754

  2. Van der Waals Interactions in Aspirin

    NASA Astrophysics Data System (ADS)

    Reilly, Anthony; Tkatchenko, Alexandre

    2015-03-01

    The ability of molecules to yield multiple solid forms, or polymorphs, has significance for diverse applications ranging from drug design and food chemistry to nonlinear optics and hydrogen storage. In particular, aspirin has been used and studied for over a century, but has only recently been shown to have an additional polymorphic form, known as form II. Since the two observed solid forms of aspirin are degenerate in terms of lattice energy, kinetic effects have been suggested to determine the metastability of the less abundant form II. Here, first-principles calculations provide an alternative explanation based on free-energy differences at room temperature. The explicit consideration of many-body van der Waals interactions in the free energy demonstrates that the stability of the most abundant form of aspirin is due to a subtle coupling between collective electronic fluctuations and quantized lattice vibrations. In addition, a systematic analysis of the elastic properties of the two forms of aspirin rules out mechanical instability of form II as making it metastable.

  3. Dielectric Genome of van der Waals Heterostructures.

    PubMed

    Andersen, Kirsten; Latini, Simone; Thygesen, Kristian S

    2015-07-01

    Vertical stacking of two-dimensional (2D) crystals, such as graphene and hexagonal boron nitride, has recently lead to a new class of materials known as van der Waals heterostructures (vdWHs) with unique and highly tunable electronic properties. Ab initio calculations should in principle provide a powerful tool for modeling and guiding the design of vdWHs, but in their traditional form such calculations are only feasible for commensurable structures with a few layers. Here we show that the dielectric properties of realistic, incommensurable vdWHs comprising hundreds of layers can be efficiently calculated using a multiscale approach where the dielectric functions of the individual layers (the dielectric building blocks) are computed ab initio and coupled together via the long-range Coulomb interaction. We use the method to illustrate the 2D-3D transition of the dielectric function of multilayer MoS2 crystals, the hybridization of quantum plasmons in thick graphene/hBN heterostructures, and to demonstrate the intricate effect of substrate screening on the non-Rydberg exciton series in supported WS2. The dielectric building blocks for a variety of 2D crystals are available in an open database together with the software for solving the coupled electrodynamic equations. PMID:26047386

  4. Van der Waals interactions involving proteins.

    PubMed Central

    Roth, C M; Neal, B L; Lenhoff, A M

    1996-01-01

    Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models, with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth. Images FIGURE 3 PMID:8789115

  5. Modern theory of van der Waals interactions

    NASA Astrophysics Data System (ADS)

    Dobson, John

    2014-03-01

    van der Waals (vdW, dispersion) interactions are important in diverse areas such as colloid, surface and nano science, cohesion of molecular crystals, and biomolecular science. They also provide competition in experiments to discover the fifth fundamental force.While vdW interactions have been understood in principle for a century, their quantitative first-principles prediction and modelling down to chemical contact separations have proven stubbornly difficult because the quantal many-electron problem is involved. After some brief historical material, the current state of the art will be discussed with particular reference to several approaches: pairwise additive, perturbative quantum chemical, vdW-DF, Lifshitz-like scattering, RPA-like, Adiabatic Connection Fluctuation Dissipation / Time Dependent DFT based etc.. A potentially useful classification will be introduced to aid in understanding the physical causes of departures from pairwise additivity, that is from the usual sum of C6R-6 contributions. These departures result in non-standard power law decays of nanostructure vdW interactions as a function of separation D, as well as surprising dependences of the attraction on the number, N, of atoms within each vdW-interacting fragment. Some further recent results on non-additivity will also be presented. Work supported by an Australian Research Council Discovery Grant.

  6. Picosecond photoresponse in van der Waals heterostructures.

    PubMed

    Massicotte, M; Schmidt, P; Vialla, F; Schädler, K G; Reserbat-Plantey, A; Watanabe, K; Taniguchi, T; Tielrooij, K J; Koppens, F H L

    2016-01-01

    Two-dimensional crystals such as graphene and transition-metal dichalcogenides demonstrate a range of unique and complementary optoelectronic properties. Assembling different two-dimensional materials in vertical heterostructures enables the combination of these properties in one device, thus creating multifunctional optoelectronic systems with superior performance. Here, we demonstrate that graphene/WSe2/graphene heterostructures ally the high photodetection efficiency of transition-metal dichalcogenides with a picosecond photoresponse comparable to that of graphene, thereby optimizing both speed and efficiency in a single photodetector. We follow the extraction of photoexcited carriers in these devices using time-resolved photocurrent measurements and demonstrate a photoresponse time as short as 5.5 ps, which we tune by applying a bias and by varying the transition-metal dichalcogenide layer thickness. Our study provides direct insight into the physical processes governing the detection speed and quantum efficiency of these van der Waals heterostuctures, such as out-of-plane carrier drift and recombination. The observation and understanding of ultrafast and efficient photodetection demonstrate the potential of hybrid transition-metal dichalcogenide-based heterostructures as a platform for future optoelectronic devices. PMID:26436565

  7. Van der Waals Interactions Involving Proteins

    NASA Technical Reports Server (NTRS)

    Roth, Charles M.; Neal, Brian L.; Lenhoff, Abraham M.

    1996-01-01

    Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.

  8. Supercurrent in van der Waals Josephson junction

    PubMed Central

    Yabuki, Naoto; Moriya, Rai; Arai, Miho; Sata, Yohta; Morikawa, Sei; Masubuchi, Satoru; Machida, Tomoki

    2016-01-01

    Supercurrent flow between two superconductors with different order parameters, a phenomenon known as the Josephson effect, can be achieved by inserting a non-superconducting material between two superconductors to decouple their wavefunctions. These Josephson junctions have been employed in fields ranging from digital to quantum electronics, yet their functionality is limited by the interface quality and use of non-superconducting material. Here we show that by exfoliating a layered dichalcogenide (NbSe2) superconductor, the van der Waals (vdW) contact between the cleaved surfaces can instead be used to construct a Josephson junction. This is made possible by recent advances in vdW heterostructure technology, with an atomically flat vdW interface free of oxidation and inter-diffusion achieved by eliminating all heat treatment during junction preparation. Here we demonstrate that this artificially created vdW interface provides sufficient decoupling of the wavefunctions of the two NbSe2 crystals, with the vdW Josephson junction exhibiting a high supercurrent transparency. PMID:26830754

  9. Picosecond photoresponse in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Massicotte, M.; Schmidt, P.; Vialla, F.; Schädler, K. G.; Reserbat-Plantey, A.; Watanabe, K.; Taniguchi, T.; Tielrooij, K. J.; Koppens, F. H. L.

    2016-01-01

    Two-dimensional crystals such as graphene and transition-metal dichalcogenides demonstrate a range of unique and complementary optoelectronic properties. Assembling different two-dimensional materials in vertical heterostructures enables the combination of these properties in one device, thus creating multifunctional optoelectronic systems with superior performance. Here, we demonstrate that graphene/WSe2/graphene heterostructures ally the high photodetection efficiency of transition-metal dichalcogenides with a picosecond photoresponse comparable to that of graphene, thereby optimizing both speed and efficiency in a single photodetector. We follow the extraction of photoexcited carriers in these devices using time-resolved photocurrent measurements and demonstrate a photoresponse time as short as 5.5 ps, which we tune by applying a bias and by varying the transition-metal dichalcogenide layer thickness. Our study provides direct insight into the physical processes governing the detection speed and quantum efficiency of these van der Waals heterostuctures, such as out-of-plane carrier drift and recombination. The observation and understanding of ultrafast and efficient photodetection demonstrate the potential of hybrid transition-metal dichalcogenide-based heterostructures as a platform for future optoelectronic devices.

  10. Supercurrent in van der Waals Josephson junction

    NASA Astrophysics Data System (ADS)

    Yabuki, Naoto; Moriya, Rai; Arai, Miho; Sata, Yohta; Morikawa, Sei; Masubuchi, Satoru; Machida, Tomoki

    2016-02-01

    Supercurrent flow between two superconductors with different order parameters, a phenomenon known as the Josephson effect, can be achieved by inserting a non-superconducting material between two superconductors to decouple their wavefunctions. These Josephson junctions have been employed in fields ranging from digital to quantum electronics, yet their functionality is limited by the interface quality and use of non-superconducting material. Here we show that by exfoliating a layered dichalcogenide (NbSe2) superconductor, the van der Waals (vdW) contact between the cleaved surfaces can instead be used to construct a Josephson junction. This is made possible by recent advances in vdW heterostructure technology, with an atomically flat vdW interface free of oxidation and inter-diffusion achieved by eliminating all heat treatment during junction preparation. Here we demonstrate that this artificially created vdW interface provides sufficient decoupling of the wavefunctions of the two NbSe2 crystals, with the vdW Josephson junction exhibiting a high supercurrent transparency.

  11. Spontaneous cavitation in a Lennard-Jones liquid: Molecular dynamics simulation and the van der Waals-Cahn-Hilliard gradient theory

    NASA Astrophysics Data System (ADS)

    Baidakov, Vladimir G.

    2016-02-01

    The process of bubble nucleation in a Lennard-Jones (LJ) liquid is studied by molecular dynamics (MD) simulation. The bubble nucleation rate J is determined by the mean life-time method at temperatures above that of the triple point in the region of negative pressures. The results of simulation are compared with classical nucleation theory (CNT) and modified classical nucleation theory (MCNT), in which the work of formation of a critical bubble is determined in the framework of the van der Waals-Cahn-Hilliard gradient theory (GT). It has been found that the values of J obtained in MD simulation systematically exceed the data of CNT, and this excess in the nucleation rate reaches 8-10 orders of magnitude close to the triple point temperature. The results of MCNT are in satisfactory agreement with the data of MD simulation. To describe the properties of vapor-phase nuclei in the framework of GT, an equation of state has been built up which describes stable, metastable and labile regions of LJ fluids. The surface tension of critical bubbles γ has been found from CNT and data of MD simulation as a function of the radius of curvature of the surface of tension R*. The dependence γ(R*) has also been calculated from GT. The Tolman length has been determined, which is negative and in modulus equal to ≈(0.1 - 0.2) σ. The paper discusses the applicability of the Tolman formula to the description of the properties of critical nuclei in nucleation.

  12. Spontaneous stacking faults in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Boussinot, G.

    2016-08-01

    The rapid developments in the manipulation of two-dimensional monoatomic layers such as graphene or h-BN allow one to create heterostructures consisting of possibly many chemically different layers, stacked owing to van der Waals attraction. We propose a Frenkel-Kontorova model including a transverse degree of freedom in order to describe local deformations in these heterostructures. We study the case where two dissimilar monolayers are alternatively stacked, and find that stacking faults may emerge spontaneously for a large enough number of stacked layers as a result of the competition between adhesion and elastic energies. This symmetry-breaking transition should become of fundamental importance for the description of three-dimensional van der Waals heterostructures as soon as a precise control on the lattice orientation of the van der Waals layers is achieved.

  13. van der Waals interactions between excited atoms in generic environments

    NASA Astrophysics Data System (ADS)

    Barcellona, Pablo; Passante, Roberto; Rizzuto, Lucia; Buhmann, Stefan Yoshi

    2016-07-01

    We consider the van der Waals force involving excited atoms in general environments, constituted by magnetodielectric bodies. We develop a dynamical approach studying the dynamics of the atoms and the field, mutually coupled. When only one atom is excited, our dynamical theory suggests that for large distances the van der Waals force acting on the ground-state atom is monotonic, while the force acting in the excited atom is spatially oscillating. We show how this latter force can be related to the known oscillating Casimir-Polder force on an excited atom near a (ground-state) body. Our force also reveals a population-induced dynamics: for times much larger that the atomic lifetime the atoms will decay to their ground states leading to the van der Waals interaction between ground-state atoms.

  14. Van der Waals stacked 2D layered materials for optoelectronics

    NASA Astrophysics Data System (ADS)

    Zhang, Wenjing; Wang, Qixing; Chen, Yu; Wang, Zhuo; Wee, Andrew T. S.

    2016-06-01

    The band gaps of many atomically thin 2D layered materials such as graphene, black phosphorus, monolayer semiconducting transition metal dichalcogenides and hBN range from 0 to 6 eV. These isolated atomic planes can be reassembled into hybrid heterostructures made layer by layer in a precisely chosen sequence. Thus, the electronic properties of 2D materials can be engineered by van der Waals stacking, and the interlayer coupling can be tuned, which opens up avenues for creating new material systems with rich functionalities and novel physical properties. Early studies suggest that van der Waals stacked 2D materials work exceptionally well, dramatically enriching the optoelectronics applications of 2D materials. Here we review recent progress in van der Waals stacked 2D materials, and discuss their potential applications in optoelectronics.

  15. Collisional stabilization of van der Waals states of ozone

    NASA Astrophysics Data System (ADS)

    Ivanov, Mikhail V.; Babikov, Dmitri

    2011-05-01

    The mixed quantum-classical theory developed earlier [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the collisional energy transfer and the ro-vibrational energy flow in a recombination reaction that forms ozone. Assumption is that the van der Waals states of ozone are formed in the O + O2 collisions, and then stabilized into the states of covalent well by collisions with bath gas. Cross sections for collision induced dissociation of van der Waals states of ozone, for their stabilization into the covalent well, and for their survival in the van der Waals well are computed. The role these states may play in the kinetics of ozone formation is discussed.

  16. The Economics of van der Waals Force Engineering

    NASA Astrophysics Data System (ADS)

    Pinto, Fabrizio

    2008-01-01

    As micro-electro-mechanical system (MEMS) fabrication continues on an ever-decreasing scale, new technological challenges must be successfully negotiated if Moore's Law is to be an even approximately valid model of the future of device miniaturization. Among the most significant obstacles is the existence of strong surface forces related to quantum mechanical van der Waals interatomic interactions, which rapidly diverge as the distance between any two neutral boundaries decreases. The van der Waals force is a contributing factor in several device failures and limitations, including, for instance, stiction and oscillator non-linearities. In the last decade, however, it has been conclusively shown that van der Waals forces are not just a MEMS limitation but can be engineered in both magnitude and sign so as to enable classes of proprietary inventions which either deliver novel capabilities or improve upon existing ones. The evolution of van der Waals force research from an almost exclusively theoretical field in quantum-electro-dynamics to an enabling nanotechnology discipline represents a useful example of the ongoing paradigm shift from government-centered to private-capital funded R&D in cutting-edge physics leading to potentially profitable products. In this paper, we discuss the reasons van der Waals force engineering may lead to the creation of thriving markets both in the short and medium terms by highlighting technical challenges that can be competitively addressed by this novel approach. We also discuss some notable obstacles to the cultural transformation of the academic research community required for the emergence of a functional van der Waals force engineering industry worldwide.

  17. Curves of growth for van der Waals broadened spectral lines

    NASA Technical Reports Server (NTRS)

    Park, C.

    1980-01-01

    Curves of growth are evaluated for a spectral line broadened by the van der Waals interactions during collisions. The growth of the equivalent widths of such lines is shown to be dependent on the product of the perturber density and the 6/10 power of the van der Waals potential coefficient. When the parameter is small, the widths grow as the 1/2 power of the optical depth as they do for the Voigt profile: but when the parameter is large, they grow as 2/3 power and, hence, faster than the Voigt profile. An approximate analytical expression for the computed growth characteristics is given.

  18. Thermal effects on van der Waals adhesive forces

    NASA Astrophysics Data System (ADS)

    Pinon, A. V.; Wierez-Kien, M.; Craciun, A. D.; Beyer, N.; Gallani, J. L.; Rastei, M. V.

    2016-01-01

    We present an experimental and theoretical study on how thermal energy alters van der Waals adhesion forces in nanoscale contacts stretched by mechanical probes. The force follows a distribution whose density function is an asymmetric bell-shaped curve presenting a temperature-dependent negative skewness. With increasing temperature the asymmetry increases whereas the most probable force value decreases. Using a 2-8 Lennard-Jones interaction potential within the reaction rate theory, we offer a theoretical framework permitting an evaluation of the microscopic parameters governing adhesion in a van der Waals nanocontact subjected to mechanical fluctuations.

  19. Excited nucleon as a van der Waals system of partons

    SciTech Connect

    Jenkovszky, L. L.; Muskeyev, A. O. Yezhov, S. N.

    2012-06-15

    Saturation in deep inelastic scattering (DIS) and deeply virtual Compton scattering (DVCS) is associated with a phase transition between the partonic gas, typical of moderate x and Q{sup 2}, and partonic fluid appearing at increasing Q{sup 2} and decreasing Bjorken x. We suggest the van der Waals equation of state to describe properly this phase transition.

  20. Statistical complexity, virial expansion, and van der Waals equation

    NASA Astrophysics Data System (ADS)

    Pennini, F.; Plastino, A.

    2016-09-01

    We investigate the notion of LMC statistical complexity with regards to a real gas and in terms of the second virial coefficient. The ensuing results are applied to the van der Waals equation. Interestingly enough, one finds a complexity-interpretation for the associated phase transition.

  1. Aqueous gating of van der Waals materials on bilayer nanopaper.

    PubMed

    Bao, Wenzhong; Fang, Zhiqiang; Wan, Jiayu; Dai, Jiaqi; Zhu, Hongli; Han, Xiaogang; Yang, Xiaofeng; Preston, Colin; Hu, Liangbing

    2014-10-28

    In this work, we report transistors made of van der Waals materials on a mesoporous paper with a smooth nanoscale surface. The aqueous transistor has a novel planar structure with source, drain, and gate electrodes on the same surface of the paper, while the mesoporous paper is used as an electrolyte reservoir. These transistors are enabled by an all-cellulose paper with nanofibrillated cellulose (NFC) on the top surface that leads to an excellent surface smoothness, while the rest of the microsized cellulose fibers can absorb electrolyte effectively. Based on two-dimensional van der Waals materials, including MoS2 and graphene, we demonstrate high-performance transistors with a large on-off ratio and low subthreshold swing. Such planar transistors with absorbed electrolyte gating can be used as sensors integrated with other components to form paper microfluidic systems. This study is significant for future paper-based electronics and biosensors. PMID:25283598

  2. Charge Transfer Excitons at van der Waals Interfaces.

    PubMed

    Zhu, Xiaoyang; Monahan, Nicholas R; Gong, Zizhou; Zhu, Haiming; Williams, Kristopher W; Nelson, Cory A

    2015-07-01

    The van der Waals interfaces of molecular donor/acceptor or graphene-like two-dimensional (2D) semiconductors are central to concepts and emerging technologies of light-electricity interconversion. Examples include, among others, solar cells, photodetectors, and light emitting diodes. A salient feature in both types of van der Waals interfaces is the poorly screened Coulomb potential that can give rise to bound electron-hole pairs across the interface, i.e., charge transfer (CT) or interlayer excitons. Here we address common features of CT excitons at both types of interfaces. We emphasize the competition between localization and delocalization in ensuring efficient charge separation. At the molecular donor/acceptor interface, electronic delocalization in real space can dictate charge carrier separation. In contrast, at the 2D semiconductor heterojunction, delocalization in momentum space due to strong exciton binding may assist in parallel momentum conservation in CT exciton formation. PMID:26001297

  3. Millimeter-wave rubidium Rydberg van der Waals spectroscopy

    SciTech Connect

    Han Jianing; Gallagher, T. F.

    2009-05-15

    We have observed the diatomic nsns{yields}ns(n+1)s{yields}(n+1)s(n+1)s microwave transitions of pairs of cold Rb Rydberg atoms for 36der Waals shift due to its near degeneracy with the nearby np{sub 3/2}np{sub 3/2} state. In fact, the energy difference and the van der Waals shift change sign at n=38 and we observe shifts of both signs. The combined excitation of the ns(n+1)s and (n+1)s(n+1)s states leads to an unusual line shape which can be described by a three-level Floquet model.

  4. Van der Waals density functional applied to adsorption systems

    NASA Astrophysics Data System (ADS)

    Hamada, Ikutaro

    2013-03-01

    The van der Waals density functional (vdW-DF) is a promising density functional to describe the van der Waals forces within density functional theory. However, despite the recent efforts, there is still room for further improvement, especially for describing molecular adsorption on metal surfaces. I will show that by choosing appropriate exchange and nonlocal correlation functionals, it is possible to calculate geometries and electronic structures for adsorption systems accurately within the framework of vdW-DF. Applicability of the present approach will be illustrated with its applications to graphene/metal, fullerene/metal, and water/graphene interfaces. This work is partly supported by a Grant-in-Aid for Scientific Research on Innovative Area (No. 23104501). AIMR was established by the World Premier International Research Center Initiative (WPI), MEXT, Japan.

  5. Photovoltaic Effect in an Electrically Tunable van der Waals Heterojunction

    PubMed Central

    2014-01-01

    Semiconductor heterostructures form the cornerstone of many electronic and optoelectronic devices and are traditionally fabricated using epitaxial growth techniques. More recently, heterostructures have also been obtained by vertical stacking of two-dimensional crystals, such as graphene and related two-dimensional materials. These layered designer materials are held together by van der Waals forces and contain atomically sharp interfaces. Here, we report on a type-II van der Waals heterojunction made of molybdenum disulfide and tungsten diselenide monolayers. The junction is electrically tunable, and under appropriate gate bias an atomically thin diode is realized. Upon optical illumination, charge transfer occurs across the planar interface and the device exhibits a photovoltaic effect. Advances in large-scale production of two-dimensional crystals could thus lead to a new photovoltaic solar technology. PMID:25057817

  6. Spin-Flavor van der Waals Forces and NN interaction

    SciTech Connect

    Alvaro Calle Cordon, Enrique Ruiz Arriola

    2011-12-01

    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 computed 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.

  7. Quantum field theory of van der Waals friction

    SciTech Connect

    Volokitin, A. I.; Persson, B. N. J.

    2006-11-15

    van der Waals friction between two semi-infinite solids, and between a small neutral particle and semi-infinite solid is studied using thermal quantum field theory in the Matsubara formulation. We show that the friction to linear order in the sliding velocity can be obtained from the equilibrium Green functions and that our treatment can be extended for bodies with complex geometry. The calculated friction agrees with the friction obtained using a dynamical modification of the Lifshitz theory, which is based on the fluctuation-dissipation theorem. We show that it should be possible to measure the van der Waals friction in noncontact friction experiment using state-of-the-art equipment.

  8. van der Waals explosion of cold Rydberg clusters

    NASA Astrophysics Data System (ADS)

    Faoro, R.; Simonelli, C.; Archimi, M.; Masella, G.; Valado, M. M.; Arimondo, E.; Mannella, R.; Ciampini, D.; Morsch, O.

    2016-03-01

    We report on the direct measurement in real space of the effect of the van der Waals forces between individual Rydberg atoms on their external degrees of freedom. Clusters of Rydberg atoms with interparticle distances of around 5 μ m are created by first generating a small number of seed excitations in a magneto-optical trap, followed by off-resonant excitation that leads to a chain of facilitated excitation events. After a variable expansion time the Rydberg atoms are field ionized, and from the arrival time distributions the size of the Rydberg cluster after expansion is calculated. Our experimental results agree well with a numerical simulation of the van der Waals explosion.

  9. Van der Waals interaction-tuned heat transfer in nanostructures

    NASA Astrophysics Data System (ADS)

    Sun, Tao; Wang, Jianxiang; Kang, Wei

    2012-12-01

    Interfaces usually impede heat transfer in heterogeneous structures. Recent experiments show that van der Waals (vdW) interactions can significantly enhance thermal conductivity parallel to the interface of a bundle of nanoribbons compared to a single layer of freestanding nanoribbon. In this paper, by simulating heat transfer in nanostructures based on a model of nonlinear one-dimensional lattices interacting via van der Waals interactions, we show that the vdW interface interaction can adjust the thermal conductivity parallel to the interface. The efficiency of the adjustment depends on the intensity of interactions and temperature. The nonlinear dependence of the conductivity on the intensity of interactions agrees well with experimental results for carbon nanotube bundles, multi-walled carbon nanotubes, multi-layer graphene, and nanoribbons.

  10. Structure and dynamics of small van der Waals complexes

    SciTech Connect

    Loreau, J.

    2014-10-06

    We illustrate computational aspects of the calculation of the potential energy surfaces of small (up to five atoms) van der Waals complexes with high-level quantum chemistry techniques such as the CCSD(T) method with extended basis sets. We discuss the compromise between the required accuracy and the computational time. Further, we show how these potential energy surfaces can be fitted and used in dynamical calculations such as non-reactive inelastic scattering.

  11. A van der Waals free energy in electrolytes revisited

    NASA Astrophysics Data System (ADS)

    Jancovici, B.

    2006-01-01

    A system of three electrolytes separated by two parallel planes is considered. Each region is described by a dielectric constant and a Coulomb fluid in the Debye-Hückel regime. In their book Dispersion Forces, Mahanty and Ninham have given the van der Waals free energy of this system. We rederive this free energy by a different method, using linear response theory and the electrostatic Maxwell stress tensor for obtaining the dispersion force.

  12. Van der Waals and Casimir-Polder interactions between neutrons

    NASA Astrophysics Data System (ADS)

    Babb, James F.; Hussein, Mahir S.

    2016-03-01

    We investigate the van der Waals interaction between neutrons using the theory of Casimir and Polder, wherein the potential for asymptotically large separations falls off as the inverse seventh power, and compare it to the similar interaction between a neutron and a proton, for which the asymptotic interaction falls off as the inverse fourth power. Modifications of the formalism to extend the validity to smaller separations using dynamic electric and magnetic dipole polarizability data are discussed.

  13. Elution of human granulocytes from nylon fibers by means of repulsive van der Waals forces.

    PubMed

    Absolom, D R; van Oss, C J; Neumann, A W

    1981-01-01

    A novel method for the isolation of granulocytes from nylon fibers is described. It is modification of filtration leukapheresis based on cellular surface thermodynamics. The system takes into account both electrical and van der Waals forces. The elution buffer contains a chelating agent and a surface active agent which lowers the surface tension of the liquid to a value intermediate between that of the surface tensions of the nylon fibers and of the granulocytes. Thus, the attractive van der Waals interaction between the fibers and the granulocytes becomes a repulsion. This results in a two- to threefold increase in cell yield. Phagocytosis, candicidal activity, and oxygen consumption did not appear to be affected through the isolation procedure. By both light and transmission electron microscopy the isolated granulocytes appeared to be morphologically intact. PMID:7314214

  14. Application of diffusion Monte Carlo to materials dominated by van der Waals interactions

    SciTech Connect

    Benali, Anouar; Shulenburger, Luke; Romero, Nichols; Kim, Jeongnim; Von Lilienfeld, Anatole

    2014-01-01

    Van der Waals forces are notoriously difficult to account for from first principles. We perform extensive calculation to assess the usefulness and validity of diffusion quantum Monte Carlo when applied to van der Waals forces. We present results for noble gas solids and clusters - archetypical van der Waals dominated assemblies, as well as a relevant pi-pi stacking supramolecular complex: DNA + intercalating anti-cancer drug Ellipticine.

  15. Application of Diffusion Monte Carlo to Materials Dominated by van der Waals Interactions

    DOE PAGESBeta

    Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; Kim, Jeongnim; von Lilienfeld, O. Anatole

    2014-06-12

    Van der Waals forces are notoriously difficult to account for from first principles. We perform extensive calculation to assess the usefulness and validity of diffusion quantum Monte Carlo when applied to van der Waals forces. We present results for noble gas solids and clusters - archetypical van der Waals dominated assemblies, as well as a relevant pi-pi stacking supramolecular complex: DNA + intercalating anti-cancer drug Ellipticine.

  16. Ionized van-der-Waals systems: Structure and interactions

    SciTech Connect

    Zuelicke, L.

    1996-12-31

    Ions of molecular systems with internal interactions partly of van-der-Waals type differ significantly from their neutral parent species in binding, structure and dynamics. Theoretical knowledge is still rather scarce. The paper discusses some recent advances from theoretical work in the field concerning (i) electronic and geometric structure of triatomic rare-gas containing cations like Ar{sub 3}{sup +} and ArHCI{sup +}, in ground and excited electronic states; (ii) potential energy surfaces for the interaction of H{sup +} or H{sup -} with diatomic molecules, in ground and excited electronic states; (iii) some features of the dynamics of these systems.

  17. Impact of van der Waals Interactions on Single Asperity Friction

    NASA Astrophysics Data System (ADS)

    Lessel, Matthias; Loskill, Peter; Hausen, Florian; Gosvami, Nitya Nand; Bennewitz, Roland; Jacobs, Karin

    2013-07-01

    Single asperity measurements on Si wafers with variable SiO2 layer thickness, yet identical roughness, revealed the influence of van der Waals (vdW) interactions on friction: on thin (1 nm) SiO2 layers, higher friction and jump-off forces were observed as compared to thick (150 nm) SiO2 layers. The vdW interactions were additionally controlled by a set of silanized Si wafers, exhibiting the same trend. The experimental results demonstrate the influence of the subsurface material and are quantitatively described by combining calculations of interactions of the involved materials and the Derjaguin-Müller-Toporov model.

  18. Impact of van der Waals interactions on single asperity friction.

    PubMed

    Lessel, Matthias; Loskill, Peter; Hausen, Florian; Gosvami, Nitya Nand; Bennewitz, Roland; Jacobs, Karin

    2013-07-19

    Single asperity measurements on Si wafers with variable SiO(2) layer thickness, yet identical roughness, revealed the influence of van der Waals (vdW) interactions on friction: on thin (1 nm) SiO(2) layers, higher friction and jump-off forces were observed as compared to thick (150 nm) SiO(2) layers. The vdW interactions were additionally controlled by a set of silanized Si wafers, exhibiting the same trend. The experimental results demonstrate the influence of the subsurface material and are quantitatively described by combining calculations of interactions of the involved materials and the Derjaguin-Müller-Toporov model. PMID:23909336

  19. Phonons in nonlocal van der Waals density functional theory

    NASA Astrophysics Data System (ADS)

    Sabatini, Riccardo; Küçükbenli, Emine; Pham, Cong Huy; de Gironcoli, Stefano

    2016-06-01

    We extend the formulation of density functional perturbation theory to treat nonlocal density functionals, accounting for van der Waals interactions, in a rigorous and efficient way. We provide a general formalism, suitable for any functional in this family, and give specific equations for the most widely used ones. We then study the lattice dynamics of graphite, comparing several nonlocal functionals and the local density approximation, showing that our recent revision of the VV10 functional [R. Sabatini et al., Phys. Rev. B 87, 041108(R) (2013), 10.1103/PhysRevB.87.041108] gives the best comparison with experiments.

  20. Hybrid Meson Potentials and the Gluonic van der Waals Force

    SciTech Connect

    O. Lakhina; E.S. Swanson

    2004-03-01

    The chromoelectric polarizability of mesons governs the strength of the gluonic van der Waals force and therefore of non-quark-exchange processes in hadronic physics. We compute the polarizability of heavy mesons with the aid of lattice gauge theory and the Born--Oppenheimer adiabatic expansion. We find that the operator product expansion breaks down at surprisingly large quarks masses due to nonperturbative gluodynamics and that previous conclusions concerning J/{psi}--nuclear matter interactions and J/{psi} dissociation in the quark-gluon plasma must be substantially modified.

  1. van der Waals forces influencing adhesion of cells

    PubMed Central

    Kendall, K.; Roberts, A. D.

    2015-01-01

    Adhesion molecules, often thought to be acting by a ‘lock and key’ mechanism, have been thought to control the adhesion of cells. While there is no doubt that a coating of adhesion molecules such as fibronectin on a surface affects cell adhesion, this paper aims to show that such surface contamination is only one factor in the equation. Starting from the baseline idea that van der Waals force is a ubiquitous attraction between all molecules, and thereby must contribute to cell adhesion, it is clear that effects from geometry, elasticity and surface molecules must all add on to the basic cell attractive force. These effects of geometry, elasticity and surface molecules are analysed. The adhesion force measured between macroscopic polymer spheres was found to be strongest when the surfaces were absolutely smooth and clean, with no projecting protruberances. Values of the measured surface energy were then about 35 mJ m−2, as expected for van der Waals attractions between the non-polar molecules. Surface projections such as abrasion roughness or dust reduced the molecular adhesion substantially. Water cut the measured surface energy to 3.4 mJ m−2. Surface active molecules lowered the adhesion still further to less than 0.3 mJ m−2. These observations do not support the lock and key concept. PMID:25533101

  2. Van der Waals Epitaxy of Ultrathin Halide Perovkistes

    NASA Astrophysics Data System (ADS)

    Wang, Yiping; Shi, Yunfeng; Shi, Jian

    We present our understanding, with CH3NH3PbX3 as a model system, on the 2D van der Waals growth and kinetics of 3D parent materials. We show the successful synthesis of ultrathin (sub-10 nm), large scale (a few tens of μm) single crystalline 2D perovskite thin films on layered mica substrate by van der Waals (VDW) epitaxy. Classical nucleation and growth model explaining conventional epitaxy has been modified to interpret the unique 2D results under VDW mechanism. The generalization of our model shows that a 3D crystal with low cohesive energy tends to favor the 2D growth while the one with strong cohesive energy has less kinetic window. With Monte Carlo simulations, we show that the fractal 2D morphology in perovskite precisely manifests the kinetic competition between VDW diffusivity and thermodynamic driving force, a unique phenomenon to VDW growth, suggesting a fundamental limit on the morphology stability of the 2D form of a 3D material. On the other hand, our single crystal thin film growth results and subsequent cryogenic study in the iodide perovskite provide a perfect resource for the exploration of its complex optical and electronic properties and unveiling the origins of its popularity in the energy conversion field.

  3. Synthesis and Investigation of van der Waals Heterostructures

    NASA Astrophysics Data System (ADS)

    McCreary, Kathleen; Hanbicki, Aubrey; Culbertson, James; Currie, Marc; Jonker, Berend

    2015-03-01

    The recent isolation of single layers of transition metal dichalcogenides (TMD) has demonstrated that reducing dimensionality can alter the material properties. In particular, MoS2, MoSe2, WS2, and WSe2 exhibit an abrupt transition from indirect to direct bandgap semiconductors at monolayer thickness. Monolayer TMDs are promising materials for electronic components due to their high mobility, high on/off ratio, and low standby power dissipation. Additionally, selective layer-by-layer stacking to form van der Waals (vdW) heterostructures may provide the ability to controllably engineer electronic, optic, and spintronic properties. Recently, several methods were investigated to achieve vdW heterostructures including sequential exfoliation, stacking of chemical vapor deposition (CVD) grown monolayers, and epitaxial growth of bilayers. We detail our CVD synthesis of the monolayer TMDs (MoS2, MoSe2, WS2 and WSe2) and the subsequent fabrication and characterization of vdW heterostructures. In our heterostructures, we observe a dramatic decrease in PL intensity compared to the monolayer constituents. The Raman spectra exhibit clear and distinct differences from a superposition of monolayer spectra, demonstrating that interactions across the van der Waals interface in these heterostructures may significantly modify the net electronic properties. We find the observed behaviors are influenced by many factors, including charge transfer, substrate effects, stacking sequence, as well as intra- and inter-layer exciton formation, which will be discussed here.

  4. Two-dimensional van der Waals C60 molecular crystal

    PubMed Central

    Reddy, C. D.; Gen Yu, Zhi; Zhang, Yong-Wei

    2015-01-01

    Two-dimensional (2D) atomic crystals, such as graphene and transition metal dichalcogenides et al. have drawn extraordinary attention recently. For these 2D materials, atoms within their monolayer are covalently bonded. An interesting question arises: Can molecules form a 2D monolayer crystal via van der Waals interactions? Here, we first study the structural stability of a free-standing infinite C60 molecular monolayer using molecular dynamic simulations, and find that the monolayer is stable up to 600 K. We further study the mechanical properties of the monolayer, and find that the elastic modulus, ultimate tensile stress and failure strain are 55–100 GPa, 90–155 MPa, and 1.5–2.3%, respectively, depending on the stretching orientation. The monolayer fails due to shearing and cavitation under uniaxial tensile loading. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the monolayer are found to be delocalized and as a result, the band gap is reduced to only 60% of the isolated C60 molecule. Interestingly, this band gap can be tuned up to ±30% using strain engineering. Owing to its thermal stability, low density, strain-tunable semi-conducting characteristics and large bending flexibility, this van der Waals molecular monolayer crystal presents aplenty opportunities for developing novel applications in nanoelectronics. PMID:26183501

  5. Quantum Monte Carlo Simulation of condensed van der Waals Systems

    NASA Astrophysics Data System (ADS)

    Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; Kim, Jeongnim; Anatole von Lilienfeld, O.

    2012-02-01

    Van der Waals forces are as ubiquitous as infamous. While post-Hartree-Fock methods enable accurate estimates of these forces in molecules and clusters, they remain elusive for dealing with many-electron condensed phase systems. We present Quantum Monte Carlo [1,2] results for condensed van der Waals systems. Interatomic many-body contributions to cohesive energies and bulk modulus will be discussed. Numerical evidence is presented for crystals of rare gas atoms, and compared to experiments and methods [3]. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DoE's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.[4pt] [1] J. Kim, K. Esler, J. McMinis and D. Ceperley, SciDAC 2010, J. of Physics: Conference series, Chattanooga, Tennessee, July 11 2011 [0pt] [2] QMCPACK simulation suite, http://qmcpack.cmscc.org (unpublished)[0pt] [3] O. A. von Lillienfeld and A. Tkatchenko, J. Chem. Phys. 132 234109 (2010)

  6. Two-dimensional van der Waals C60 molecular crystal

    NASA Astrophysics Data System (ADS)

    Reddy, C. D.; Gen Yu, Zhi; Zhang, Yong-Wei

    2015-07-01

    Two-dimensional (2D) atomic crystals, such as graphene and transition metal dichalcogenides et al. have drawn extraordinary attention recently. For these 2D materials, atoms within their monolayer are covalently bonded. An interesting question arises: Can molecules form a 2D monolayer crystal via van der Waals interactions? Here, we first study the structural stability of a free-standing infinite C60 molecular monolayer using molecular dynamic simulations, and find that the monolayer is stable up to 600 K. We further study the mechanical properties of the monolayer, and find that the elastic modulus, ultimate tensile stress and failure strain are 55-100 GPa, 90-155 MPa, and 1.5-2.3%, respectively, depending on the stretching orientation. The monolayer fails due to shearing and cavitation under uniaxial tensile loading. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the monolayer are found to be delocalized and as a result, the band gap is reduced to only 60% of the isolated C60 molecule. Interestingly, this band gap can be tuned up to ±30% using strain engineering. Owing to its thermal stability, low density, strain-tunable semi-conducting characteristics and large bending flexibility, this van der Waals molecular monolayer crystal presents aplenty opportunities for developing novel applications in nanoelectronics.

  7. van der Waals interaction as a summable asymptotic series

    NASA Astrophysics Data System (ADS)

    Perdew, John P.; Ruzsinszky, Adrienn; Sun, Jianwei; Glindmeyer, Stephen; Csonka, Gabor I.

    2012-12-01

    The dynamic multipole polarizabilities and thus the second-order van der Waals coefficients C2k of all orders are known exactly for the interaction between two classical spherical conducting shells, each of uniform electron density ρ with outer radius R and thickness t. The result is C2k=-ck(t/R)4πρ[(2R)2]k. The ck approach a limiting constant value, so the infinite series for the van der Waals interaction at separation d, -C6/d6-C8/d8-⋯, can be summed analytically, diverging only for d≤2R. This divergence can be removed without changing the asymptotic series. Real quasispherical objects like nanoclusters, fullerenes, and even atoms can be approximated by this spherical-shell model, with R fixed by the true static dipole polarizability. Once t/R is fixed, all the higher coefficients are determined by just C6 and C8. Finally, we compare the exact C2k to those from a pair interaction model, which works for solid spheres (t=R) but not for fullerenes.

  8. Opportunities and challenges of 2D magnetic van der Waals materials: magnetic graphene?

    NASA Astrophysics Data System (ADS)

    Park, Je-Geun

    2016-08-01

    There has been a huge increase of interests in two-dimensional van der Waals materials over the past ten years or so with the conspicuous absence of one particular class of materials: magnetic van der Waals systems. In this Viewpoint, we point it out and illustrate how we might be able to benefit from exploring these so-far neglected materials.

  9. Van der Waals Epitaxy of Functional Oxide Heterostructures

    NASA Astrophysics Data System (ADS)

    Chu, Ying-Hao

    In the diligent pursuit of low-power consumption, multifunctional, and environmentally friendly electronics, more sophisticated requirements on functional materials are on demand. Recently, the discovery of 2D layered materials has created a revolution to this field. Pioneered by graphene, these new 2D materials exhibit abundant unusual physical phenomena that is undiscovered in bulk forms. These materials are characterized with their layer form and almost pure 2D electronic behavior. The confinement of charge and heat transport at such ultrathin planes offers possibilities to overcome the bottleneck of present device development in thickness limitation, and thus push the technologies into next generation. Van der Waals epitaxy, an epitaxial growth method to combine 2D and 3D materials, is one of current reliable manufacturing processes to fabricate 2D materials by growing these 2D materials epitaxially on 3D materials. Then, transferring the 2D materials to the substrates for practical applications. In the mean time, van der Waals epitaxy has also been used to create free-standing 3D materials by growing 3D materials on 2D materials and then removing them from 2D materials since the interfacial boding between 2D and 3D materials should be weak van der Waals bonds. In this study, we intend to take the same concept, but to integrate a family of functional materials in order to open new avenue to flexible electronics. Due to the interplay of lattice, charge, orbital, and spin degrees of freedom, correlated electrons in oxides generate a rich spectrum of competing phases and physical properties. Recently, lots of studies have suggested that oxide heterostructures provide a powerful route to create and manipulate the degrees of freedom and offer new possibilities for next generation devices, thus create a new playground for researchers to investigate novel physics and the emergence of fascinating states of condensed matter. In this talk, we use a 2D layered material as

  10. Effects of zero van der Waals and zero electrostatic forces on droplet sedimentation

    NASA Technical Reports Server (NTRS)

    Omenyi, S. N.; Snyder, R. S.; Van Oss, C. J.; Absolom, D. R.; Neumann, A. W.

    1981-01-01

    The present investigation provides a confirmation of the dependence of droplet sedimentation on particle concentration. It is shown that it is possible to determine the maximum particle concentration which can remain stable on a given liquid from droplet sedimentation experiments. Droplet sedimentation can be reduced but not totally eliminated by the addition of appropriate amounts of dimethyl sulfoxide (DMSO) to reduce the van der Waals forces to zero. It was found that, at 12% DMSO, a maximum particle concentration of 6.3 x 10 to the 8th cells/ml of glutaraldehyde-fixed human erythrocytes suspended in physiological saline can remain stable on a D2O cushion.

  11. Coincident-site lattice matching during van der Waals epitaxy

    PubMed Central

    Boschker, Jos E.; Galves, Lauren A.; Flissikowski, Timur; Lopes, Joao Marcelo J.; Riechert, Henning; Calarco, Raffaella

    2015-01-01

    Van der Waals (vdW) epitaxy is an attractive method for the fabrication of vdW heterostructures. Here Sb2Te3 films grown on three different kind of graphene substrates (monolayer epitaxial graphene, quasi freestanding bilayer graphene and the SiC (6√3 × 6√3)R30° buffer layer) are used to study the vdW epitaxy between two 2-dimensionally (2D) bonded materials. It is shown that the Sb2Te3 /graphene interface is stable and that coincidence lattices are formed between the epilayers and substrate that depend on the size of the surface unit cell. This demonstrates that there is a significant, although relatively weak, interfacial interaction between the two materials. Lattice matching is thus relevant for vdW epitaxy with two 2D bonded materials and a fundamental design parameter for vdW heterostructures. PMID:26658715

  12. Body-assisted van der Waals interaction between two atoms

    SciTech Connect

    Safari, Hassan; Buhmann, Stefan Yoshi; Welsch, Dirk-Gunnar; Ho Trung Dung

    2006-10-15

    Using fourth-order perturbation theory, a general formula for the van der Waals potential of two neutral, unpolarized, ground-state atoms in the presence of an arbitrary arrangement of dispersing and absorbing magnetodielectric bodies is derived. The theory is applied to two atoms in bulk material and in front of a planar multilayer system, with special emphasis on the cases of a perfectly reflecting plate and a semi-infinite half space. It is demonstrated that the enhancement and reduction of the two-atom interaction due to the presence of a perfectly reflecting plate can be understood, at least in the nonretarded limit, by using the method of image charges. For the semi-infinite half space, both analytical and numerical results are presented.

  13. Characterization of rarefaction waves in van der Waals fluids

    NASA Astrophysics Data System (ADS)

    Yuen, Albert; Barnard, John J.

    2015-12-01

    We calculate the isentropic evolution of an instantaneously heated foil, assuming a van der Waals equation of state with the Maxwell construction. The analysis by Yuen and Barnard [Phys. Rev. E 92, 033019 (2015), 10.1103/PhysRevE.92.033019] is extended for the particular case of three degrees of freedom. We assume heating to temperatures in the vicinity of the critical point. The self-similar profiles of the rarefaction waves describing the evolution of the foil display plateaus in density and temperature due to a phase transition from the single-phase to the two-phase regime. The hydrodynamic equations are expressed in a dimensionless form and the solutions form a set of universal curves, depending on a single parameter: the dimensionless initial entropy. We characterize the rarefaction waves by calculating how the plateau length, density, pressure, temperature, velocity, internal energy, and sound speed vary with dimensionless initial entropy.

  14. Heterostructures based on inorganic and organic van der Waals systems

    SciTech Connect

    Lee, Gwan-Hyoung; Lee, Chul-Ho; Zande, Arend M. van der; Han, Minyong; Cui, Xu; Arefe, Ghidewon; Hone, James; Nuckolls, Colin; Heinz, Tony F.; Kim, Philip

    2014-09-01

    The two-dimensional limit of layered materials has recently been realized through the use of van der Waals (vdW) heterostructures composed of weakly interacting layers. In this paper, we describe two different classes of vdW heterostructures: inorganic vdW heterostructures prepared by co-lamination and restacking; and organic-inorganic hetero-epitaxy created by physical vapor deposition of organic molecule crystals on an inorganic vdW substrate. Both types of heterostructures exhibit atomically clean vdW interfaces. Employing such vdW heterostructures, we have demonstrated various novel devices, including graphene/hexagonal boron nitride (hBN) and MoS{sub 2} heterostructures for memory devices; graphene/MoS{sub 2}/WSe{sub 2}/graphene vertical p-n junctions for photovoltaic devices, and organic crystals on hBN with graphene electrodes for high-performance transistors.

  15. Van der Waals Interactions in Density Functional Theory: Intermolecular Complexes

    NASA Astrophysics Data System (ADS)

    Kannemann, Felix; Becke, Axel

    2010-03-01

    Conventional density functional theory (GGA and hybrid functionals) fails to account for dispersion interactions and is therefore not applicable to systems where van der Waals interactions play a dominant role, such as intermolecular complexes and biomolecules. The exchange-hole dipole moment (XDM) dispersion model of Becke and Johnson [A. D. Becke and E. R. Johnson, J. Chem. Phys. 127, 154108 (2007)] corrects for this deficiency. We have previously shown that the XDM dispersion model can be combined with standard GGA functionals (PW86 for exchange and PBE for correlation) to give accurate binding energy curves for rare-gas diatomics [F. O. Kannemann and A. D. Becke, J. Chem. Theory Comput. 5, 719 (2009)]. Here we present further tests of the GGA-XDM method using benchmark sets including hydrogen bonding, electrostatic, dispersion and stacking interactions, and systems ranging from rare-gas diatomics to biomolecular complexes.

  16. Van der Waals Density Functional Theory with Applications

    NASA Astrophysics Data System (ADS)

    Langreth, David C.

    2004-03-01

    We discuss the development of electronic density functionals that are applicable for weakly bound systems where the van der Waals interaction and its ramifications become important. Our current functionals approach the correct asymptotic dependence at large distances and are seamless at small distances. The first form of the functional, appropriate for layered systems, has been recently applied to graphite, boron nitride, and molybdenum sulfide [H. Rydberg et al., Phys. Rev. Lett. 91, 126402 (2003) and D. C. Langreth, Int. J. Quant. Chem. (submitted), see http//:www.physics.rutgers.edu/ ˜langreth/preprints/dft2003.pdf]. The second form of the functional [M. Dion it et al. (to be published)] is appropriate for arbitrary geometries. Recent results on rare gas dimers and the benzene dimer suggest promise for this method as well.

  17. A crossover in anisotropic nanomechanochemistry of van der Waals crystals

    SciTech Connect

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

    2015-12-07

    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{sup −13} s from the passage of shock front, lateral collision produces NO{sub 2} 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{sup −12} s, shock normal to multilayers becomes more reactive, producing H{sub 2}O 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.

  18. Characterization of rarefaction waves in van der Waals fluids.

    PubMed

    Yuen, Albert; Barnard, John J

    2015-12-01

    We calculate the isentropic evolution of an instantaneously heated foil, assuming a van der Waals equation of state with the Maxwell construction. The analysis by Yuen and Barnard [Phys. Rev. E 92, 033019 (2015)] is extended for the particular case of three degrees of freedom. We assume heating to temperatures in the vicinity of the critical point. The self-similar profiles of the rarefaction waves describing the evolution of the foil display plateaus in density and temperature due to a phase transition from the single-phase to the two-phase regime. The hydrodynamic equations are expressed in a dimensionless form and the solutions form a set of universal curves, depending on a single parameter: the dimensionless initial entropy. We characterize the rarefaction waves by calculating how the plateau length, density, pressure, temperature, velocity, internal energy, and sound speed vary with dimensionless initial entropy. PMID:26764692

  19. 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.

  20. Band Gap Engineering of PbI2 by Incommensurate Van der Waals Epitaxy

    NASA Astrophysics Data System (ADS)

    Wang, Yiping; Shi, Jian

    Van der Waals epitaxial growth had been thought to have trivial contribution on inducing substantial epitaxial strain in thin films due to its weak nature of Van der Waals interfacial energy. Due to this, electrical and optical structure engineering via Van der Waals epitaxial strain has been rarely studied. However, by appropriate film-substrate selection, we show that significant band structure engineering could be achieved in a soft thin film material PbI2 via Van der Waals epitaxy. The thickness dependent photoluminescence of single crystal PbI2 flakes was studied and attributed to the substrate-film coupling effect via incommensurate Van der Waals epitaxy. It is proposed that the Van der Waals strain is resulted from the soft nature of PbI2 and large Van der Waals interaction due to the involvement of heavy elements. Such strain plays vital roles in modifying the band gap of PbI2. The deformation potential theory is used to quantitatively unveil the correlation between thickness, strain and band gap change. Our hypothesis is confirmed by the subsequent mechanical bending test and Raman characterization.

  1. Tuning the van der Waals Interaction of Graphene with Molecules via Doping

    NASA Astrophysics Data System (ADS)

    Huttmann, Felix; Martínez-Galera, Antonio J.; Caciuc, Vasile; Atodiresei, Nicolae; Schumacher, Stefan; Standop, Sebastian; Hamada, Ikutaro; Wehling, Tim O.; Blügel, Stefan; Michely, Thomas

    2015-12-01

    We use scanning tunneling microscopy to visualize and thermal desorption spectroscopy to quantitatively measure that the binding of naphthalene molecules to graphene, a case of pure van der Waals interaction, strengthens with n and weakens with p doping of graphene. Density-functional theory calculations that include the van der Waals interaction in a seamless, ab initio way accurately reproduce the observed trend in binding energies. Based on a model calculation, we propose that the van der Waals interaction is modified by changing the spatial extent of graphene's π orbitals via doping.

  2. Tuning the van der Waals Interaction of Graphene with Molecules via Doping.

    PubMed

    Huttmann, Felix; Martínez-Galera, Antonio J; Caciuc, Vasile; Atodiresei, Nicolae; Schumacher, Stefan; Standop, Sebastian; Hamada, Ikutaro; Wehling, Tim O; Blügel, Stefan; Michely, Thomas

    2015-12-01

    We use scanning tunneling microscopy to visualize and thermal desorption spectroscopy to quantitatively measure that the binding of naphthalene molecules to graphene, a case of pure van der Waals interaction, strengthens with n and weakens with p doping of graphene. Density-functional theory calculations that include the van der Waals interaction in a seamless, ab initio way accurately reproduce the observed trend in binding energies. Based on a model calculation, we propose that the van der Waals interaction is modified by changing the spatial extent of graphene's π orbitals via doping. PMID:26684126

  3. Nuclear spin-spin coupling in a van der Waals-bonded system: xenon dimer.

    PubMed

    Vaara, Juha; Hanni, Matti; Jokisaari, Jukka

    2013-03-14

    Nuclear spin-spin coupling over van der Waals bond has recently been observed via the frequency shift of solute protons in a solution containing optically hyperpolarized (129)Xe nuclei. We carry out a first-principles computational study of the prototypic van der Waals-bonded xenon dimer, where the spin-spin coupling between two magnetically non-equivalent isotopes, J((129)Xe - (131)Xe), is observable. We use relativistic theory at the four-component Dirac-Hartree-Fock and Dirac-density-functional theory levels using novel completeness-optimized Gaussian basis sets and choosing the functional based on a comparison with correlated ab initio methods at the nonrelativistic level. J-coupling curves are provided at different levels of theory as functions of the internuclear distance in the xenon dimer, demonstrating cross-coupling effects between relativity and electron correlation for this property. Calculations on small Xe clusters are used to estimate the importance of many-atom effects on J((129)Xe - (131)Xe). Possibilities of observing J((129)Xe - (131)Xe) in liquid xenon are critically examined, based on molecular dynamics simulation. A simplistic spherical model is set up for the xenon dimer confined in a cavity, such as in microporous materials. It is shown that the on the average shorter internuclear distance enforced by the confinement increases the magnitude of the coupling as compared to the bulk liquid case, rendering J((129)Xe - (131)Xe) in a cavity a feasible target for experimental investigation. PMID:23514495

  4. Gate tunable WSe2-BP van der Waals heterojunction devices

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Zhang, Ting Ting; Zhang, Jing; Xiang, Jianyong; Yu, Hua; Wu, Shuang; Lu, Xiaobo; Wang, Guole; Wen, Fusheng; Liu, Zhongyuan; Yang, Rong; Shi, Dongxia; Zhang, Guangyu

    2016-02-01

    Due to the weak screening effect, the concentration and type of charge carriers in 2D semiconductor heterostructures can be effectively tuned by electrostatic gating, enabling us to realize different types of heterojunctions in a single device. Such `type tunable' properties are useful for designing novel electrical or optoelectrical devices. Here, we demonstrate a `type tunable' heterojunction device construct with two pieces of ambipolar 2D semiconductors: WSe2 and black phosphorus (BP). This heterojunction could be tuned to either the p-p junction or n-n junction by gate modulation. The p-p junction shows a large current rectification ratio while the n-n junction shows a negligible current rectification ratio, indicating a large valence band offset and a small conduction band offset at the WSe2/BP interface. In the optoelectrical measurements, we found the amplitude and even the polarity of photocurrent could be modulated by electrostatic gating. Our study could further enhance the understanding of designing devices based on these `type tunable' van der Waals heterojunctions. Moreover, the properties of the WSe2/BP interface were also experimentally identified through the electrical and optoelectrical measurements in our study.Due to the weak screening effect, the concentration and type of charge carriers in 2D semiconductor heterostructures can be effectively tuned by electrostatic gating, enabling us to realize different types of heterojunctions in a single device. Such `type tunable' properties are useful for designing novel electrical or optoelectrical devices. Here, we demonstrate a `type tunable' heterojunction device construct with two pieces of ambipolar 2D semiconductors: WSe2 and black phosphorus (BP). This heterojunction could be tuned to either the p-p junction or n-n junction by gate modulation. The p-p junction shows a large current rectification ratio while the n-n junction shows a negligible current rectification ratio, indicating a large valence

  5. Surface energy and wettability of van der Waals structures

    NASA Astrophysics Data System (ADS)

    Annamalai, Meenakshi; Gopinadhan, Kalon; Han, Sang A.; Saha, Surajit; Park, Hye Jeong; Cho, Eun Bi; Kumar, Brijesh; Patra, Abhijeet; Kim, Sang-Woo; Venkatesan, T.

    2016-03-01

    The wetting behaviour of surfaces is believed to be affected by van der Waals (vdW) forces; however, there is no clear demonstration of this. With the isolation of two-dimensional vdW layered materials it is possible to test this hypothesis. In this paper, we report the wetting behaviour of vdW heterostructures which include chemical vapor deposition (CVD) grown graphene, molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on few layers of hexagon boron nitride (h-BN) and SiO2/Si. Our study clearly shows that while this class of two-dimensional materials are not completely wetting transparent, there seems to be a significant amount of influence on their wetting properties by the underlying substrate due to dominant vdW forces. Contact angle measurements indicate that graphene and graphene-like layered transitional metal dichalcogenides invariably have intrinsically dispersive surfaces with a dominating London-vdW force-mediated wettability.The wetting behaviour of surfaces is believed to be affected by van der Waals (vdW) forces; however, there is no clear demonstration of this. With the isolation of two-dimensional vdW layered materials it is possible to test this hypothesis. In this paper, we report the wetting behaviour of vdW heterostructures which include chemical vapor deposition (CVD) grown graphene, molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on few layers of hexagon boron nitride (h-BN) and SiO2/Si. Our study clearly shows that while this class of two-dimensional materials are not completely wetting transparent, there seems to be a significant amount of influence on their wetting properties by the underlying substrate due to dominant vdW forces. Contact angle measurements indicate that graphene and graphene-like layered transitional metal dichalcogenides invariably have intrinsically dispersive surfaces with a dominating London-vdW force-mediated wettability. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06705

  6. Excitons in one-dimensional van der Waals materials: Sb2S3 nanoribbons

    NASA Astrophysics Data System (ADS)

    Caruso, Fabio; Filip, Marina R.; Giustino, Feliciano

    2015-09-01

    Antimony sulphide Sb2S3 has emerged as a promising material for a variety of energy applications ranging from solar cells to thermoelectrics and solid-state batteries. The most distinctive feature of Sb2S3 is its crystal structure, which consists of parallel 1-nm-wide ribbons held together by weak van der Waals forces. This structure clearly suggests that it should be possible to isolate individual Sb2S3 ribbons using micromechanical or liquid-phase exfoliation techniques. However, it is not clear yet how to identify the ribbons postexfoliation using standard optical probes. Using state-of-the-art first-principles calculations based on many-body perturbation theory, here we show that individual ribbons of Sb2S3 carry optical signatures clearly distinct from those of bulk Sb2S3 . In particular, we find a large blueshift of the optical absorption edge (from 1.38 to 2.30 eV) resulting from the interplay between a reduced screening and the formation of bound excitons. In addition, we observe a transition from an indirect band gap to a direct gap, suggesting an enhanced photoluminescence in the green. These unique fingerprints will enable extending the research on van der Waals materials to the case of one-dimensional chalchogenides.

  7. Theoretical investigation of van der Waals forces between solid surfaces at nanoscales

    NASA Astrophysics Data System (ADS)

    Kudryavtsev, Yaroslav V.; Gelinck, Edwin; Fischer, Hartmut R.

    2009-08-01

    A theoretical investigation of van der Waals forces acting between two solid silicon surfaces at separations from zero to approximately 20 nm is presented. We focused our efforts on the analysis of different factors that can cause deviations from the classical pressure-distance dependence p ˜ 1/ D3. It is demonstrated that a layer (oxide or water) at any of the surfaces influences the pressure up to distances, which are an order of magnitude larger than its own thickness. A jump on the p( D) curve is expected at contact of the adsorbed liquid layers. The retardation of van der Waals forces at 5 < D < 20 nm has the similar effect on the pressure as 1 nm oxide layers. At the far end of this range the pressure decreases by 30% due to the retardation. Nanoscale roughness plays a great role when the surfaces are close-to-contact, the crucial factor is the height distribution of asperities. However, their curvature and surface density are also important, as well as the amount of adsorbed water.

  8. Hemiquantal mechanics. I. Vibrational predissociation of van der Waals molecules

    NASA Astrophysics Data System (ADS)

    Halcomb, Lawrence L.; Diestler, D. J.

    1986-03-01

    The ``hemiquantal'' equations (HQE), which pertain to a system consisting of a quantally-behaving (``light'') subsystem coupled to a classically-behaving (``heavy'') one, result from a partial classical limit of Heisenberg's equations of motion. In effect, all heavy particles are required to follow precisely their classical trajectories. The HQE are applied to vibrational predissociation in a collinear model of the van der Waals molecule He ṡ ṡ ṡI2(B). Here, the vibration of I2 is the classical subsystem and the motion of He relative to the center of mass of I2 is the quantal subsystem. In this case, the HQE comprise a partial differential equation (Schrödinger's equation for the He motion) coupled to two ordinary differential equations (Hamilton's equations for the I2 vibration). These were solved numerically on the CYBER 205 supercomputer by means of an algorithm that uses a second-order predictor-corrector for Hamilton's equations and second-order time differencing for Schrödinger's equation. A scheme based on the fast Fourier transform was used to evaluate the spatial derivative of the wave function. The computed rates of vibrational predissociation are compared with the results of previous quasiclassical and fully quantal calculations and with experimental results.

  9. Spatially Correlated Disorder in Epitaxial van der Waals Heterostructures

    NASA Astrophysics Data System (ADS)

    Laanait, Nouamane; Zhang, Zhan; Schleputz, Christian; Liu, Ying; Wojcik, Michael; Myers-Ward, Rachael; Gaskill, D. Kurt; Fenter, Paul; Li, Lian

    The structural cohesion of van der Waals (vdW) heterostructures relies upon a cooperative balance between strong intra-layer bonded interactions and weak inter-layer coupling. The confinement of extended defects to within a single vdW layer and competing interactions introduced by epitaxial constraints could generate fundamentally new structural disorders. Here we report on the presence of spatially correlated and localized disorder states that coexist with the near perfect crystallographic order along the growth direction of epitaxial vdW heterostructure of Bi2Se3/graphene/SiC grown by molecular beam epitaxy. With the depth penetration of hard X-ray diffraction microscopy and high-resolution surface scattering, we imaged local structural configurations from the atomic to mesoscopic length scales, and found that these disorder states result as a confluence of atomic scale modulations in the strength of vdW layer-layer interactions and nanoscale boundary conditions imposed by the substrate. These findings reveal a vast landscape of novel disorder states that can be manifested in epitaxial vdW heterostructures. Supported by the Wigner Fellowship program at Oak Ridge Nat'l Lab.

  10. Peptide folding driven by Van der Waals interactions.

    PubMed

    Sung, Shen-Shu

    2015-09-01

    Contrary to the widespread view that hydrogen bonding and its entropy effect play a dominant role in protein folding, folding into helical and hairpin-like structures is observed in molecular dynamics (MD) simulations without hydrogen bonding in the peptide-solvent system. In the widely used point charge model, hydrogen bonding is calculated as part of the interaction between atomic partial charges. It is removed from these simulations by setting atomic charges of the peptide and water to zero. Because of the structural difference between the peptide and water, van der Waals (VDW) interactions favor peptide intramolecular interactions and are a major contributing factor to the structural compactness. These compact structures are amino acid sequence dependent and closely resemble standard secondary structures, as a consequence of VDW interactions and covalent bonding constraints. Hydrogen bonding is a short range interaction and it locks the approximate structure into the specific secondary structure when it is included in the simulation. In contrast to standard molecular simulations where the total energy is dominated by charge-charge interactions, these simulation results will give us a new view of the folding mechanism. PMID:26013298

  11. Photocurrent generation with two-dimensional van der Waals semiconductors.

    PubMed

    Buscema, Michele; Island, Joshua O; Groenendijk, Dirk J; Blanter, Sofya I; Steele, Gary A; van der Zant, Herre S J; Castellanos-Gomez, Andres

    2015-06-01

    Two-dimensional (2D) materials have attracted a great deal of interest in recent years. This family of materials allows for the realization of versatile electronic devices and holds promise for next-generation (opto)electronics. Their electronic properties strongly depend on the number of layers, making them interesting from a fundamental standpoint. For electronic applications, semiconducting 2D materials benefit from sizable mobilities and large on/off ratios, due to the large modulation achievable via the gate field-effect. Moreover, being mechanically strong and flexible, these materials can withstand large strain (>10%) before rupture, making them interesting for strain engineering and flexible devices. Even in their single layer form, semiconducting 2D materials have demonstrated efficient light absorption, enabling large responsivity in photodetectors. Therefore, semiconducting layered 2D materials are strong candidates for optoelectronic applications, especially for photodetection. Here, we review the state-of-the-art in photodetectors based on semiconducting 2D materials, focusing on the transition metal dichalcogenides, novel van der Waals materials, black phosphorus, and heterostructures. PMID:25909688

  12. Surface energy and wettability of van der Waals structures.

    PubMed

    Annamalai, Meenakshi; Gopinadhan, Kalon; Han, Sang A; Saha, Surajit; Park, Hye Jeong; Cho, Eun Bi; Kumar, Brijesh; Patra, Abhijeet; Kim, Sang-Woo; Venkatesan, T

    2016-03-14

    The wetting behaviour of surfaces is believed to be affected by van der Waals (vdW) forces; however, there is no clear demonstration of this. With the isolation of two-dimensional vdW layered materials it is possible to test this hypothesis. In this paper, we report the wetting behaviour of vdW heterostructures which include chemical vapor deposition (CVD) grown graphene, molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on few layers of hexagon boron nitride (h-BN) and SiO2/Si. Our study clearly shows that while this class of two-dimensional materials are not completely wetting transparent, there seems to be a significant amount of influence on their wetting properties by the underlying substrate due to dominant vdW forces. Contact angle measurements indicate that graphene and graphene-like layered transitional metal dichalcogenides invariably have intrinsically dispersive surfaces with a dominating London-vdW force-mediated wettability. PMID:26910437

  13. Gate tunable WSe2-BP van der Waals heterojunction devices.

    PubMed

    Chen, Peng; Zhang, Ting Ting; zhang, Jing; Xiang, Jianyong; Yu, Hua; Wu, Shuang; Lu, Xiaobo; Wang, Guole; Wen, Fusheng; Liu, Zhongyuan; Yang, Rong; Shi, Dongxia; Zhang, Guangyu

    2016-02-14

    Due to the weak screening effect, the concentration and type of charge carriers in 2D semiconductor heterostructures can be effectively tuned by electrostatic gating, enabling us to realize different types of heterojunctions in a single device. Such 'type tunable' properties are useful for designing novel electrical or optoelectrical devices. Here, we demonstrate a 'type tunable' heterojunction device construct with two pieces of ambipolar 2D semiconductors: WSe2 and black phosphorus (BP). This heterojunction could be tuned to either the p-p junction or n-n junction by gate modulation. The p-p junction shows a large current rectification ratio while the n-n junction shows a negligible current rectification ratio, indicating a large valence band offset and a small conduction band offset at the WSe2/BP interface. In the optoelectrical measurements, we found the amplitude and even the polarity of photocurrent could be modulated by electrostatic gating. Our study could further enhance the understanding of designing devices based on these 'type tunable' van der Waals heterojunctions. Moreover, the properties of the WSe2/BP interface were also experimentally identified through the electrical and optoelectrical measurements in our study. PMID:26810387

  14. Effects of van der Waals interaction on nanoparticle adsorption

    NASA Astrophysics Data System (ADS)

    Poddar, Nitun; Amar, Jacques

    2014-03-01

    The results of molecular dynamics (MD) simulations carried out using an all-atom model in order to understand the structure, diffusion, and binding of dodecanethiol (DDT)-coated Au nanoparticles (NPs) at the toluene-air interface are presented. We find that due to the strong attraction between DDT and toluene, the NP lies mainly below the interface. As a result, the coefficient for diffusion along the interface is close to the Stokes-Einstein prediction for 3D bulk diffusion. We also find that, due to the small ratio of ligand length to NP diameter, there is little spontaneous asymmetry in the NP coating. We have also used our MD results along with analytical expressions for the van der Waals (VdW) interactions to estimate corrections to the adsorption energy for DDT-coated Au NPs at the toluene-vapor interface as well as for alkanethiol-coated NPs at the water-vapor interface. In both cases, we find that the core-solvent interaction may significantly reduce the binding energy. We also find that the competition between this interaction and short-range attraction to the interface leads to well-defined activation barriers for interfacial desorption as well as for NP adsorption from the solvent. This work was supported by NSF Grant No. CHE-1012896.

  15. Van der Waals interactions in density functional theory

    NASA Astrophysics Data System (ADS)

    Langreth, David C.

    2009-03-01

    The van der Waals density functional which we introduced half a decade agoootnotetextM. Dion et al. Phys. Rev. Lett. 92, 246401 (2004). and its self-consistent generalizationootnotetextT. Thonhauser et al., Phys. Rev. B 76, 125112 (2007). will be briefly reviewed. There are many collaborators in the application review that will follow, not only those who worked in the physics department at Rutgers% ootnotetextMaxime Dion, Aaron Puzder, T. Thonhauser, Valentino R. Cooper, Shen Li, Eamonn Murray, Lingzhu Kong, and Kyuho Lee. and at Chalmers,% ootnotetextHenrik Rydberg, Svetla Chakarova-K"ack, Jesper Kleis, Elsebeth Schr"oder, Per Hyldgaard, and Bengt I. Lundqvist. but also at Denmarks Technical University,% ootnotetextAndrei Kelkkanen, Poul G. Moses, Jesper Kleis, and Bengt I. Lundqvist. the chemistry department at Rutgers,% ootnotetextKonhoa Li, Jing Li, Yves Chabal, and Wilma K. Olson. and most recently at the University of Texas at Dallas.% ootnotetextNour Nijem and Yves Chabal. I will expand on our recent review article,ootnotetextD. C. Langreth et al., J. Phys. Cond. Mat. (in press). which hopefully will be published before the present talk, and include applications by other groups not listed below. If possible, I will also review results from a more recent collaboration to study nucleosomal DNA and beyond.

  16. Inflationary magnetogenesis, derivative couplings, and relativistic Van der Waals interactions

    NASA Astrophysics Data System (ADS)

    Giovannini, Massimo

    2015-08-01

    When the gauge fields have derivative couplings to scalars, like in the case of the relativistic theory of Van der Waals (or Casimir-Polder) interactions, conformal invariance is broken but the magnetic and electric susceptibilities are not bound to coincide. We analyze the formation of large-scale magnetic fields in slow-roll inflation and find that they are generated at the level of a few hundredths of a nG and over typical length scales between few Mpc and 100 Mpc. Using a new time parametrization that reduces to conformal time but only for coincident susceptibilities, the gauge action is quantized while the evolution equations of the corresponding mode functions are more easily solvable. The power spectra depend on the normalized rates of variation of the two susceptibilities (or of the corresponding gauge couplings) and on the absolute value of their ratio at the beginning of inflation. We pin down explicit regions in the parameter space where all the physical requirements (i.e., the backreaction constraints, the magnetogenesis bounds and the naturalness of the initial conditions of the scenario) are jointly satisfied. Weakly coupled initial data are favored if the gauge couplings are of the same order at the end of inflation. Duality is systematically used to simplify the analysis of the wide parameter space of the model.

  17. Van der Waals coefficients beyond the classical shell model

    SciTech Connect

    Tao, Jianmin; Fang, Yuan; Hao, Pan; Scuseria, G. E.; Ruzsinszky, Adrienn; Perdew, John P.

    2015-01-14

    Van der Waals (vdW) coefficients can be accurately generated and understood by modelling the dynamic multipole polarizability of each interacting object. Accurate static polarizabilities are the key to accurate dynamic polarizabilities and vdW coefficients. In this work, we present and study in detail a hollow-sphere model for the dynamic multipole polarizability proposed recently by two of the present authors (JT and JPP) to simulate the vdW coefficients for inhomogeneous systems that allow for a cavity. The inputs to this model are the accurate static multipole polarizabilities and the electron density. A simplification of the full hollow-sphere model, the single-frequency approximation (SFA), circumvents the need for a detailed electron density and for a double numerical integration over space. We find that the hollow-sphere model in SFA is not only accurate for nanoclusters and cage molecules (e.g., fullerenes) but also yields vdW coefficients among atoms, fullerenes, and small clusters in good agreement with expensive time-dependent density functional calculations. However, the classical shell model (CSM), which inputs the static dipole polarizabilities and estimates the static higher-order multipole polarizabilities therefrom, is accurate for the higher-order vdW coefficients only when the interacting objects are large. For the lowest-order vdW coefficient C{sub 6}, SFA and CSM are exactly the same. The higher-order (C{sub 8} and C{sub 10}) terms of the vdW expansion can be almost as important as the C{sub 6} term in molecular crystals. Application to a variety of clusters shows that there is strong non-additivity of the long-range vdW interactions between nanoclusters.

  18. Development of Polarizable Models for Molecular Mechanical Calculations IV: van der Waals parameterization

    PubMed Central

    Wang, Junmei; Cieplak, Piotr; Li, Jie; Cai, Qin; Hsieh, MengJuei; Luo, Ray; Duan, Yong

    2012-01-01

    In the previous publications of this series, we presented a set of Thole induced dipole interaction models using four types of screening functions. In this work, we document our effort to refine the van der Waals parameters for the Thole polarizable models. Following the philosophy of AMBER force field development, the van der Waals (vdW) parameters were tuned for the Thole model with linear screening function to reproduce both the ab initio interaction energies and the experimental densities of pure liquids. An in-house genetic algorithm was applied to maximize the fitness of “chromosomes” which is a function of the root-mean-square errors (RMSE) of interaction energy and liquid density. To efficiently explore the vdW parameter space, a novel approach was developed to estimate the liquid densities for a given vdW parameter set using the mean residue-residue interaction energies through interpolation/extrapolation. This approach allowed the costly molecular dynamics simulations be performed at the end of each optimization cycle only and eliminated the simulations during the cycle. Test results show notable improvements over the original AMBER FF99 vdW parameter set as indicated by the reduction in errors of the calculated pure liquid density (d), heat of vaporization (Hvap) and hydration energy. The average percent error (APE) of the densities of 59 pure liquids was reduced from 5.33% to 2.97%; the RMSE of Hvap was reduced from 1.98 kcal/mol to 1.38 kcal/mol; the RMSE of solvation free energies of 15 compounds was reduced from 1.56 kcal/mol to 1.38 kcal/mol. For the interaction energies of 1639 dimers, the overall performance of the optimized vdW set is slightly better than the original FF99 vdW set (RMSE of 1.56 versus 1.63 kcal/mol). The optimized vdW parameter set was also evaluated for the exponential screening function used in the Amoeba force field to assess its applicability for different types of screening functions. Encouragingly, comparable

  19. Development of polarizable models for molecular mechanical calculations. 4. van der Waals parametrization.

    PubMed

    Wang, Junmei; Cieplak, Piotr; Li, Jie; Cai, Qin; Hsieh, Meng-Juei; Luo, Ray; Duan, Yong

    2012-06-21

    In the previous publications of this series, we presented a set of Thole induced dipole interaction models using four types of screening functions. In this work, we document our effort to refine the van der Waals parameters for the Thole polarizable models. Following the philosophy of AMBER force field development, the van der Waals (vdW) parameters were tuned for the Thole model with linear screening function to reproduce both the ab initio interaction energies and the experimental densities of pure liquids. An in-house genetic algorithm was applied to maximize the fitness of "chromosomes" which is a function of the root-mean-square errors (RMSE) of interaction energy and liquid density. To efficiently explore the vdW parameter space, a novel approach was developed to estimate the liquid densities for a given vdW parameter set using the mean residue-residue interaction energies through interpolation/extrapolation. This approach allowed the costly molecular dynamics simulations be performed at the end of each optimization cycle only and eliminated the simulations during the cycle. Test results show notable improvements over the original AMBER FF99 vdW parameter set, as indicated by the reduction in errors of the calculated pure liquid densities (d), heats of vaporization (H(vap)), and hydration energies. The average percent error (APE) of the densities of 59 pure liquids was reduced from 5.33 to 2.97%; the RMSE of H(vap) was reduced from 1.98 to 1.38 kcal/mol; the RMSE of solvation free energies of 15 compounds was reduced from 1.56 to 1.38 kcal/mol. For the interaction energies of 1639 dimers, the overall performance of the optimized vdW set is slightly better than the original FF99 vdW set (RMSE of 1.56 versus 1.63 kcal/mol). The optimized vdW parameter set was also evaluated for the exponential screening function used in the Amoeba force field to assess its applicability for different types of screening functions. Encouragingly, comparable performance was

  20. Van der Waals interactions and the limits of isolated atom models at interfaces

    PubMed Central

    Kawai, Shigeki; Foster, Adam S.; Björkman, Torbjörn; Nowakowska, Sylwia; Björk, Jonas; Canova, Filippo Federici; Gade, Lutz H.; Jung, Thomas A.; Meyer, Ernst

    2016-01-01

    Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar–Xe, Kr–Xe and Xe–Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal–organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems. PMID:27174162

  1. Van der Waals interactions and the limits of isolated atom models at interfaces

    NASA Astrophysics Data System (ADS)

    Kawai, Shigeki; Foster, Adam S.; Björkman, Torbjörn; Nowakowska, Sylwia; Björk, Jonas; Canova, Filippo Federici; Gade, Lutz H.; Jung, Thomas A.; Meyer, Ernst

    2016-05-01

    Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar-Xe, Kr-Xe and Xe-Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal-organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems.

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

    PubMed Central

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Liangbo; West, Damien; Meunier, Vincent; Zhang, Shengbai

    2016-01-01

    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. PMID:27160484

  3. Van der Waals interactions and the limits of isolated atom models at interfaces.

    PubMed

    Kawai, Shigeki; Foster, Adam S; Björkman, Torbjörn; Nowakowska, Sylwia; Björk, Jonas; Canova, Filippo Federici; Gade, Lutz H; Jung, Thomas A; Meyer, Ernst

    2016-01-01

    Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar-Xe, Kr-Xe and Xe-Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal-organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems. PMID:27174162

  4. Understanding the nanoscale local buckling behavior of vertically aligned MWCNT arrays with van der Waals interactions.

    PubMed

    Li, Yupeng; Kim, Hyung-ick; Wei, Bingqing; Kang, Junmo; Choi, Jae-boong; Nam, Jae-Do; Suhr, Jonghwan

    2015-09-14

    The local buckling behavior of vertically aligned carbon nanotubes (VACNTs) has been investigated and interpreted in the view of a collective nanotube response by taking van der Waals interactions into account. To the best of our knowledge, this is the first report on the case of collective VACNT behavior regarding van der Waals force among nanotubes as a lateral support effect during the buckling process. The local buckling propagation and development of VACNTs were experimentally observed and theoretically analyzed by employing finite element modeling with lateral support from van der Waals interactions among nanotubes. Both experimental and theoretical analyses show that VACNTs buckled in the bottom region with many short waves and almost identical wavelengths, indicating a high mode buckling. Furthermore, the propagation and development mechanism of buckling waves follow the wave damping effect. PMID:26242771

  5. Nano-photonic phenomena in van der Waals heterostructures (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Basov, Dmitri N.

    2015-09-01

    van der Waals (vdW) crystals consist of individual atomic planes coupled by vdW interaction, similar to graphene monolayers in bulk graphite. We investigated van der Waals heterostructures assembled from atomically thin layers of graphene and hexagonal boron nitride (hBN). We launched, detected and imaged plasmonic, phonon polaritonic and hybrid plasmon-phonon polariton waves in a setting of an antenna based nano-infrared apparatus. Hyperbolic phonon polaritons in hBN enabled sub-diffractional focusing in infrared frequencies. Because electronic, plasmonic and phonon polaritonic properties in van der Waals heterstructures are intertwined, gate voltage and/or details of layer assembly enable efficient control of nano-photonic effects.

  6. Quantum vacuum photon modes and repulsive Lifshitz-van der Waals interactions

    NASA Astrophysics Data System (ADS)

    Dellieu, Louis; Deparis, Olivier; Muller, Jérôme; Kolaric, Branko; Sarrazin, Michaël

    2015-12-01

    The bridge between quantum vacuum photon modes and properties of patterned surfaces is currently being established on solid theoretical grounds. Based on these foundations, the manipulation of quantum vacuum photon modes in a nanostructured cavity is theoretically shown to be able to change the Lifshitz-van der Waals forces from attractive to repulsive regime. Since this concept relies on surface nanopatterning instead of chemical composition changes, it drastically relaxes the usual conditions for achieving repulsive Lifshitz-van der Waals forces. As a case study, the potential interaction energy between a nanopatterned polyethylene slab and a flat polyethylene slab with water as the intervening medium is calculated. Extremely small corrugation heights (<10 nm) are shown to be able to change the Lifshitz-van der Waals force from attractive to repulsive, the interaction strength being controlled by the corrugation height. This new approach could lead to various applications in surface science.

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

    PubMed

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Liangbo; West, Damien; Meunier, Vincent; Zhang, Shengbai

    2016-01-01

    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. PMID:27160484

  8. Measurement of the van der Waals interaction by atom trajectory imaging

    NASA Astrophysics Data System (ADS)

    Thaicharoen, N.; Schwarzkopf, A.; Raithel, G.

    2015-10-01

    We study the repulsive van der Waals interaction of cold rubidium 70 S1 /2 Rydberg atoms by analysis of time-delayed pair-correlation functions. After excitation, Rydberg atoms are allowed to accelerate under the influence of the van der Waals force. Their positions are then measured using a single-atom imaging technique. From the average pair-correlation function of the atom positions we obtain the initial atom-pair separation and the terminal velocity, which yield the van der Waals interaction coefficient C6. The measured C6 value agrees well with calculations. The experimental method has been validated by simulations. The data hint at anisotropy in the overall expansion, caused by the shape of the excitation volume. Our measurement implies that the interacting entities are individual Rydberg atoms, not groups of atoms that coherently share a Rydberg excitation.

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

    NASA Astrophysics Data System (ADS)

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Liangbo; West, Damien; Meunier, Vincent; Zhang, Shengbai

    2016-05-01

    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.

  10. Van der Waals interactions among alkali Rydberg atoms with excitonic states

    NASA Astrophysics Data System (ADS)

    Zoubi, Hashem

    2015-09-01

    We investigate the influence of the appearance of excitonic states on van der Waals interactions among two Rydberg atoms. The atoms are assumed to be in different Rydberg states, e.g., in the | {ns}> and | {np}> states. The resonant dipole-dipole interactions yield symmetric and antisymmetric excitons, with energy splitting that give rise to new resonances as the atoms approach each other. Only away from these resonances can the van der Waals coefficients, C6sp, be defined. We calculate the C6 coefficients for alkali atoms and present the results for lithium by applying perturbation theory. At short interatomic distances of several μ {{m}}, we show that the widely used simple model of two-level systems for excitons in Rydberg atoms breaks down, and the correct representation implies multi-level atoms. Even though, at larger distances one can keep the two-level systems but in including van der Waals interactions among the atoms .

  11. Understanding the nanoscale local buckling behavior of vertically aligned MWCNT arrays with van der Waals interactions

    NASA Astrophysics Data System (ADS)

    Li, Yupeng; Kim, Hyung-Ick; Wei, Bingqing; Kang, Junmo; Choi, Jae-Boong; Nam, Jae-Do; Suhr, Jonghwan

    2015-08-01

    The local buckling behavior of vertically aligned carbon nanotubes (VACNTs) has been investigated and interpreted in the view of a collective nanotube response by taking van der Waals interactions into account. To the best of our knowledge, this is the first report on the case of collective VACNT behavior regarding van der Waals force among nanotubes as a lateral support effect during the buckling process. The local buckling propagation and development of VACNTs were experimentally observed and theoretically analyzed by employing finite element modeling with lateral support from van der Waals interactions among nanotubes. Both experimental and theoretical analyses show that VACNTs buckled in the bottom region with many short waves and almost identical wavelengths, indicating a high mode buckling. Furthermore, the propagation and development mechanism of buckling waves follow the wave damping effect.The local buckling behavior of vertically aligned carbon nanotubes (VACNTs) has been investigated and interpreted in the view of a collective nanotube response by taking van der Waals interactions into account. To the best of our knowledge, this is the first report on the case of collective VACNT behavior regarding van der Waals force among nanotubes as a lateral support effect during the buckling process. The local buckling propagation and development of VACNTs were experimentally observed and theoretically analyzed by employing finite element modeling with lateral support from van der Waals interactions among nanotubes. Both experimental and theoretical analyses show that VACNTs buckled in the bottom region with many short waves and almost identical wavelengths, indicating a high mode buckling. Furthermore, the propagation and development mechanism of buckling waves follow the wave damping effect. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03581c

  12. Observation of long-lived van der Waals molecules in an optical lattice

    NASA Astrophysics Data System (ADS)

    Kato, Shinya; Yamazaki, Rekishu; Shibata, Kosuke; Yamamoto, Ryuta; Yamada, Hirotaka; Takahashi, Yoshiro

    2012-10-01

    We observe long-lived tightly bound van der Waals molecules of ytterbium in a three-dimensional optical lattice with a lifetime of 8.0 s. The molecules, state-selectively produced by a photoassociation technique from a Bose-Einstein condensate or an atomic Mott insulator, are successfully detected with a photodissociation method where the molecules are photodissociated into two atoms and the atoms are captured by a magneto-optical trap or optical molasses, for the fluorescence detection. This work will open up various possibilities of research with van der Waals molecules in an optical lattice.

  13. General theory based on fluctuational electrodynamics for van der Waals interactions in colloidal systems

    SciTech Connect

    Yannopapas, Vassilios

    2007-12-15

    A rigorous theory for the determination of the van der Waals interactions in colloidal systems is presented. The method is based on fluctuational electrodynamics and a multiple-scattering method which provides the electromagnetic Green's tensor. In particular, expressions for the Green's tensor are presented for arbitrary, finite collections of colloidal particles, for infinitely periodic or defected crystals, as well as for finite slabs of crystals. The presented formalism allows for ab initio calculations of the van der Waals interactions in colloidal systems since it takes fully into account retardation, many-body, multipolar, and near-field effects.

  14. A high-pressure van der Waals compound in solid nitrogen-helium mixtures

    NASA Technical Reports Server (NTRS)

    Vos, W. L.; Finger, L. W.; Hemley, R. J.; Hu, J. Z.; Mao, H. K.; Schouten, J. A.

    1992-01-01

    A detailed diamond anvil-cell study using synchrotron X-ray diffraction, Raman scattering, and optical microscopy has been conducted for the He-N system, with a view to the weakly-bound van der Waals molecule interactions that can be formed in the gas phase. High pressure is found to stabilize the formation of a stoichiometric, solid van der Waals compound of He(N2)11 composition which may exemplify a novel class of compounds found at high pressures in the interiors of the outer planets and their satellites.

  15. A theoretical study of the rovibrational levels of the bosonic van der Waals neon trimer.

    PubMed

    Salci, Moses; Levin, Sergey B; Elander, Nils; Yarevsky, Evgeny

    2008-10-01

    The eigenenergies and root mean square radii of the rovibrational levels (J = 0-3) of the weakly bound bosonic van der Waals neon trimer were calculated using a full angular momentum three-dimensional finite element method. The differing results of three previous studies for zero angular momentum are discussed, explained, and compared with the results presented here. PMID:19045087

  16. Low-Voltage Complementary Electronics from Ion-Gel-Gated Vertical Van der Waals Heterostructures.

    PubMed

    Choi, Yongsuk; Kang, Junmo; Jariwala, Deep; Kang, Moon Sung; Marks, Tobin J; Hersam, Mark C; Cho, Jeong Ho

    2016-05-01

    Low-voltage complementary circuits comprising n-type and p-type van der Waals heterojunction vertical field-effect transistors (VFETs) are demonstrated. The resulting VFETs possess high on-state current densities (>3000 A cm(-2) ) and on/off current ratios (>10(4) ) in a narrow voltage window (<3 V). PMID:27002478

  17. A van der Waals Equation of State for a Dilute Boson Gas

    ERIC Educational Resources Information Center

    Deeney, F. A.; O'Leary, J. P.

    2012-01-01

    An equation of state of a system is a relationship that connects the thermodynamic variables of the system such as pressure and temperature. Such equations are well known for classical gases but less so for quantum systems. In this paper we develop a van der Waals equation of state for a dilute boson gas that may be used to explain the occurrence…

  18. First principles calculations of solid-state thermionic transport in layered van der Waals heterostructures.

    PubMed

    Wang, Xiaoming; Zebarjadi, Mona; Esfarjani, Keivan

    2016-08-21

    This work aims at understanding solid-state energy conversion and transport in layered (van der Waals) heterostructures in contact with metallic electrodes via a first-principles approach. As an illustration, a graphene/phosphorene/graphene heterostructure in contact with gold electrodes is studied by using density functional theory (DFT)-based first principles calculations combined with real space Green's function (GF) formalism. We show that for a monolayer phosphorene, quantum tunneling dominates the transport. By adding more phosphorene layers, one can switch from tunneling-dominated transport to thermionic-dominated transport, resulting in transporting more heat per charge carrier, thus, enhancing the cooling coefficient of performance. The use of layered van der Waals heterostructures has two advantages: (a) thermionic transport barriers can be tuned by changing the number of layers, and (b) thermal conductance across these non-covalent structures is very weak. The phonon thermal conductance of the present van der Waals heterostructure is found to be 4.1 MW m(-2) K(-1) which is one order of magnitude lower than the lowest value for that of covalently-bonded interfaces. The thermionic coefficient of performance for the proposed device is 18.5 at 600 K corresponding to an equivalent ZT of 0.13, which is significant for nanoscale devices. This study shows that layered van der Waals structures have great potential to be used as solid-state energy-conversion devices. PMID:27314610

  19. Dynamical screening of the van der Waals interaction between graphene layers.

    PubMed

    Dappe, Y J; Bolcatto, P G; Ortega, J; Flores, F

    2012-10-24

    The interaction between graphene layers is analyzed combining local orbital DFT and second order perturbation theory. For this purpose we use the linear combination of atomic orbitals-orbital occupancy (LCAO-OO) formalism, that allows us to separate the interaction energy as the sum of a weak chemical interaction between graphene layers plus the van der Waals interaction (Dappe et al 2006 Phys. Rev. B 74 205434). In this work, the weak chemical interaction is calculated by means of corrected-LDA calculations using an atomic-like sp(3)d(5) basis set. The van der Waals interaction is calculated by means of second order perturbation theory using an atom-atom interaction approximation and the atomic-like-orbital occupancies. We also analyze the effect of dynamical screening in the van der Waals interaction using a simple model. We find that this dynamical screening reduces by 40% the van der Waals interaction. Taking this effect into account, we obtain a graphene-graphene interaction energy of 70 ± 5 meV/atom in reasonable agreement with the experimental evidence. PMID:23032606

  20. Dynamical screening of the van der Waals interaction between graphene layers

    NASA Astrophysics Data System (ADS)

    Dappe, Y. J.; Bolcatto, P. G.; Ortega, J.; Flores, F.

    2012-10-01

    The interaction between graphene layers is analyzed combining local orbital DFT and second order perturbation theory. For this purpose we use the linear combination of atomic orbitals-orbital occupancy (LCAO-OO) formalism, that allows us to separate the interaction energy as the sum of a weak chemical interaction between graphene layers plus the van der Waals interaction (Dappe et al 2006 Phys. Rev. B 74 205434). In this work, the weak chemical interaction is calculated by means of corrected-LDA calculations using an atomic-like sp3d5 basis set. The van der Waals interaction is calculated by means of second order perturbation theory using an atom-atom interaction approximation and the atomic-like-orbital occupancies. We also analyze the effect of dynamical screening in the van der Waals interaction using a simple model. We find that this dynamical screening reduces by 40% the van der Waals interaction. Taking this effect into account, we obtain a graphene-graphene interaction energy of 70 ± 5 meV/atom in reasonable agreement with the experimental evidence.

  1. Generalized van der Waals Hamiltonian: periodic orbits and C1 nonintegrability.

    PubMed

    Guirao, Juan L G; Llibre, Jaume; Vera, Juan A

    2012-03-01

    The aim of this paper is to study the periodic orbits of the generalized van der Waals Hamiltonian system. The tool for studying such periodic orbits is the averaging theory. Moreover, for this Hamiltonian system we provide information on its C(1) nonintegrability, i.e., on the existence of a second first integral of class C(1). PMID:22587198

  2. First kind symmetric periodic solutions of the generalized van der Waals Hamiltonian

    NASA Astrophysics Data System (ADS)

    Alberti, Angelo; Vidal, Claudio

    2016-07-01

    The aim of this paper is to prove the existence of a new symmetric family of periodic solutions of the generalized van der Waals Hamiltonian. In fact, we prove the existence of several families of first kind symmetric periodic solutions as continuation of circular orbits of the Kepler problem in the spatial case.

  3. Maxwell's Relations for a van der Waals Gas and a Nuclear Paramagnetic System.

    ERIC Educational Resources Information Center

    Herlihy, James; And Others

    1981-01-01

    Since Maxwell's relations are derived in general form from the first to second laws, and students often wonder what they mean and how they are used, appropriate partition functions for van der Waals gas and the nuclear paramagnetic system are used to obtain entropy expressions and equations of state. (Author/SK)

  4. van der Waals Density Functional Theory vdW-DFq for Semihard Materials

    NASA Astrophysics Data System (ADS)

    Peng, Qing; de, Suvranu

    There are a large number of materials with mild stiffness, which are not as soft as tissues and not as strong as metals. These semihard materials includes energetic materials, molecular crystals, layered materials, and van der Waals crystals. The integrity and mechanical stability are mainly determined by the interactions between instantaneously induced dipoles, the so called London dispersion force or van der Waals force. It is challenging to accurately model the structural and mechanical properties of these semihard materials in the frame of density functional theory where the non-local correlation functionals are not well known. Here we propose a van der Waals density functional named vdW-DFq to accurately model the density and geometry of semihard materials. Using β-cyclotetramethylene tetranitramine as a prototype, we adjust the enhancement factor of the exchange energy functional with generalized gradient approximations. We find this method to be simple and robust over a wide tuning range when calibrating the functional on-demand with experimental data. With a calibrated value q = 1 . 05 , the proposed vdW-DFq method shows good performance in predicting the geometries of 11 common energetic material molecular crystals and 3 typical layered van der Waals crystals. The authors would like to acknowledge the generous financial support from the Defense Threat Reduction Agency (DTRA) Grant # HDTRA1-13-1-0025.

  5. Approximating the 3D Character of a Van Der Waals Atom-Solid Potential

    NASA Astrophysics Data System (ADS)

    Bruch, L. W.

    2016-04-01

    A truncated Fourier decomposition of the atom-substrate potential energy is developed for three-dimensional models of van der Waals systems, specifically for adsorption on the basal plane surface of graphite or the (111) face of a face-centered-cubic lattice. This provides a framework for analysis of a priori calculations of physical adsorption energies.

  6. Control of excitons in multi-layer van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Calman, E. V.; Dorow, C. J.; Fogler, M. M.; Butov, L. V.; Hu, S.; Mishchenko, A.; Geim, A. K.

    2016-03-01

    We report an experimental study of excitons in a double quantum well van der Waals heterostructure made of atomically thin layers of MoS2 and hexagonal boron nitride. The emission of neutral and charged excitons is controlled by gate voltage, temperature, and both the helicity and the power of optical excitation.

  7. Dynamics of Gold Nanoparticles on Carbon Nanostructures Driven by van der Waals and Electrostatic Interactions.

    PubMed

    La Torre, Alessandro; Gimenez-Lopez, Maria del Carmen; Fay, Michael W; Lucas, Carlos Herreros; Brown, Paul D; Khlobystov, Andrei N

    2015-06-01

    Transmission electron microscopy studies on the assembly and growth of gold nanoparticles on carbon nanotubes supported on few-layer graphene and amorphous carbon reveal a competition between van der Waals forces and electrostatic interactions, enabling controlled positioning and sizing of adsorbed nanoparticles at the nanochannels formed between the carbon nanotube and the few-layer graph-ene surface. PMID:25689488

  8. Bonded Paths and van der Waals Interactions in Orpiment, As2S3

    SciTech Connect

    Gibbs, Gerald V.; Wallace, Adam F.; Zallen, Richard; Downs, R. T.; Ross, Nancy L.; Cox, David F.; Rosso, Kevin M.

    2010-06-17

    Bond critical properties and bond paths have been calculated for the thioarsenide molecular crystal orpiment, As2S3. In addition to the intramolecular As-S bond paths and van der Waals As-S and S-S bond paths within the layers, intermolecular S-S, As-S and As-As van der Waals paths exist between the layers. The S-S bond paths between the layers are identified with the main interlayer restoring forces responsible for the vibrational internal-mode splitting and the low frequency rigid layer modes previously documented in infrared and Raman studies of orpiment. These S-S bond paths are comparable with those calculated for orthorhombic native sulfur and the As4Sn (n = 3,4,5) molecules for several arsenide molecular crystals. The As-S bond paths show that the two nonequivalent arsenic atoms are each coordinated by a highly distorted octahedral array of sulfur atoms. The octahedra consist of three As-S intramolecular bonded interactions and three longer van der Waals interactions (two intramolecular and one intermolecular). One of the arsenic atoms is also coordinated by an arsenic atom in an interlayer As-As bonded interaction. Laplacian isosurface envelopes calculated for the arsenic and sulfur atoms are comparable with those calculated for native arsenic and orthorhombic sulfur. The intermolecular As-S bond paths connect Lewis acid domains on arsenic and an Lewis base domains on sulfur. Van der Waals interactions are traditionally defined as attractive interactions other than those ascribed to bond formation. However, theoretical evidence and arguments, as well as the connection between the bond paths and the vibrational spectra, indicate that the van der Waals interactions in orpiment are directed bonded interactions in the Slater sense. The experimental bond lengths for the As-S and S-S bonded interactions decrease nonlinearly with the increasing value of the electron density at the bond critical point, concomitant with a decrease in the bonded radii of arsenic and

  9. Optimizing Protein-Protein van der Waals Interactions for the AMBER ff9x/ff12 Force Field.

    PubMed

    Chapman, Dail E; Steck, Jonathan K; Nerenberg, Paul S

    2014-01-14

    The quality of molecular dynamics (MD) simulations relies heavily on the accuracy of the underlying force field. In recent years, considerable effort has been put into developing more accurate dihedral angle potentials for MD force fields, but relatively little work has focused on the nonbonded parameters, many of which are two decades old. In this work, we assess the accuracy of protein-protein van der Waals interactions in the AMBER ff9x/ff12 force field. Across a test set of 44 neat organic liquids containing the moieties present in proteins, we find root-mean-square (RMS) errors of 1.26 kcal/mol in enthalpy of vaporization and 0.36 g/cm(3) in liquid densities. We then optimize the van der Waals radii and well depths for all of the relevant atom types using these observables, which lowers the RMS errors in enthalpy of vaporization and liquid density of our validation set to 0.59 kcal/mol (53% reduction) and 0.019 g/cm(3) (46% reduction), respectively. Limitations in our parameter optimization were evident for certain atom types, however, and we discuss the implications of these observations for future force field development. PMID:26579910

  10. Band gap engineering of a soft inorganic compound PbI2 by incommensurate van der Waals epitaxy

    NASA Astrophysics Data System (ADS)

    Wang, Yiping; Sun, Yi-Yang; Zhang, Shengbai; Lu, Toh-Ming; Shi, Jian

    2016-01-01

    Van der Waals epitaxial growth had been thought to have trivial contribution on inducing substantial epitaxial strain in thin films due to its weak nature of van der Waals interfacial energy. Due to this, electrical and optical structure engineering via van der Waals epitaxial strain has been rarely studied. In this report, we show that significant band structure engineering could be achieved in a soft thin film material PbI2 via van der Waals epitaxy. The thickness dependent photoluminescence of single crystal PbI2 flakes was studied and attributed to the substrate-film coupling effect via incommensurate van der Waals epitaxy. It is proposed that the van der Waals strain is resulted from the soft nature of PbI2 and large van der Waals interaction due to the involvement of heavy elements. Such strain plays vital roles in modifying the band gap of PbI2. The deformation potential theory is used to quantitatively unveil the correlation between thickness, strain, and band gap change. Our hypothesis is confirmed by the subsequent mechanical bending test and Raman characterization.

  11. In-situ epitaxial growth of graphene/h-BN van der Waals heterostructures by molecular beam epitaxy

    PubMed Central

    Zuo, Zheng; Xu, Zhongguang; Zheng, Renjing; Khanaki, Alireza; Zheng, Jian-Guo; Liu, Jianlin

    2015-01-01

    Van der Waals materials have received a great deal of attention for their exceptional layered structures and exotic properties, which can open up various device applications in nanoelectronics. However, in situ epitaxial growth of dissimilar van der Waals materials remains challenging. Here we demonstrate a solution for fabricating van der Waals heterostructures. Graphene/hexagonal boron nitride (h-BN) heterostructures were synthesized on cobalt substrates by using molecular beam epitaxy. Various characterizations were carried out to evaluate the heterostructures. Wafer-scale heterostructures consisting of single-layer/bilayer graphene and multilayer h-BN were achieved. The mismatch angle between graphene and h-BN is below 1°. PMID:26442629

  12. How van der Waals interactions determine the unique properties of water.

    PubMed

    Morawietz, Tobias; Singraber, Andreas; Dellago, Christoph; Behler, Jörg

    2016-07-26

    Whereas the interactions between water molecules are dominated by strongly directional hydrogen bonds (HBs), it was recently proposed that relatively weak, isotropic van der Waals (vdW) forces are essential for understanding the properties of liquid water and ice. This insight was derived from ab initio computer simulations, which provide an unbiased description of water at the atomic level and yield information on the underlying molecular forces. However, the high computational cost of such simulations prevents the systematic investigation of the influence of vdW forces on the thermodynamic anomalies of water. Here, we develop efficient ab initio-quality neural network potentials and use them to demonstrate that vdW interactions are crucial for the formation of water's density maximum and its negative volume of melting. Both phenomena can be explained by the flexibility of the HB network, which is the result of a delicate balance of weak vdW forces, causing, e.g., a pronounced expansion of the second solvation shell upon cooling that induces the density maximum. PMID:27402761

  13. An accurate Van der Waals-type equation of state for the Lennard-Jones fluid

    SciTech Connect

    Mecke, M.; Mueller, A.; Winkelmann, J.

    1996-03-01

    A new equation of state (EOS) is proposed for the Helmholtz energy F of the Lennard-Jones fluid which represents the thermodynamic properties over a wide range of temperatures and densities. The EOS is written in the form of a generalized van der Waals equation, F= F{sub H} + F{sub A}, where F{sub H} is a hard body contribution and FA an attractive dispersion force contribution. The expression for F{sub H} is closely related to the hybrid Barker-Henderson pertubation theory. The construction of FA is accomplished with the Setzmann-Wagner optimization procedure on the basis of virial coefficients and critically assessed computer simulation data. A comparison with the EOS shows improvement in the description of the vapor-liquid coexistence properties, the pvT data, and in peculiar, of the caloric properties. A comparison with the EOS of Kolafa and Nezbeda which appeared after the bulk of this work was finished shows still an improvement in the standard deviations of the pressure and internal energy by about 30%.

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

    PubMed

    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 μm(2)) 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

  15. Prediction of physicochemical properties of organic molecules using van der Waals surface electrostatic potentials.

    PubMed

    Kim, Chan Kyung; Lee, Kyung A; Hyun, Kwan Hoon; Park, Heung Jin; Kwack, In Young; Kim, Chang Kon; Lee, Hai Whang; Lee, Bon-Su

    2004-12-01

    The generalized interaction properties function (GIPF) methodology developed by Politzer and coworkers, which calculated molecular surface electrostatic potential (MSESP) on a density envelope surface, was modified by calculating the MSESP on a much simpler van der Waals (vdW) surface of a molecule. In this work, vdW molecular surfaces were obtained from the fully optimized structures confirmed by frequency calculations at B3LYP/6-31G(d) level of theory. Multiple linear regressions for normal boiling point, heats of vaporization, heats of sublimation, heats of fusion, liquid density, and solid density were performed using GIPF variables from vdW model surface. Results from our model are compared with those from Politzer and coworkers. The surface-dependent beta (and gamma) values are dependent on the surface models but the surface-independent alpha and regression coefficients (r) are constant when vdW surface and density surface with 0.001 a.u. contour value are compared. This interesting phenomenon is explained by linear dependencies of GIPF variables. PMID:15484184

  16. Cavitation inception of a van der Waals fluid at a sack-wall obstacle

    NASA Astrophysics Data System (ADS)

    Kähler, G.; Bonelli, F.; Gonnella, G.; Lamura, A.

    2015-12-01

    Cavitation in a liquid moving past a constraint is numerically investigated by means of a free-energy lattice Boltzmann simulation based on the van der Waals equation of state. The fluid is streamed past an obstacle, and depending on the pressure drop between inlet and outlet, vapor formation underneath the corner of the sack-wall is observed. The circumstances of cavitation formation are investigated and it is found that the local bulk pressure and mean stress are insufficient to explain the phenomenon. Results obtained in this study strongly suggest that the viscous stress, interfacial contributions to the local pressure, and the Laplace pressure are relevant to the opening of a vapor cavity. This can be described by a generalization of Joseph's criterion that includes these contributions. A macroscopic investigation measuring mass flow rate behavior and discharge coefficient was also performed. As theoretically predicted, mass flow rate increases linearly with the square root of the pressure drop. However, when cavitation occurs, the mass flow growth rate is reduced and eventually it collapses into a choked flow state. In the cavitating regime, as theoretically predicted and experimentally verified, the discharge coefficient grows with the Nurick cavitation number.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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.

  19. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

    SciTech Connect

    Ganesh, P.; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A.; Kent, Paul R. C.

    2014-11-03

    In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.

  20. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods.

    PubMed

    Ganesh, P; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A; Kent, Paul R C

    2014-12-01

    Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium-carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches. PMID:26583215

  1. Electrical and optical properties of SnS2/WSe2 van der Waals Heterojunction FETs

    NASA Astrophysics Data System (ADS)

    Zubair, Ahmad; Nourbakhsh, Amirhasan; Dresselhaus, Mildred; Palacios, Tomas

    Two dimensional crystals based on atomically thin films of transition metal dichalcogenides offer an exciting platform for various optoelectronic applications. Their unique crystal properties make them particularly attractive for van der Waals heterostructures which open up an additional degree of freedom to tailor the material properties into new physics and device applications. In this work, we explore, for the first time, the optoelectronic properties of van der Waals SnS2/WSe2 heterojunction. WSe2 is an ambipolar semiconductor while SnS2 is an n-type wide bandgap semiconductor. We use the pickup and dry transfer methods to fabricate SnS2/WSe2 heterojunction transistors (hetero-FETs). We observe negative differential transconductance in the SnS2/WSe2 hetero-FET. Also, the heterostructure couples strongly to incident light and shows high photovoltaic responsivity which can find applications in nano-devices such as photo-detectors and solar cells.

  2. A simplified implementation of van der Waals density functionals for first-principles molecular dynamics applications

    NASA Astrophysics Data System (ADS)

    Wu, Jun; Gygi, François

    2012-06-01

    We present a simplified implementation of the non-local van der Waals correlation functional introduced by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)] and reformulated by Román-Pérez et al. [Phys. Rev. Lett. 103, 096102 (2009)]. The proposed numerical approach removes the logarithmic singularity of the kernel function. Complete expressions of the self-consistent correlation potential and of the stress tensor are given. Combined with various choices of exchange functionals, five versions of van der Waals density functionals are implemented. Applications to the computation of the interaction energy of the benzene-water complex and to the computation of the equilibrium cell parameters of the benzene crystal are presented. As an example of crystal structure calculation involving a mixture of hydrogen bonding and dispersion interactions, we compute the equilibrium structure of two polymorphs of aspirin (2-acetoxybenzoic acid, C9H8O4) in the P21/c monoclinic structure.

  3. Steady dynamics of exothermic chemical wave fronts in van der Waals fluids.

    PubMed

    Dumazer, G; Antoine, C; Lemarchand, A; Nowakowski, B

    2009-12-01

    We study the steady dynamics of an exothermic Fisher-Kolmogorov-Petrovsky-Piskunov chemical wave front traveling in a one-dimensional van der Waals fluid. The propagating wave is initiated by a nonuniformity in reactant concentration contrary to usual combustion ignition processes. The heat release and activation energy of the reaction play the role of control parameters. We recently proved that the propagation of an exothermic chemical wave front in a perfect gas displays a forbidden interval of stationary wave front speeds [G. Dumazer, M. Leda, B. Nowakowski, and A. Lemarchand, Phys. Rev. E 78, 016309 (2008)]. We examine how this result is modified for nonideal fluids and determine the effect of the van der Waals parameters and fluid density on the bifurcation between diffusion flames and Chapman-Jouguet detonation waves as heat release increases. Analytical predictions are confirmed by the numerical solution of the hydrodynamic equations including reaction kinetics. PMID:20365269

  4. Energetics, dynamics, and reactions of rydberg state molecules in van der Waals clusters

    SciTech Connect

    Shang, Q.Y.; Bernstein, E.R.

    1994-12-31

    In the past 10 years the study of van der Waals clusters has grown enormously; perhaps one of the best indications of this growth, in both activity and sophistication, is the advent of this review issue devoted to such research. Van der Waals clusters, synthesized one molecule or atom at a time and accessed according to size and structure, provide a molecule by molecule view of the solvation process, its energetics, solute/solvent dynamics, and eventually even unimolecular and bimolecular chemical reactions. The clusters treated most frequently and discussed in this review are of the form solute or chromophore (solvent)n, with n varying from 1 to more than 100. These clusters are most typically generated in a supersonic beam; both large and small clusters can be synthesized by controlling the expansion conditions.

  5. Direct Measurement of the van der Waals Interaction between Two Rydberg Atoms

    NASA Astrophysics Data System (ADS)

    Béguin, L.; Vernier, A.; Chicireanu, R.; Lahaye, T.; Browaeys, A.

    2013-06-01

    We report the direct measurement of the van der Waals interaction between two isolated, single Rydberg atoms separated by a controlled distance of a few micrometers. Working in a regime where the single-atom Rabi frequency for excitation to the Rydberg state is comparable to the interaction, we observe partial Rydberg blockade, whereby the time-dependent populations of the various two-atom states exhibit coherent oscillations with several frequencies. Quantitative comparison of the data with a simple model based on the optical Bloch equations allows us to extract the van der Waals energy, and observe its characteristic C6/R6 dependence. The measured C6 coefficients agree well with ab initio calculations, and we observe their dramatic increase with the principal quantum number n of the Rydberg state.

  6. Exact traveling wave solutions of the van der Waals normal form for fluidized granular matter

    NASA Astrophysics Data System (ADS)

    Abourabia, A. M.; Morad, A. M.

    2015-11-01

    Analytical solutions of the van der Waals normal form for fluidized granular media have been done to study the phase separation phenomenon by using two different exact methods. The Painlevé analysis is discussed to illustrate the integrability of the model equation. An auto-Bäcklund transformation is presented via the truncated expansion and symbolic computation. The results show that the exact solutions of the model introduce solitary waves of different types. The solutions of the hydrodynamic model and the van der Waals equation exhibit a behavior similar to the one observed in molecular dynamic simulations such that two pairs of shock and rarefaction waves appear and move away, giving rise to the bubbles. The dispersion properties and the relation between group and phase velocities of the model equation are studied using the plane wave assumption. The diagrams are drawn to illustrate the physical properties of the exact solutions, and indicate their stability and bifurcation.

  7. Two dimensional graphene nanogenerator by coulomb dragging: Moving van der Waals heterostructure

    SciTech Connect

    Zhong, Huikai; Li, Xiaoqiang; Wu, Zhiqian; Zhang, Shengjiao; Xu, Zhijuan; Chen, Hongsheng; Lin, Shisheng

    2015-06-15

    Harvesting energy from environment is the current focus of scientific community. Here, we demonstrate a graphene nanogenerator, which is based on moving van der Waals heterostructure formed between graphene and two dimensional (2D) graphene oxide (GO). This nanogenerator can convert mechanical energy into electricity with a voltage output of around 10 mV. Systematic experiments reveal the generated electricity originates from the coulomb interaction induced momentum transfer between 2D GO and holes in graphene. 2D boron nitride was also demonstrated to be effective in the framework of moving van der Waals heterostructure nanogenerator. This investigation of nanogenerator based on the interaction between 2D macromolecule materials will be important to understand the origin of the flow-induced potential in nanomaterials and may have great potential in practical applications.

  8. Van der Waals pressure and its effect on trapped interlayer molecules

    NASA Astrophysics Data System (ADS)

    Vasu, K. S.; Prestat, E.; Abraham, J.; Dix, J.; Kashtiban, R. J.; Beheshtian, J.; Sloan, J.; Carbone, P.; Neek-Amal, M.; Haigh, S. J.; Geim, A. K.; Nair, R. R.

    2016-07-01

    Van der Waals assembly of two-dimensional crystals continue attract intense interest due to the prospect of designing novel materials with on-demand properties. One of the unique features of this technology is the possibility of trapping molecules between two-dimensional crystals. The trapped molecules are predicted to experience pressures as high as 1 GPa. Here we report measurements of this interfacial pressure by capturing pressure-sensitive molecules and studying their structural and conformational changes. Pressures of 1.2+/-0.3 GPa are found using Raman spectrometry for molecular layers of 1-nm in thickness. We further show that this pressure can induce chemical reactions, and several trapped salts are found to react with water at room temperature, leading to two-dimensional crystals of the corresponding oxides. This pressure and its effect should be taken into account in studies of van der Waals heterostructures and can also be exploited to modify materials confined at the atomic interfaces.

  9. The van der Waals interactions in rare-gas dimers: the role of interparticle interactions.

    PubMed

    Chen, Yu-Ting; Hui, Kerwin; Chai, Jeng-Da

    2016-01-28

    We investigate the potential energy curves of rare-gas dimers with various ranges and strengths of interparticle interactions (nuclear-electron, electron-electron, and nuclear-nuclear interactions). Our investigation is based on the highly accurate coupled-cluster theory associated with those interparticle interactions. For comparison, the performances of the corresponding Hartree-Fock theory, second-order Møller-Plesset perturbation theory, and density functional theory are also investigated. Our results reveal that when the interparticle interactions retain the long-range Coulomb tails, the nature of van der Waals interactions in the rare-gas dimers remains similar. By contrast, when the interparticle interactions are sufficiently short-range, the conventional van der Waals interactions in the rare-gas dimers completely disappear, yielding purely repulsive potential energy curves. PMID:26738722

  10. van der Waals Interactions on the Mesoscale: Open-Science Implementation, Anisotropy, Retardation, and Solvent Effects.

    PubMed

    Dryden, Daniel M; Hopkins, Jaime C; Denoyer, Lin K; Poudel, Lokendra; Steinmetz, Nicole F; Ching, Wai-Yim; Podgornik, Rudolf; Parsegian, Adrian; French, Roger H

    2015-09-22

    The self-assembly of heterogeneous mesoscale systems is mediated by long-range interactions, including van der Waals forces. Diverse mesoscale architectures, built of optically and morphologically anisotropic elements such as DNA, collagen, single-walled carbon nanotubes, and inorganic materials, require a tool to calculate the forces, torques, interaction energies, and Hamaker coefficients that govern assembly in such systems. The mesoscale Lifshitz theory of van der Waals interactions can accurately describe solvent and temperature effects, retardation, and optically and morphologically anisotropic materials for cylindrical and planar interaction geometries. The Gecko Hamaker open-science software implementation of this theory enables new and sophisticated insights into the properties of important organic/inorganic systems: interactions show an extended range of magnitudes and retardation rates, DNA interactions show an imprint of base pair composition, certain SWCNT interactions display retardation-dependent nonmonotonicity, and interactions are mapped across a range of material systems in order to facilitate rational mesoscale design. PMID:25815562

  11. A cohesive law for carbon nanotube/polymer interfaces based on the van der Waals force

    NASA Astrophysics Data System (ADS)

    Jiang, L. Y.; Huang, Y.; Jiang, H.; Ravichandran, G.; Gao, H.; Hwang, K. C.; Liu, B.

    2006-11-01

    We have established the cohesive law for interfaces between a carbon nanotube (CNT) and polymer that are not well bonded and are characterized by the van der Waals force. The tensile cohesive strength and cohesive energy are given in terms of the area density of carbon nanotube and volume density of polymer, as well as the parameters in the van der Waals force. For a CNT in an infinite polymer, the shear cohesive stress vanishes, and the tensile cohesive stress depends only on the opening displacement. For a CNT in a finite polymer matrix, the tensile cohesive stress remains the same, but the shear cohesive stress depends on both opening and sliding displacements, i.e., the tension/shear coupling. The simple, analytical expressions of the cohesive law are useful to study the interaction between CNT and polymer, such as in CNT-reinforced composites. The effect of polymer surface roughness on the cohesive law is also studied.

  12. van der Waals forces in density functional theory: Perturbational long-range electron-interaction corrections

    SciTech Connect

    Angyan, Janos G.; Gerber, Iann C.; Savin, Andreas; Toulouse, Julien

    2005-07-15

    Long-range exchange and correlation effects, responsible for the failure of currently used approximate density functionals in describing van der Waals forces, are taken into account explicitly after a separation of the electron-electron interaction in the Hamiltonian into short- and long-range components. We propose a 'range-separated hybrid' functional based on a local density approximation for the short-range exchange-correlation energy, combined with a long-range exact exchange energy. Long-range correlation effects are added by a second-order perturbational treatment. The resulting scheme is general and is particularly well adapted to describe van der Waals complexes, such as rare gas dimers.

  13. Microwave spectra of van der Waals complexes of importance in planetary atmospheres

    NASA Astrophysics Data System (ADS)

    Suenram, R. D.; Lovas, F. J.

    1990-05-01

    The Fourier-transform Fabry-Perot pulsed-molecular-beam microwave spectrometer at NIST was used to study the microwave spectra of a number of molecular dimers and trimers that may be present in planetary atmospheres. The weak van der Waals bonds associated with these species usually give rise to rotational-tunneling splittings in the microwave spectra. The microwave spectrum of the water dimer species was used to illustrate the complications that can arise in the study of the rotational spectra of these loosely bound species. In addition to the water dimer species, the microwave spectra of the following hydrogen-bonded and van der Waals complexes were studied: (CO2)2-H2O, CO2-(H2O)2, CO2-H2S, N2-H2O, CO-H2O, SO2-H2O, and O3-H2O.

  14. On the pseudopotential approximation in the van der Waals density functional calculations

    NASA Astrophysics Data System (ADS)

    Hamada, Ikutaro; Callsen, Martin

    The van der Waals density functional (vdW-DF) is a density functional that is able to describe van der Waals and covalent interactions in a seamless fashion, and has been applied to a variety of systems. In practical calculations, the pseudopotential (PP) approximation has been employed, for which the PPs should be generated consistently for the chosen exchange correlation XC functional. However, usually PPs generated with a generalized gradient approximation (GGA) XC functional are used and the effect of the approximation to the XC functional applied in the PP generation is scarcely discussed. In this work, we discuss the appropriate XC functionals in the PP generation for the vdW-DF calculations. Furthermore, we compare the vdW-DF results for several systems using the PP's generated with appropriate XC and those with GGA XC.

  15. Nuclear spin-spin coupling anisotropy in the van der Waals-bonded 129Xe dimer.

    PubMed

    Jokisaari, Jukka; Vaara, Juha

    2013-07-21

    The spin-spin coupling constant, J, in the van der Waals-bonded (129)Xe-(129)Xe dimer cannot be determined experimentally because of the magnetic equivalence of the two nuclei. In contrast, the anisotropy of the coupling tensor, ΔJ, can be obtained from the so called effective dipole-dipole coupling determined in a solid state inclusion compound whose cages accommodate two xenon atoms. For the determination of the experimental ΔJ((129)Xe, (129)Xe) we exploited the data reported earlier in this journal. [D. H. Brouwer et al., Phys. Chem. Chem. Phys., 2007, 9, 1093.] The experimental value and the value obtained from relativistic first-principles computation are in perfect agreement. To the best of our knowledge this is the first investigation of spin-spin coupling anisotropy in a van der Waals-bonded system. PMID:23743998

  16. Spectroscopic measurement of the titanium-helium van der Waals molecule: TiHe

    NASA Astrophysics Data System (ADS)

    Quiros, Nancy; Tariq, Naima; Weinstein, Jonathan

    2016-05-01

    Atoms that are weakly bound by the van der Waals (vdW) interaction are known as van der Waals molecules. The existence and formation of vdW molecules is favorable at low temperatures due to their weak binding energy. We have used laser ablation and helium buffer gas cooling to create the exotic vdW diatomic molecule made of titanium (Ti) and helium (He). TiHe molecules were detected through laser-induced-fluorescence spectroscopy closely blue-detuned from the a3F2 --> y3F3 atomic Ti transition at 25227 cm-1. Measurements of the binding energy of TiHe were obtained by studying its equilibrium thermodynamic properties. It is believed the molecules are formed from the constituent cold atoms through three-body recombination. Progress towards measuring the three-body recombination rate coefficient will be discussed. This material is based upon work supported by National Science Foundation under Grant No. PHY 1265905.

  17. Van der Waals heterostructure of phosphorene and hexagonal boron nitride: First-principles modeling

    NASA Astrophysics Data System (ADS)

    Peng, Zhang; Jing, Wang; Xiang-Mei, Duan

    2016-03-01

    We have studied the structural and electronic properties of a hybrid hexagonal boron nitride with phosphorene nanocomposite using ab initio density functional calculations. It is found that the interaction between the hexagonal boron nitride and phosphorene is dominated by the weak van der Waals interaction, with their own intrinsic electronic properties preserved. Furthermore, the band gap of the nanocomposite is dependent on the interfacial distance. Our results could shed light on the design of new devices based on van der Waals heterostructure. Projected supported by the National Natural Science Foundation of China (Grant No. 11574167), the New Century 151 Talents Project of Zhejiang Province,China, and the K. C. Wong Magna Foundation in Ningbo University, China.

  18. Microwave spectra of van der Waals complexes of importance in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Suenram, R. D.; Lovas, F. J.

    1990-01-01

    The Fourier-transform Fabry-Perot pulsed-molecular-beam microwave spectrometer at NIST was used to study the microwave spectra of a number of molecular dimers and trimers that may be present in planetary atmospheres. The weak van der Waals bonds associated with these species usually give rise to rotational-tunneling splittings in the microwave spectra. The microwave spectrum of the water dimer species was used to illustrate the complications that can arise in the study of the rotational spectra of these loosely bound species. In addition to the water dimer species, the microwave spectra of the following hydrogen-bonded and van der Waals complexes were studied: (CO2)2-H2O, CO2-(H2O)2, CO2-H2S, N2-H2O, CO-H2O, SO2-H2O, and O3-H2O.

  19. First principles calculations of solid-state thermionic transport in layered van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoming; Zebarjadi, Mona; Esfarjani, Keivan

    2016-08-01

    This work aims at understanding solid-state energy conversion and transport in layered (van der Waals) heterostructures in contact with metallic electrodes via a first-principles approach. As an illustration, a graphene/phosphorene/graphene heterostructure in contact with gold electrodes is studied by using density functional theory (DFT)-based first principles calculations combined with real space Green's function (GF) formalism. We show that for a monolayer phosphorene, quantum tunneling dominates the transport. By adding more phosphorene layers, one can switch from tunneling-dominated transport to thermionic-dominated transport, resulting in transporting more heat per charge carrier, thus, enhancing the cooling coefficient of performance. The use of layered van der Waals heterostructures has two advantages: (a) thermionic transport barriers can be tuned by changing the number of layers, and (b) thermal conductance across these non-covalent structures is very weak. The phonon thermal conductance of the present van der Waals heterostructure is found to be 4.1 MW m-2 K-1 which is one order of magnitude lower than the lowest value for that of covalently-bonded interfaces. The thermionic coefficient of performance for the proposed device is 18.5 at 600 K corresponding to an equivalent ZT of 0.13, which is significant for nanoscale devices. This study shows that layered van der Waals structures have great potential to be used as solid-state energy-conversion devices.This work aims at understanding solid-state energy conversion and transport in layered (van der Waals) heterostructures in contact with metallic electrodes via a first-principles approach. As an illustration, a graphene/phosphorene/graphene heterostructure in contact with gold electrodes is studied by using density functional theory (DFT)-based first principles calculations combined with real space Green's function (GF) formalism. We show that for a monolayer phosphorene, quantum tunneling dominates the

  20. EXPERIMENTAL AND THEORETICAL STUDIES OF THE CN-AR VAN DER WAALS COMPLEX

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The CN-Ar van der Waals complex has been observed using B2E+-X2E+ and A2II-X2E+ electronic transitions. The spectra yielded a dissociation energy of D0"=109+2 cm1 and a zero point rational constant of B0"=0.067+0.005 cm-1 for CN(x)-Ar. The dissociation energy for Cn(A)-Ar was found to be D0"=132+2...

  1. van der Waals epitaxy and photoresponse of two-dimensional CdSe plates.

    PubMed

    Zhu, Dan-Dan; Xia, Jing; Wang, Lei; Li, Xuan-Ze; Tian, Li-Feng; Meng, Xiang-Min

    2016-06-01

    Here we demonstrate the first growth of two-dimensional (2D) single-crystalline CdSe plates on mica substrates via van der Waals epitaxy. The as-synthesized 2D plates exhibit hexagonal, truncated triangular and triangular shapes with the lateral size around several microns. Photodetectors based on 2D CdSe plates present a fast response time of 24 ms, revealing that 2D CdSe is a promising building block for ultrathin optoelectronic devices. PMID:27199079

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

    DOE PAGESBeta

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; West, Damien; Meunier, Vincent; Zhang, Shengbai; Liang, Linagbo

    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

  3. The van der Waals interaction in one, two, and three dimensions

    NASA Astrophysics Data System (ADS)

    Ipsen, A. C.; Splittorff, K.

    2015-02-01

    The van der Waals interaction between two polarizable atoms is considered. In three dimensions, the standard form with an attractive 1/R6 potential is obtained from second-order quantum perturbation theory. When the electron motion is restricted to lower dimensions (but the 1/R Coulomb potential is retained), new terms in the expansion appear and alter both the sign and the R-dependence of the interaction.

  4. Estimation of Some Parameters from Morse-Morse-Spline-Van Der Waals Intermolecular Potential

    SciTech Connect

    Coroiu, I.

    2007-04-23

    Some parameters such as transport cross-sections and isotopic thermal diffusion factor have been calculated from an improved intermolecular potential, Morse-Morse-Spline-van der Waals (MMSV) potential proposed by R.A. Aziz et al. The treatment was completely classical and no corrections for quantum effects were made. The results would be employed for isotope separations of different spherical and quasi-spherical molecules.

  5. van der Waals epitaxy and photoresponse of two-dimensional CdSe plates

    NASA Astrophysics Data System (ADS)

    Zhu, Dan-Dan; Xia, Jing; Wang, Lei; Li, Xuan-Ze; Tian, Li-Feng; Meng, Xiang-Min

    2016-06-01

    Here we demonstrate the first growth of two-dimensional (2D) single-crystalline CdSe plates on mica substrates via van der Waals epitaxy. The as-synthesized 2D plates exhibit hexagonal, truncated triangular and triangular shapes with the lateral size around several microns. Photodetectors based on 2D CdSe plates present a fast response time of 24 ms, revealing that 2D CdSe is a promising building block for ultrathin optoelectronic devices.

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

    SciTech Connect

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; Liang, Chen; Damien, West; Meunier, Vincent; Zhang, Prof. Shengbai

    2016-01-01

    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 coherent 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

  7. Black phosphorene/monolayer transition-metal dichalcogenides as two dimensional van der Waals heterostructures: a first-principles study.

    PubMed

    You, Baiqing; Wang, Xiaocha; Zheng, Zhida; Mi, Wenbo

    2016-03-14

    The electronic structure of black phosphorene (BP)/monolayer 1H-XT2 (X = Mo, W; T = S, Se, Te) two dimensional (2D) van der Waals heterostructures have been calculated by the first-principles method. It is found that the electronic band structures of both BP and XT2 are preserved in the combined van der Waals heterostructures. The WSe2/BP van der Waals heterostructure demonstrates a type-I band alignment, but the MoS2/BP, MoSe2/BP, MoTe2/BP, WS2/BP and WTe2/BP van der Waals heterostructures demonstrate a type-II band alignment. In particular, the n-type XT2/p-type BP van der Waals heterostructures can be applied in p-n diode and logical devices. Strong spin splitting appears in all of the heterostructures when considering the spin orbital coupling. Our results play a significant role in the prediction of novel 2D van der Waals heterostructures that have potential applications in spin-filter devices, spin field effect transistors, optoelectronic devices, etc. PMID:26899350

  8. The hot pick-up technique for batch assembly of van der Waals heterostructures

    PubMed Central

    Pizzocchero, Filippo; Gammelgaard, Lene; Jessen, Bjarke S.; Caridad, José M.; Wang, Lei; Hone, James; Bøggild, Peter; Booth, Timothy J.

    2016-01-01

    The assembly of individual two-dimensional materials into van der Waals heterostructures enables the construction of layered three-dimensional materials with desirable electronic and optical properties. A core problem in the fabrication of these structures is the formation of clean interfaces between the individual two-dimensional materials which would affect device performance. We present here a technique for the rapid batch fabrication of van der Waals heterostructures, demonstrated by the controlled production of 22 mono-, bi- and trilayer graphene stacks encapsulated in hexagonal boron nitride with close to 100% yield. For the monolayer devices, we found semiclassical mean-free paths up to 0.9 μm, with the narrowest samples showing clear indications of the transport being affected by boundary scattering. The presented method readily lends itself to fabrication of van der Waals heterostructures in both ambient and controlled atmospheres, while the ability to assemble pre-patterned layers paves the way for complex three-dimensional architectures. PMID:27305833

  9. Large area molybdenum disulphide- epitaxial graphene vertical Van der Waals heterostructures.

    PubMed

    Pierucci, Debora; Henck, Hugo; Naylor, Carl H; Sediri, Haikel; Lhuillier, Emmanuel; Balan, Adrian; Rault, Julien E; Dappe, Yannick J; Bertran, François; Fèvre, Patrick Le; Johnson, A T Charlie; Ouerghi, Abdelkarim

    2016-01-01

    Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design. PMID:27246929

  10. Large area molybdenum disulphide- epitaxial graphene vertical Van der Waals heterostructures

    PubMed Central

    Pierucci, Debora; Henck, Hugo; Naylor, Carl H.; Sediri, Haikel; Lhuillier, Emmanuel; Balan, Adrian; Rault, Julien E.; Dappe, Yannick J.; Bertran, François; Fèvre, Patrick Le; Johnson, A. T. Charlie; Ouerghi, Abdelkarim

    2016-01-01

    Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design. PMID:27246929

  11. The hot pick-up technique for batch assembly of van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Pizzocchero, Filippo; Gammelgaard, Lene; Jessen, Bjarke S.; Caridad, José M.; Wang, Lei; Hone, James; Bøggild, Peter; Booth, Timothy J.

    2016-06-01

    The assembly of individual two-dimensional materials into van der Waals heterostructures enables the construction of layered three-dimensional materials with desirable electronic and optical properties. A core problem in the fabrication of these structures is the formation of clean interfaces between the individual two-dimensional materials which would affect device performance. We present here a technique for the rapid batch fabrication of van der Waals heterostructures, demonstrated by the controlled production of 22 mono-, bi- and trilayer graphene stacks encapsulated in hexagonal boron nitride with close to 100% yield. For the monolayer devices, we found semiclassical mean-free paths up to 0.9 μm, with the narrowest samples showing clear indications of the transport being affected by boundary scattering. The presented method readily lends itself to fabrication of van der Waals heterostructures in both ambient and controlled atmospheres, while the ability to assemble pre-patterned layers paves the way for complex three-dimensional architectures.

  12. van der Waals torque and force between dielectrically anisotropic layered media

    NASA Astrophysics Data System (ADS)

    Lu, Bing-Sui; Podgornik, Rudolf

    2016-07-01

    We analyse van der Waals interactions between a pair of dielectrically anisotropic plane-layered media interacting across a dielectrically isotropic solvent medium. We develop a general formalism based on transfer matrices to investigate the van der Waals torque and force in the limit of weak birefringence and dielectric matching between the ordinary axes of the anisotropic layers and the solvent. We apply this formalism to study the following systems: (i) a pair of single anisotropic layers, (ii) a single anisotropic layer interacting with a multilayered slab consisting of alternating anisotropic and isotropic layers, and (iii) a pair of multilayered slabs each consisting of alternating anisotropic and isotropic layers, looking at the cases where the optic axes lie parallel and/or perpendicular to the plane of the layers. For the first case, the optic axes of the oppositely facing anisotropic layers of the two interacting slabs generally possess an angular mismatch, and within each multilayered slab the optic axes may either be the same or undergo constant angular increments across the anisotropic layers. In particular, we examine how the behaviors of the van der Waals torque and force can be "tuned" by adjusting the layer thicknesses, the relative angular increment within each slab, and the angular mismatch between the slabs.

  13. van der Waals torque and force between dielectrically anisotropic layered media.

    PubMed

    Lu, Bing-Sui; Podgornik, Rudolf

    2016-07-28

    We analyse van der Waals interactions between a pair of dielectrically anisotropic plane-layered media interacting across a dielectrically isotropic solvent medium. We develop a general formalism based on transfer matrices to investigate the van der Waals torque and force in the limit of weak birefringence and dielectric matching between the ordinary axes of the anisotropic layers and the solvent. We apply this formalism to study the following systems: (i) a pair of single anisotropic layers, (ii) a single anisotropic layer interacting with a multilayered slab consisting of alternating anisotropic and isotropic layers, and (iii) a pair of multilayered slabs each consisting of alternating anisotropic and isotropic layers, looking at the cases where the optic axes lie parallel and/or perpendicular to the plane of the layers. For the first case, the optic axes of the oppositely facing anisotropic layers of the two interacting slabs generally possess an angular mismatch, and within each multilayered slab the optic axes may either be the same or undergo constant angular increments across the anisotropic layers. In particular, we examine how the behaviors of the van der Waals torque and force can be "tuned" by adjusting the layer thicknesses, the relative angular increment within each slab, and the angular mismatch between the slabs. PMID:27475386

  14. Study of van der Waals bonding and interactions in metal organic framework materials.

    PubMed

    Zuluaga, Sebastian; Canepa, Pieremanuele; Tan, Kui; Chabal, Yves J; Thonhauser, Timo

    2014-04-01

    Metal organic framework (MOF) materials have attracted a lot of attention due to their numerous applications in fields such as hydrogen storage, carbon capture and gas sequestration. In all these applications, van der Waals forces dominate the interaction between the small guest molecules and the walls of the MOFs. In this review article, we describe how a combined theoretical and experimental approach can successfully be used to study those weak interactions and elucidate the adsorption mechanisms important for various applications. On the theory side, we show that, while standard density functional theory is not capable of correctly describing van der Waals interactions, functionals especially designed to include van der Waals forces exist, yielding results in remarkable agreement with experiment. From the experimental point of view, we show examples in which IR adsorption and Raman spectroscopy are essential to study molecule/MOF interactions. Importantly, we emphasize throughout this review that a combination of theory and experiment is crucial to effectively gain further understanding. In particular, we review such combined studies for the adsorption mechanism of small molecules in MOFs, the chemical stability of MOFs under humid conditions, water cluster formation inside MOFs, and the diffusion of small molecules into MOFs. The understanding of these phenomena is critical for the rational design of new MOFs with desired properties. PMID:24613989

  15. The hot pick-up technique for batch assembly of van der Waals heterostructures.

    PubMed

    Pizzocchero, Filippo; Gammelgaard, Lene; Jessen, Bjarke S; Caridad, José M; Wang, Lei; Hone, James; Bøggild, Peter; Booth, Timothy J

    2016-01-01

    The assembly of individual two-dimensional materials into van der Waals heterostructures enables the construction of layered three-dimensional materials with desirable electronic and optical properties. A core problem in the fabrication of these structures is the formation of clean interfaces between the individual two-dimensional materials which would affect device performance. We present here a technique for the rapid batch fabrication of van der Waals heterostructures, demonstrated by the controlled production of 22 mono-, bi- and trilayer graphene stacks encapsulated in hexagonal boron nitride with close to 100% yield. For the monolayer devices, we found semiclassical mean-free paths up to 0.9 μm, with the narrowest samples showing clear indications of the transport being affected by boundary scattering. The presented method readily lends itself to fabrication of van der Waals heterostructures in both ambient and controlled atmospheres, while the ability to assemble pre-patterned layers paves the way for complex three-dimensional architectures. PMID:27305833

  16. Effect of van der Waals interactions on the structural and binding properties of GaSe

    NASA Astrophysics Data System (ADS)

    Sarkisov, Sergey Y.; Kosobutsky, Alexey V.; Shandakov, Sergey D.

    2015-12-01

    The influence of van der Waals interactions on the lattice parameters, band structure, elastic moduli and binding energy of layered GaSe compound has been studied using projector-augmented wave method within density functional theory. We employed the conventional local/semilocal exchange-correlation functionals and recently developed van der Waals functionals which are able to describe dispersion forces. It is found that application of van der Waals density functionals allows to substantially increase the accuracy of calculations of the lattice constants a and c and interlayer distance in GaSe at ambient conditions and under hydrostatic pressure. The pressure dependences of the a-parameter, Ga-Ga, Ga-Se bond lengths and Ga-Ga-Se bond angle are characterized by a relatively low curvature, while c(p) has a distinct downward bowing due to nonlinear shrinking of the interlayer spacing. From the calculated binding energy curves we deduce the interlayer binding energy of GaSe, which is found to be in the range 0.172-0.197 eV/layer (14.2-16.2 meV/Å2).

  17. Physisorption of nucleobases on graphene: a comparative van der Waals study

    NASA Astrophysics Data System (ADS)

    Le, Duy; Kara, Abdelkader; Schröder, Elsebeth; Hyldgaard, Per; Rahman, Talat S.

    2012-10-01

    The physisorption of the nucleobases adenine (A), cytosine (C), guanine (G), thymine (T), and uracil (U) on graphene is studied using several variants of the density functional theory (DFT): the generalized gradient approximation with the inclusion of van der Waals interaction (vdW) based on the TS approach (Tkatchenko and Scheffer 2009 Phys. Rev. Lett. 102 073005) and our simplified version of this approach (here called sTS), the van der Waals density functional vdW-DF (Dion et al 2004 Phys. Rev. Lett. 92 246401) and vdW-DF2 (Lee et al 2010 Phys. Rev. B 82 081101), and DFT-D2 (Grimme 2006 J. Comput. Chem. 27 1787) and DFT-D3 (Grimme et al 2010 J. Chem. Phys. 132 154104) methods. The binding energies of nucleobases on graphene are found to be in the following order: G > A > T > C > U within TS, sTS, vdW-DF, and DFT-D2, and in the following order: G > A > T ˜ C > U within DFT-D3 and vdW-DF2. The binding separations are found to be different within different methods and in the following order: DFT-D2 < TS < DFT-D3 ˜ vdW-DF2 < vdW-DF. We also comment on the efficiency of combining the DFT-D approach and vdW-DF to study systems with van der Waals interactions.

  18. The effects of van der Waals attractions on cloud droplet growth by coalescence

    NASA Technical Reports Server (NTRS)

    Rogers, Jan R.; Davis, Robert H.

    1990-01-01

    The inclusion of van der Waals attractions in the interaction between cloud droplets has been recently shown to significantly increase the collision efficiencies of the smaller droplets. In the current work, these larger values for the collision efficiencies are used in a population dynamics model of the droplet size distribution evolution with time, in hopes of at least partially resolving the long-standing paradox in cloud microphysics that predicted rates of the onset of precipitation are generally much lower than those which are observed. Evolutions of several initial cloud droplet spectra have been tracked in time. Size evolutions are compared as predicted from the use of collision efficiencies computed using two different models to allow for droplet-droplet contact: one which considers slip flow effects only, and one which considers the combined effects of van der Waals forces and slip flow. The rate at which the droplet mass density function shifts to larger droplet sizes is increased by typically 20-25 percent, when collision efficiencies which include van der Waals forces are used.

  19. Large area molybdenum disulphide- epitaxial graphene vertical Van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Pierucci, Debora; Henck, Hugo; Naylor, Carl H.; Sediri, Haikel; Lhuillier, Emmanuel; Balan, Adrian; Rault, Julien E.; Dappe, Yannick J.; Bertran, François; Fèvre, Patrick Le; Johnson, A. T. Charlie; Ouerghi, Abdelkarim

    2016-06-01

    Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design.

  20. Short-range Cut-Off of the Summed-Up van der Waals Series

    NASA Astrophysics Data System (ADS)

    Patra, Abhirup; Perdew, John P.

    2015-03-01

    van der Waals interactions are important in typical van der Waals-bound systems such as noble-gas, hydrocarbon, alkali and alkaline-earth dimers. The summed-up van der Waals series works well and gives an accurate result at large separation between two atoms. But it has a strong singularity at short non-zero separation, where the two atoms touch. In this work we remove that singularity with a reasonable and physical choice of the cut-off distance. Only one fitting parameter has been introduced for the short-range cut off. The parameter in our model has been optimized for each system, and a system-averaged value has been used to get the final binding energy curves. When this correction is added to the binding energy curve from the semilocal density functional meta-GGA-MS2, we get vdW- corrected binding energy curve. These curves are compared with the results of other vdW-corrected methods such as PBE-D2 and vdW-DF2 .Binding energy curves are in reasonable agreement with those from experiment. These curves also predict reasonably good equilibrium bond length. Supported by NSF (DMR).

  1. Van der Waals, Casimir, and Lifshitz forces in soft matter

    NASA Astrophysics Data System (ADS)

    Kats, E. I.

    2015-09-01

    E M Lifshitz's theory of fluctuation molecular forces (Zh. Eksp. Teor. Fiz., Vol. 29, p. 94, 1955 [Sov. Phys. JETP, Vol. 2, 73, 1956]) and related problems are introduced from a historical perspective. Applications of the theory to soft matter physics are discussed, together with some new predictions (for example, the stability of smectic or cholesteric liquid crystal films).

  2. Effects of truncating van der Waals interactions in lipid bilayer simulations

    PubMed Central

    Huang, Kun; García, Angel E.

    2014-01-01

    In membrane simulations, it is known that truncating electrostatic interactions results in artificial ordering of lipids at the truncation distance. However, less attention has been paid to the effect of truncating van der Waals (VDW) interactions. Since the VDW potential decays as r−6, it is frequently neglected beyond a cutoff of around 1 nm. In some cases, analytical dispersion corrections appropriate for isotropic systems are applied to the pressure and the potential energy. In this work, we systematically study the effect of truncating VDW interactions at different cutoffs in 1,2-Dipalmitoyl-sn-glycero-3-phosphocholine bilayers with the Berger force field. We show that the area per lipid decreases systematically when the VDW cutoff (rc) increases. This dependence persists even when dispersion corrections are applied. Since the analytical form of the dispersion correction is only appropriate for isotropic systems, we suggest that a long VDW cutoff should be used in preference over a short VDW cutoff. To determine the appropriate cutoff, we simulate liquid pentadecane with the Berger parameters and find that rc ≥ 1.4 nm is sufficient to reproduce the density and the heat of vaporization of pentadecane. Bilayers simulated with rc ≥ 1.4 nm show an improved agreement with experiments in both the form factors and the deuterium order parameters. Finally, we report that the VDW cutoff has a significant impact on the lipid flip-flop energetics and an inappropriate short VDW cutoff results in a bilayer that is prone to form water defects across the bilayer. PMID:25217953

  3. Turbulent mixing of a slightly supercritical van der Waals fluid at low-Mach number

    NASA Astrophysics Data System (ADS)

    Battista, F.; Picano, F.; Casciola, C. M.

    2014-05-01

    Supercritical fluids near the critical point are characterized by liquid-like densities and gas-like transport properties. These features are purposely exploited in different contexts ranging from natural products extraction/fractionation to aerospace propulsion. Large part of studies concerns this last context, focusing on the dynamics of supercritical fluids at high Mach number where compressibility and thermodynamics strictly interact. Despite the widespread use also at low Mach number, the turbulent mixing properties of slightly supercritical fluids have still not investigated in detail in this regime. This topic is addressed here by dealing with Direct Numerical Simulations of a coaxial jet of a slightly supercritical van der Waals fluid. Since acoustic effects are irrelevant in the low Mach number conditions found in many industrial applications, the numerical model is based on a suitable low-Mach number expansion of the governing equation. According to experimental observations, the weakly supercritical regime is characterized by the formation of finger-like structures - the so-called ligaments - in the shear layers separating the two streams. The mechanism of ligament formation at vanishing Mach number is extracted from the simulations and a detailed statistical characterization is provided. Ligaments always form whenever a high density contrast occurs, independently of real or perfect gas behaviors. The difference between real and perfect gas conditions is found in the ligament small-scale structure. More intense density gradients and thinner interfaces characterize the near critical fluid in comparison with the smoother behavior of the perfect gas. A phenomenological interpretation is here provided on the basis of the real gas thermodynamics properties.

  4. Effects of truncating van der Waals interactions in lipid bilayer simulations

    SciTech Connect

    Huang, Kun; García, Angel E.

    2014-09-14

    In membrane simulations, it is known that truncating electrostatic interactions results in artificial ordering of lipids at the truncation distance. However, less attention has been paid to the effect of truncating van der Waals (VDW) interactions. Since the VDW potential decays as r{sup −6}, it is frequently neglected beyond a cutoff of around 1 nm. In some cases, analytical dispersion corrections appropriate for isotropic systems are applied to the pressure and the potential energy. In this work, we systematically study the effect of truncating VDW interactions at different cutoffs in 1,2-Dipalmitoyl-sn-glycero-3-phosphocholine bilayers with the Berger force field. We show that the area per lipid decreases systematically when the VDW cutoff (r{sub c}) increases. This dependence persists even when dispersion corrections are applied. Since the analytical form of the dispersion correction is only appropriate for isotropic systems, we suggest that a long VDW cutoff should be used in preference over a short VDW cutoff. To determine the appropriate cutoff, we simulate liquid pentadecane with the Berger parameters and find that r{sub c} ≥ 1.4 nm is sufficient to reproduce the density and the heat of vaporization of pentadecane. Bilayers simulated with r{sub c} ≥ 1.4 nm show an improved agreement with experiments in both the form factors and the deuterium order parameters. Finally, we report that the VDW cutoff has a significant impact on the lipid flip-flop energetics and an inappropriate short VDW cutoff results in a bilayer that is prone to form water defects across the bilayer.

  5. Turbulent mixing of a slightly supercritical van der Waals fluid at low-Mach number

    SciTech Connect

    Battista, F.; Casciola, C. M.; Picano, F.

    2014-05-15

    Supercritical fluids near the critical point are characterized by liquid-like densities and gas-like transport properties. These features are purposely exploited in different contexts ranging from natural products extraction/fractionation to aerospace propulsion. Large part of studies concerns this last context, focusing on the dynamics of supercritical fluids at high Mach number where compressibility and thermodynamics strictly interact. Despite the widespread use also at low Mach number, the turbulent mixing properties of slightly supercritical fluids have still not investigated in detail in this regime. This topic is addressed here by dealing with Direct Numerical Simulations of a coaxial jet of a slightly supercritical van der Waals fluid. Since acoustic effects are irrelevant in the low Mach number conditions found in many industrial applications, the numerical model is based on a suitable low-Mach number expansion of the governing equation. According to experimental observations, the weakly supercritical regime is characterized by the formation of finger-like structures – the so-called ligaments – in the shear layers separating the two streams. The mechanism of ligament formation at vanishing Mach number is extracted from the simulations and a detailed statistical characterization is provided. Ligaments always form whenever a high density contrast occurs, independently of real or perfect gas behaviors. The difference between real and perfect gas conditions is found in the ligament small-scale structure. More intense density gradients and thinner interfaces characterize the near critical fluid in comparison with the smoother behavior of the perfect gas. A phenomenological interpretation is here provided on the basis of the real gas thermodynamics properties.

  6. 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

  7. Microwave and ab initio studies of rare gas-methane van der Waals complexes

    NASA Astrophysics Data System (ADS)

    Liu, Yaqian; Jäger, Wolfgang

    2004-05-01

    Rotational spectra of the weakly bound Kr-methane van der Waals complex were recorded using a pulsed molecular beam Fourier transform microwave spectrometer in the range from 3.5 to 18 GHz. Spectra of 25 isotopomers of Kr-methane were assigned and analyzed. For isotopomers containing CH4, 13CH4, and CD4, two sets of transitions with K=0 and one with K=1 were recorded, correlating to the j=0, 1, and 2 rotational levels of free methane, respectively (j is the rotational angular momentum quantum number of the methane monomer). For isotopomers containing CH3D and CHD3, two K=0 components were recorded, correlating to the jk=00 and 11 rotational levels of free methane (k corresponds to the projection of j onto the C3 axis of CH3D and CHD3). The obtained spectroscopic results were used to derive van der Waals bond distance R, van der Waals stretching frequency νs, and the corresponding stretching force constant ks. Nuclear spin statistical weights of individual states were obtained from molecular symmetry group analyses and were compared with the observed relative transition intensities. The tentatively assigned j=2 transitions were more intense than predicted from symmetry considerations. This is attributed to a relatively large effective dipole moment of this state, supported by ab initio dipole moment calculations. Ab initio potential energy calculations of Kr-CH4 and Ar-CH4 were done at the coupled cluster level of theory, with single and double excitations and perturbative inclusion of triple excitations, using the aug-cc-pVTZ basis set supplemented with bond functions. The theoretical results show that the angular dynamics of the dimer does not change significantly when the binding partner of methane changes from Ar to Kr. The dipole moment of Ar-CH4 was calculated at various configurations, providing a qualitative explanation for the unsuccessful spectral searches for rotational transitions of Ar-CH4.

  8. The Dielectric Function for Water and Its Application to van der Waals Forces.

    PubMed

    Dagastine; Prieve; White

    2000-11-15

    The dielectric response, varepsilon(ixi), for water (which is required in Lifshitz theory to calculate the van der Waals interactions in aqueous systems) is commonly constructed, in the absence of complete spectral data, by fitting a damped-harmonic-oscillator model to absorption data. Two sets of parameters for the model have been developed corresponding to different constraints: Parsegian and Weiss (J. Colloid Interface Sci., 1981, 81, 285) and Roth and Lenhoff (J. Colloid Interface Sci., 1996, 179, 637). These different representations of the dielectric response lead to significant differences in the van der Waals force calculated from Lifshitz theory. In this work, more recent and complete spectral data for water were compiled from the literature and direct integration of the Kramers-Kronig relations was used to construct a new varepsilon(ixi) for water at 298 degrees K. This approach also allows a number of different types of spectral measurements (such as infrared spectroscopy, microwave resonance techniques, and x-ray inelastic scattering) in the compilation of absorption data over a large frequency range (on the order of 8 to 10 decades in frequency). A Kramers-Kronig integration was employed to construct the real and imaginary parts of varepsilon(omega), varepsilon'(omega), and varepsilon"(omega) for water from the different spectral measurements before calculation of varepsilon(ixi) from its integral definition. The resulting new varepsilon(ixi) is intermediate between the Parsegian-Weiss and Roth-Lenhoff representations of varepsilon(ixi), does not use a model, and treats the conversion of absorption data as rigorously as possible. We believe the varepsilon(ixi) from the present work is the most reliable construction for use in van der Waals force calculations using Lifshitz theory. The extension of the varepsilon(ixi) construction to other temperatures is also discussed. Copyright 2000 Academic Press. PMID:11049685

  9. Local Probe Spectroscopy of Two-Dimensional van der Waals Heterostructures

    NASA Astrophysics Data System (ADS)

    Yankowitz, Matthew Abraham

    A large family of materials, collectively known as "van der Waals materials", have attracted enormous research attention over the past decade following the realization that they could be isolated into individual crystalline monolayers, with charge carriers behaving effectively two-dimensionally. More recently, an even larger class of composite materials has been realized, made possible by combining the isolated atomic layers of different materials into "van der Waals heterostructures", which can exhibit electronic and optical behaviors not observed in the parent materials alone. This thesis describes efforts to characterize the atomic-scale structural and electronic properties of these van der Waals materials and heterostructures through scanning tunneling microscopy measurements. The majority of this work addresses the properties of monolayer and few-layer graphene, whose charge carriers are described by massless and massive chiral Dirac Hamiltonians, respectively. In heterostructures with hexagonal boron nitride, an insulating isomorph of graphene, we observe electronic interference patterns between the two materials which depend on their relative rotation. As a result, replica Dirac cones are formed in the valence and conduction bands of graphene, with their energy tuned by the rotation. Further, we are able to dynamically drag the graphene lattice in these heterostructures, owing to an interaction between the scanning probe tip and the domain walls formed by the electronic interference pattern. Similar dragging is observed in domain walls of trilayer graphene, whose electronic properties are found to depend on the stacking configuration of the three layers. Scanning tunneling spectroscopy provides a direct method for visualizing the scattering pathways of electrons in these materials. By analyzing the scattering, we can directly infer properties of the band structures and local environments of these heterostructures. In bilayer graphene, we map the electrically

  10. Nanoscopy of Surface-Induced van der Waals-Zeeman Transitions

    SciTech Connect

    Hamamda, M.; Grucker, J.; Dutier, G.; Perales, F.; Baudon, J.; Ducloy, M.; Bocvarski, V.

    2008-10-22

    van der Waals transitions among magnetic sub-levels of a metastable rare gas atom passing near a surface immersed in a magnetic field, are described. Related transition amplitudes are calculated using both the sudden and the Landau-Zener approximations. Experimental data for Ne*({sup 3}P{sub 2}) atoms traversing a copper grating are presented. For a pair of surfaces (e.g. the opposite edges of a slit) and a sufficiently large coherence width, Fresnel's biprism interference fringes are obtained. From this interference pattern, detailed information about the transition amplitude at a sub-nanometric scale can be derived. The effect of gravity on this pattern is examined.

  11. Infrared vibrational predissociation of van der Waals clusters: applications to isotope separation

    SciTech Connect

    Philippoz, J.M.; Zellweger, J.M.; van den Bergh, H.; Monot, R.

    1984-08-30

    Isotope separation is demonstrated following the selective infrared laser-induced photodissociation of van der Waals clusters in a free jet. Irradiation of a natural abundance mixture of SF/sub 6/ isotopomers diluted in argon with a 20-W cw CO/sub 2/ laser gives overall enrichment factors in excess of 1.1. By adjusting the wavelength one can either enrich or deplete the center of the free jet in any one of the sulfur isotopes. Furthermore, unselective photodissociation of clusters can be used to enhance the separation of isotopes in a recently reported selective condensation method. 8 references, 3 figures.

  12. 3D van der Waals σ-model and its topological excitations

    NASA Astrophysics Data System (ADS)

    Bulgadaev, S. A.

    2001-09-01

    It is shown that the 3D vector van der Waals nonlinear σ-model (NSM) on a sphere S2 has two types of topological excitations: reminiscent vortices and instantons of 2D NSM. The first ones, the hedgehogs, are described by the homotopic group π2(S2) = Z and have logarithmic energies. They are an analog of 2D vortices. The second ones, corresponding to 2D instantons, are the hopfions. They are described by the homotopic group π3(S2) = Z, or the Hopf invariant HinZ, and have finite energy. The possibility of a topological phase transition in this model and its applications are briefly discussed.

  13. Electron transport calculations with Wannier functions in van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Dong, Wushi; Lopez-Bezanilla, Alejandro; Littlewood, Peter; Andreas Roelofs'group at Argonne National Lab Collaboration

    The vertical stacking of 2D materials forming van der Waals heterostructures (vdWHs) exhibits a wide range of interesting properties. A combined approach based on the Green's function formalism and a mean-field description of the electronic structure is used to calculate vertical electron transport in vdWHs. Tight-binding parameters obtained from Maximally Localized Wannier Functions enable us to model quantum electron transport at low computational costs. Our analysis of electron transport efficiencies provides the foundation and motivation for experimental works.

  14. Construction of van der Waals magnetic tunnel junction using ferromagnetic layered dichalcogenide

    SciTech Connect

    Arai, Miho; Moriya, Rai Yabuki, Naoto; Masubuchi, Satoru; Ueno, Keiji; Machida, Tomoki

    2015-09-07

    We investigate the micromechanical exfoliation and van der Waals (vdW) assembly of ferromagnetic layered dichalcogenide Fe{sub 0.25}TaS{sub 2}. The vdW interlayer coupling at the Fe-intercalated plane of Fe{sub 0.25}TaS{sub 2} allows exfoliation of flakes. A vdW junction between the cleaved crystal surfaces is constructed by dry transfer method. We observe tunnel magnetoresistance in the resulting junction under an external magnetic field applied perpendicular to the plane, demonstrating spin-polarized tunneling between the ferromagnetic layered material and the vdW junction.

  15. Stability of an attractive bosonic cloud with van der Waals interaction

    SciTech Connect

    Biswas, Anindya; Das, Tapan Kumar; Salasnich, Luca; Chakrabarti, Barnali

    2010-10-15

    We investigate the structure and stability of Bose-Einstein condensates of {sup 7}Li atoms with realistic van der Waals interactions by using the potential harmonic expansion method. Besides the known low-density metastable solution with a contact {delta}-function interaction, we find a stable branch at a higher density which corresponds to the formation of an atomic cluster. Comparison with the results of a nonlocal effective interaction is also presented. We analyze the effect of trap size on the transition between the two branches of solutions. We also compute the loss rate of a Bose condensate due to two- and three-body collisions.

  16. Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M.; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J.; Li, Lain-Jong; Wallace, Robert M.; Datta, Suman; Robinson, Joshua A.

    2015-06-01

    Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics.

  17. Virtual Resonance and Frequency Difference Generation by van der Waals Interaction

    NASA Astrophysics Data System (ADS)

    Tetard, L.; Passian, A.; Eslami, S.; Jalili, N.; Farahi, R. H.; Thundat, T.

    2011-05-01

    The ability to explore the interior of materials for the presence of inhomogeneities was recently demonstrated by mode synthesizing atomic force microscopy [L. Tetard, A. Passian, and T. Thundat, Nature Nanotech. 5, 105 (2009).NNAABX1748-338710.1038/nnano.2009.454]. Proposing a semiempirical nonlinear force, we show that difference frequency ω- generation, regarded as the simplest synthesized mode, occurs optimally when the force is tuned to van der Waals form. From a parametric study of the probe-sample excitation, we show that the predicted ω- oscillation agrees well with experiments. We then introduce the concept of virtual resonance to show that probe oscillations at ω- can efficiently be enhanced.

  18. Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures.

    PubMed

    Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J; Li, Lain-Jong; Wallace, Robert M; Datta, Suman; Robinson, Joshua A

    2015-01-01

    Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics. PMID:26088295

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

    SciTech Connect

    Xia, Congxin Xue, Bin; Wang, Tianxing; Peng, Yuting; Jia, Yu

    2015-11-09

    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.

  20. Observing the interplay between surface and bulk optical nonlinearities in thin van der Waals crystals

    PubMed Central

    Deckoff-Jones, Skylar; Zhang, Jingjing; Petoukhoff, Christopher E.; Man, Michael K.L.; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel M.; Talbayev, Diyar; Madéo, Julien; Dani, Keshav M.

    2016-01-01

    Van der Waals materials, existing in a range of thicknesses from monolayer to bulk, allow for interplay between surface and bulk nonlinearities, which otherwise dominate only at atomically-thin or bulk extremes, respectively. Here, we observe an unexpected peak in intensity of the generated second harmonic signal versus the thickness of Indium Selenide crystals, in contrast to the quadratic increase expected from thin crystals. We explain this by interference effects between surface and bulk nonlinearities, which offer a new handle on engineering the nonlinear optical response of 2D materials and their heterostructures. PMID:26936437

  1. Spectroscopy of DABCO-rare-gas and DABCO-DABCO van der Waals complexes

    NASA Astrophysics Data System (ADS)

    van den Hock, G.; Consalvo, D.; Parker, D. H.; Reuss, J.

    1993-03-01

    The excited electronic origin bands of several DABCO containing van der Waals complexes have been observed via (1+1) resonance enhanced multi-photon ionization. Sharp resonances with widths of about 3 cm-1 are seen for DABCO-Rg n=1,2,3 (Rg is Ar, Kr or Xe), for the DABCO-DABCO dimer and for DABCO-DABCO-Ar. The origins of the rare-gas complexes are blue shifted with respect to the monomer origin. Broad features originating from DABCO-Rg n complexes with high n, appear to higher energies than the complex origins, with widths of 120 cm-1.

  2. Microwaves Probe Dipole Blockade and van der Waals Forces in a Cold Rydberg Gas.

    PubMed

    Teixeira, R Celistrino; Hermann-Avigliano, C; Nguyen, T L; Cantat-Moltrecht, T; Raimond, J M; Haroche, S; Gleyzes, S; Brune, M

    2015-07-01

    We show that microwave spectroscopy of a dense Rydberg gas trapped on a superconducting atom chip in the dipole blockade regime reveals directly the dipole-dipole many-body interaction energy spectrum. We use this method to investigate the expansion of the Rydberg cloud under the effect of repulsive van der Waals forces and the breakdown of the frozen gas approximation. This study opens a promising route for quantum simulation of many-body systems and quantum information transport in chains of strongly interacting Rydberg atoms. PMID:26182093

  3. Nonadiabatic alignment of van der Waals--force-bound argon dimers by femtosecond laser pulses

    SciTech Connect

    Wu, J.; Vredenborg, A.; Ulrich, B.; Schmidt, L. Ph. H.; Meckel, M.; Voss, S.; Sann, H.; Kim, H.; Jahnke, T.; Doerner, R.

    2011-06-15

    We demonstrated that the weak van der Waals-force-bound argon dimer can be nonadiabatically aligned by nonresonant femtosecond laser pulses, showing periodic alignment and anti-alignment revivals after the extinction of the laser pulse. Based on the measured nonadiabatic alignment trace, the rotational constant of the argon dimer ground state is determined to be B{sub 0}= 0.05756 {+-} 0.00004 cm{sup -1}. Noticeable alignment dependence of frustrated tunneling ionization and bond-softening induced dissociation of the argon dimer are observed.

  4. Thermally programmable gas storage and release in single crystals of an organic van der Waals host.

    PubMed

    Enright, Gary D; Udachin, Konstantin A; Moudrakovski, Igor L; Ripmeester, John A

    2003-08-20

    A single crystal of a low density form of guest-free p-tert-butylcalix[4]arene can take up and release small guest molecules by controlling the temperature and pressure without changing the structure. Using NMR spectroscopy with flowing hyperpolarized xenon, we have shown that at room temperature access of xenon to the pore system is difficult, whereas it is relatively easy at 100 degrees C. There are good prospects for simple van der Waals materials such as the title material to be used as programmable zeolite mimics. PMID:12914432

  5. Observing the interplay between surface and bulk optical nonlinearities in thin van der Waals crystals

    NASA Astrophysics Data System (ADS)

    Deckoff-Jones, Skylar; Zhang, Jingjing; Petoukhoff, Christopher E.; Man, Michael K. L.; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel M.; Talbayev, Diyar; Madéo, Julien; Dani, Keshav M.

    2016-03-01

    Van der Waals materials, existing in a range of thicknesses from monolayer to bulk, allow for interplay between surface and bulk nonlinearities, which otherwise dominate only at atomically-thin or bulk extremes, respectively. Here, we observe an unexpected peak in intensity of the generated second harmonic signal versus the thickness of Indium Selenide crystals, in contrast to the quadratic increase expected from thin crystals. We explain this by interference effects between surface and bulk nonlinearities, which offer a new handle on engineering the nonlinear optical response of 2D materials and their heterostructures.

  6. Evidence for strong van der Waals type Rydberg-Rydberg interaction in a thermal vapor.

    PubMed

    Baluktsian, T; Huber, B; Löw, R; Pfau, T

    2013-03-22

    We present evidence for Rydberg-Rydberg interaction in a gas of rubidium atoms above room temperature. Rabi oscillations on the nanosecond time scale to different Rydberg states are investigated in a vapor cell experiment. Analyzing the atomic time evolution and comparing to a dephasing model, we find a scaling with the Rydberg quantum number n that is consistent with van der Waals interaction. Our results show that the interaction strength can be larger than the kinetic energy scale (Doppler width), which is the requirement for realization of thermal quantum devices in the GHz regime. PMID:25166800

  7. Observing the interplay between surface and bulk optical nonlinearities in thin van der Waals crystals.

    PubMed

    Deckoff-Jones, Skylar; Zhang, Jingjing; Petoukhoff, Christopher E; Man, Michael K L; Lei, Sidong; Vajtai, Robert; Ajayan, Pulickel M; Talbayev, Diyar; Madéo, Julien; Dani, Keshav M

    2016-01-01

    Van der Waals materials, existing in a range of thicknesses from monolayer to bulk, allow for interplay between surface and bulk nonlinearities, which otherwise dominate only at atomically-thin or bulk extremes, respectively. Here, we observe an unexpected peak in intensity of the generated second harmonic signal versus the thickness of Indium Selenide crystals, in contrast to the quadratic increase expected from thin crystals. We explain this by interference effects between surface and bulk nonlinearities, which offer a new handle on engineering the nonlinear optical response of 2D materials and their heterostructures. PMID:26936437

  8. Ground-state van der Waals forces in planar multilayer magnetodielectrics

    SciTech Connect

    Buhmann, Stefan Yoshi; Welsch, Dirk-Gunnar; Kampf, Thomas

    2005-09-15

    Within the frame of lowest-order perturbation theory, the van der Waals potential of a ground-state atom placed within an arbitrary dispersing and absorbing magnetodielectric multilayer system is given. Examples of an atom situated in front of a magnetodielectric plate or between two such plates are studied in detail. Special emphasis is placed on the competing attractive and repulsive force components associated with the electric and magnetic matter properties, respectively, and conditions for the formation of repulsive potential walls are given. Both numerical and analytical results are presented.

  9. Nonlocal van der Waals functionals: the case of rare-gas dimers and solids.

    PubMed

    Tran, Fabien; Hutter, Jürg

    2013-05-28

    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)] 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)]. An analysis of the results in terms of energy decomposition is also provided. PMID:23742450

  10. Fabrication and characterization of PbSe nanostructures on van der Waals surfaces of GaSe layered semiconductor crystals

    NASA Astrophysics Data System (ADS)

    Kudrynskyi, Z. R.; Bakhtinov, A. P.; Vodopyanov, V. N.; Kovalyuk, Z. D.; Tovarnitskii, M. V.; Lytvyn, O. S.

    2015-11-01

    The growth morphology, composition and structure of PbSe nanostructures grown on the atomically smooth, clean, nanoporous and oxidized van der Waals (0001) surfaces of GaSe layered crystals were studied by means of atomic force microscopy, x-ray diffractometry, photoelectron spectroscopy and Raman spectroscopy. Semiconductor heterostructures were grown by the hot-wall technique in vacuum. Nanoporous GaSe substrates were fabricated by the thermal annealing of layered crystals in a molecular hydrogen atmosphere. The irradiation of the GaSe(0001) surface by UV radiation was used to fabricate thin Ga2O3 layers with thickness < 2 nm. It was found that the narrow gap semiconductor PbSe shows a tendency to form clusters with a square or rectangular symmetry on the clean low-energy (0001) GaSe surface, and (001)-oriented growth of PbSe thin films takes place on this surface. Using this growth technique it is possible to grow PbSe nanostructures with different morphologies: continuous epitaxial layers with thickness < 10 nm on the uncontaminated p-GaSe(0001) surfaces, homogeneous arrays of quantum dots with a high lateral density (more than 1011 cm-2) on the oxidized van der Waals (0001) surfaces and faceted square pillar-like nanostructures with a low lateral density (˜108 cm-2) on the nanoporous GaSe substrates. We exploit the ‘vapor-liquid-solid’ growth with low-melting metal (Ga) catalyst of PbSe crystalline branched nanostructures via a surface-defect-assisted mechanism.

  11. Atomically Sharp Interface in an h-BN-epitaxial graphene van der Waals Heterostructure

    PubMed Central

    Sediri, Haikel; Pierucci, Debora; Hajlaoui, Mahdi; Henck, Hugo; Patriarche, Gilles; Dappe, Yannick J.; Yuan, Sheng; Toury, Bérangère; Belkhou, Rachid; Silly, Mathieu G.; Sirotti, Fausto; Boutchich, Mohamed; Ouerghi, Abdelkarim

    2015-01-01

    Stacking various two-dimensional atomic crystals is a feasible approach to creating unique multilayered van der Waals heterostructures with tailored properties. Herein for the first time, we present a controlled preparation of large-area h-BN/graphene heterostructures via a simple chemical deposition of h-BN layers on epitaxial graphene/SiC(0001). Van der Waals forces, which are responsible for the cohesion of the multilayer system, give rise to an abrupt interface without interdiffusion between graphene and h-BN, as shown by X-ray Photoemission Spectroscopy (XPS) and direct observation using scanning and High-Resolution Transmission Electron Microscopy (STEM/HRTEM). The electronic properties of graphene, such as the Dirac cone, remain intact and no significant charge transfer i.e. doping, is observed. These results are supported by Density Functional Theory (DFT) calculations. We demonstrate that the h-BN capped graphene allows the fabrication of vdW heterostructures without altering the electronic properties of graphene. PMID:26585245

  12. Transition metals-graphene interaction: the role of the screened van der Waals energy

    NASA Astrophysics Data System (ADS)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi

    2015-03-01

    The interaction of graphene with transition metals is of particular interest for practical applications, which include for instance the efficient production of high-quality graphene. The accurate theoretical description of transition metals-graphene interfaces, however, is a particularly challenging problem due to the complex interplay between van der Waals (vdW) and hybridization effects. Here we apply the DFT/vdW-WF2s method, which allows to augment semi-local Density Functional Theory through the introduction of screened vdW interactions. Notably, we find that a reliable modeling of the van der Waals interaction should account for complex metal screening effects, that are due to the combined contributions of the p- and s-like quasi-free electrons, and the more localized d-states. The resulting geometry and energetic properties are in good agreement with experimental data and sophisticates theoretical calculations. Moreover, the Maximally Localized Wannier Functions underlying the DFT/vdW-WF2s method allow for an intuitive understanding of the complex binding mechanism.

  13. van der Waals Solids from Self-Assembled Nanoscale Building Blocks.

    PubMed

    Choi, Bonnie; Yu, Jaeeun; Paley, Daniel W; Trinh, M Tuan; Paley, Maria V; Karch, Jessica M; Crowther, Andrew C; Lee, Chul-Ho; Lalancette, Roger A; Zhu, Xiaoyang; Kim, Philip; Steigerwald, Michael L; Nuckolls, Colin; Roy, Xavier

    2016-02-10

    Traditional atomic van der Waals materials such as graphene, hexagonal boron-nitride, and transition metal dichalcogenides have received widespread attention due to the wealth of unusual physical and chemical behaviors that arise when charges, spins, and vibrations are confined to a plane. Though not as widespread as their atomic counterparts, molecule-based two-dimensional (2D) layered solids offer significant benefits; their structural flexibility will enable the development of materials with tunable properties. Here we describe a layered van der Waals solid self-assembled from a structure-directing building block and C60 fullerene. The resulting crystalline solid contains a corrugated monolayer of neutral fullerenes and can be mechanically exfoliated. The absorption spectrum of the bulk solid shows an optical gap of 390 ± 40 meV that is consistent with thermal activation energy obtained from electrical transport measurement. We find that the dimensional confinement of fullerenes significantly modulates the optical and electronic properties compared to the bulk solid. PMID:26829055

  14. Van der Waals pressure and its effect on trapped interlayer molecules

    PubMed Central

    Vasu, K. S.; Prestat, E.; Abraham, J.; Dix, J.; Kashtiban, R. J.; Beheshtian, J.; Sloan, J.; Carbone, P.; Neek-Amal, M.; Haigh, S. J.; Geim, A. K.; Nair, R. R.

    2016-01-01

    Van der Waals assembly of two-dimensional crystals continue attract intense interest due to the prospect of designing novel materials with on-demand properties. One of the unique features of this technology is the possibility of trapping molecules between two-dimensional crystals. The trapped molecules are predicted to experience pressures as high as 1 GPa. Here we report measurements of this interfacial pressure by capturing pressure-sensitive molecules and studying their structural and conformational changes. Pressures of 1.2±0.3 GPa are found using Raman spectrometry for molecular layers of 1-nm in thickness. We further show that this pressure can induce chemical reactions, and several trapped salts are found to react with water at room temperature, leading to two-dimensional crystals of the corresponding oxides. This pressure and its effect should be taken into account in studies of van der Waals heterostructures and can also be exploited to modify materials confined at the atomic interfaces. PMID:27385262

  15. Direct measurement of the van der Waals interaction between two Rydberg atoms

    NASA Astrophysics Data System (ADS)

    Browaeys, A.

    2013-05-01

    This talk will report on the direct measurement of the van der Waals interaction between two isolated, single Rydberg atoms separated by a controlled distance of a few micrometers. By working in a regime where the single-atom Rabi frequency of the laser used for excitation to the Rydberg state is comparable to the interaction energy, we observe a partial Rydberg blockade, whereby the time-dependent populations of the various two-atom states exhibit coherent oscillations with several frequencies. A quantitative comparison of the data with a simple model based on the optical Bloch equations allows us to extract the van der Waals energy, and to observe its characteristic C6 /R6 dependence. The magnitude of the measured C6 coefficient agrees well with ab-initio calculations, and we observe its dramatic increase with the principal quantum number n of the Rydberg state. Our results demonstrate a good degree of experimental control, which opens interesting perspectives in quantum information processing and quantum simulation using long-range interactions between atoms.

  16. Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

    PubMed

    He, Yongmin; Yang, Yang; Zhang, Zhuhua; Gong, Yongji; Zhou, Wu; Hu, Zhili; Ye, Gonglan; Zhang, Xiang; Bianco, Elisabeth; Lei, Sidong; Jin, Zehua; Zou, Xiaolong; Yang, Yingchao; Zhang, Yuan; Xie, Erqing; Lou, Jun; Yakobson, Boris; Vajtai, Robert; Li, Bo; Ajayan, Pulickel

    2016-05-11

    Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being particularly more sensitive to strain. This demonstration of strain engineering in van der Waals heterostructures opens a new route toward fabricating flexible electronics. PMID:27120401

  17. Band Alignment and Minigaps in Monolayer MoS2-Graphene van der Waals Heterostructures.

    PubMed

    Pierucci, Debora; Henck, Hugo; Avila, Jose; Balan, Adrian; Naylor, Carl H; Patriarche, Gilles; Dappe, Yannick J; Silly, Mathieu G; Sirotti, Fausto; Johnson, A T Charlie; Asensio, Maria C; Ouerghi, Abdelkarim

    2016-07-13

    Two-dimensional layered MoS2 shows great potential for nanoelectronic and optoelectronic devices due to its high photosensitivity, which is the result of its indirect to direct band gap transition when the bulk dimension is reduced to a single monolayer. Here, we present an exhaustive study of the band alignment and relativistic properties of a van der Waals heterostructure formed between single layers of MoS2 and graphene. A sharp, high-quality MoS2-graphene interface was obtained and characterized by micro-Raman spectroscopy, high-resolution X-ray photoemission spectroscopy (HRXPS), and scanning high-resolution transmission electron microscopy (STEM/HRTEM). Moreover, direct band structure determination of the MoS2/graphene van der Waals heterostructure monolayer was carried out using angle-resolved photoemission spectroscopy (ARPES), shedding light on essential features such as doping, Fermi velocity, hybridization, and band-offset of the low energy electronic dynamics found at the interface. We show that, close to the Fermi level, graphene exhibits a robust, almost perfect, gapless, and n-doped Dirac cone and no significant charge transfer doping is detected from MoS2 to graphene. However, modification of the graphene band structure occurs at rather larger binding energies, as the opening of several miniband-gaps is observed. These miniband-gaps resulting from the overlay of MoS2 and the graphene layer lattice impose a superperiodic potential. PMID:27281693

  18. The role of van der Waals forces in the performance of molecular diodes

    NASA Astrophysics Data System (ADS)

    Nerngchamnong, Nisachol; Yuan, Li; Qi, Dong-Chen; Li, Jiang; Thompson, Damien; Nijhuis, Christian A.

    2013-02-01

    One of the main goals of organic and molecular electronics is to relate the performance and electronic function of devices to the chemical structure and intermolecular interactions of the organic component inside them, which can take the form of an organic thin film, a self-assembled monolayer or a single molecule. This goal is difficult to achieve because organic and molecular electronic devices are complex physical-organic systems that consist of at least two electrodes, an organic component and two (different) organic/inorganic interfaces. Singling out the contribution of each of these components remains challenging. So far, strong π-π interactions have mainly been considered for the rational design and optimization of the performances of organic electronic devices, and weaker intermolecular interactions have largely been ignored. Here, we show experimentally that subtle changes in the intermolecular van der Waals interactions in the active component of a molecular diode dramatically impact the performance of the device. In particular, we observe an odd-even effect as the number of alkyl units is varied in a ferrocene-alkanethiolate self-assembled monolayer. As a result of a more favourable van der Waals interaction, junctions made from an odd number of alkyl units have a lower packing energy (by ~0.4-0.6 kcal mol-1), rectify currents 10 times more efficiently, give a 10% higher yield in working devices, and can be made two to three times more reproducibly than junctions made from an even number of alkyl units.

  19. Adsorption by design: Tuning atom-graphene van der Waals interactions via mechanical strain

    NASA Astrophysics Data System (ADS)

    Nichols, Nathan S.; Del Maestro, Adrian; Wexler, Carlos; Kotov, Valeri N.

    2016-05-01

    We aim to understand how the van der Waals force between neutral adatoms and a graphene layer is modified by uniaxial strain and electron correlation effects. A detailed analysis is presented for three atoms (He, H, and Na) and graphene strain ranging from weak to moderately strong. We show that the van der Waals potential can be significantly enhanced by strain, and present applications of our results to the problem of elastic scattering of atoms from graphene. In particular, we find that quantum reflection can be significantly suppressed by strain, meaning that dissipative inelastic effects near the surface become of increased importance. Furthermore, we introduce a method to independently estimate the Lennard-Jones parameters used in an effective model of He interacting with graphene, and determine how they depend on strain. At short distances, we find that strain tends to reduce the interaction strength by pushing the location of the adsorption potential minima to higher distances above the deformed graphene sheet. This opens up the exciting possibility of mechanically engineering an adsorption potential, with implications for the formation and observation of anisotropic low-dimensional superfluid phases.

  20. Understanding corrosion inhibition with van der Waals DFT methods: the case of benzotriazole.

    PubMed

    Gattinoni, Chiara; Michaelides, Angelos

    2015-01-01

    The corrosion of materials is an undesirable and costly process affecting many areas of technology and everyday life. As such, considerable effort has gone into understanding and preventing it. Organic molecule based coatings can in certain circumstances act as effective corrosion inhibitors. Although they have been used to great effect for more than sixty years, how they function at the atomic-level is still a matter of debate. In this work, computer simulation approaches based on density functional theory are used to investigate benzotriazole (BTAH), one of the most widely used and studied corrosion inhibitors for copper. In particular, the structures formed by protonated and deprotonated BTAH molecules on Cu(111) have been determined and linked to their inhibiting properties. It is found that hydrogen bonding, van der Waals interactions and steric repulsions all contribute in shaping how BTAH molecules adsorb, with flat-lying structures preferred at low coverage and upright configurations preferred at high coverage. The interaction of the dehydrogenated benzotriazole molecule (BTA) with the copper surface is instead dominated by strong chemisorption via the azole moiety with the aid of copper adatoms. Structures of dimers or chains are found to be the most stable structures at all coverages, in good agreement with scanning tunnelling microscopy results. Benzotriazole thus shows a complex phase behaviour in which van der Waals forces play an important role and which depends on coverage and on its protonation state and all of these factors feasibly contribute to its effectiveness as a corrosion inhibitor. PMID:25907526

  1. Elastic properties of van der Waals epitaxy grown bismuth telluride 2D nanosheets

    NASA Astrophysics Data System (ADS)

    Guo, Lingling; Yan, Haoming; Moore, Quentarius; Buettner, Michael; Song, Jinhui; Li, Lin; Araujo, Paulo T.; Wang, Hung-Ta

    2015-07-01

    Bismuth telluride (Bi2Te3) two-dimensional (2D) nanosheets prepared by van der Waals epitaxy were successfully detached, transferred, and suspended for nano-indentation measurements to be performed on freestanding circular nanosheets. The Young's modulus acquired by fitting linear elastic behaviors of 26 samples (thickness: 5-14 nm) is only 11.7-25.7 GPa, significantly smaller than the bulk in-plane Young's modulus (50-55 GPa). Compliant and robust Bi2Te3 2D nanosheets suggest the feasibility of the elastic strain engineering of topological surface states.Bismuth telluride (Bi2Te3) two-dimensional (2D) nanosheets prepared by van der Waals epitaxy were successfully detached, transferred, and suspended for nano-indentation measurements to be performed on freestanding circular nanosheets. The Young's modulus acquired by fitting linear elastic behaviors of 26 samples (thickness: 5-14 nm) is only 11.7-25.7 GPa, significantly smaller than the bulk in-plane Young's modulus (50-55 GPa). Compliant and robust Bi2Te3 2D nanosheets suggest the feasibility of the elastic strain engineering of topological surface states. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03282b

  2. Mapping van der Waals forces with frequency modulation dynamic force microscopy

    NASA Astrophysics Data System (ADS)

    Polesel-Maris, J.; Guo, H.; Zambelli, T.; Gauthier, S.

    2006-08-01

    Nanometre-size gold clusters supported on MoS2(0001) are investigated by means of ultrahigh-vacuum frequency modulation dynamic force microscopy. Topography and frequency shift images are simultaneously obtained using the average tunnelling current to regulate the tip-substrate distance. Two families of clusters are observed, giving different frequency shift images. While the topographic and frequency shift profiles have similar shapes on small clusters (size \\lesssim 1 nm), they are quite different near the top of large clusters (size \\gtrsim 4 nm): the topographic profile is rounded, but the frequency shift profile exhibits rather steep edges and a depression near the centre of the island. It is demonstrated that these differences result from the finite range of van der Waals forces. On small islands, the frequency shift is dominated by the interaction of the tip with the substrate. On large islands, it is dominated by the interaction with the island. The particular observed shape results from the geometry of the island. These interpretations are comforted by analytical and numerical calculations. In particular, the characteristic shape of the frequency shift profiles on large islands can be reproduced by introducing realistic parameters and considering only the contribution of van der Waals forces.

  3. Potential-energy surface and van der Waals motions of p-difluorobenzene-argon cation

    NASA Astrophysics Data System (ADS)

    Makarewicz, Jan

    2005-07-01

    The structure and dynamics of the van der Waals complex of argon with the p-difluorobenzene cation are investigated using the ab initio theory. The restricted open-shell Møller-Plesset second-order perturbation method combined with the augmented correlation-consistent polarized valence double-ζ basis set is employed to determine the electronic ground-state potential-energy surface of the cationic complex. This surface is extremely flat in a wide region of the configuration space of the Ar atom which moves almost freely over the monomer ring. However, it is bound to the monomer stronger in the cationic than in the neutral complex. Its binding energy is calculated to be 621cm-1 at a distance of 3.445Å from the monomer center. The calculated dissociation energy of 572cm-1 agrees perfectly with the experimental value of 572±6cm-1 [S. M. Belm, R. J. Moulds, and D. Lawrence, J. Chem. Phys. 115, 10709 (2001)]. The effect of a strong coupling of large-amplitude intermolecular motions on the character of van der Waals vibrational states is investigated. The vibrational structure of the spectrum of the complex is explained and its earlier assignment is partly corrected.

  4. Density-functional description of polymer crystals: A comparative study of recent van der Waals functionals.

    PubMed

    Pham, Thinh H; Ramprasad, Rampi; Nguyen, Huy-Viet

    2016-06-01

    Due to the lack of treatment of long-range dispersion energies, density functional theory with local and semilocal approximations of exchange-correlation energy is known to fail in describing van der Waals complexes, including polymer crystals. This limitation can be overcome by using a different class of functionals, called van der Waals density functional (vdW-DF), originally developed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. In this work, we performed a systematic study of structural properties of polymeric crystals using the original vdW-DF functional by Dion et al. and its variants and refinements. Our study shows that this class of functional outperforms the conventional LDA or PBE functionals and gives results with similar accuracy to that of empirical dispersion-corrected schemes such as DFT-D. This study suggests the use of vdW-DF2 functional - a revised version of vdW-DF functional - to obtain a high-fidelity prediction of structural and other properties of polymeric materials. PMID:27276968

  5. Microwave and ab initio studies of the Xe-CH4 van der Waals complex

    NASA Astrophysics Data System (ADS)

    Wen, Qing; Jäger, Wolfgang

    2006-01-01

    An ab initio potential-energy surface of the Xe-CH4 van der Waals complex was constructed at the coupled cluster level of theory with single, double, and perturbatively included triple excitations. The recently developed small-core pseudopotential and augmented correlation-consistent polarized valence quadruple-zeta basis set was used for the xenon atom and Dunning's augmented correlation-consistent polarized valence triple-zeta basis set for the other atoms. The basis sets were supplemented with bond functions. Dipole moments were also calculated at various configurations. Rotational spectra of the Xe-CH4 van der Waals complex were recorded using a pulsed-nozzle Fourier transform microwave spectrometer. The isotopomers studied include those of CH4,CH134,CD4,CH3D, and CHD3 with the five most abundant Xe isotopes. Transitions within three internal rotor states, namely, the j =0,K=0;j=1,K=0; and j =2,K=1 states, were observed and assigned. Nuclear quadrupole hyperfine structures due to the presence of Xe131(I=3/2) were detected and analyzed. It was found that the j =1,K=0 state is perturbed by a Coriolis interaction with a nearby j =1,K=1 state. For isotopomers containing CH3D and CHD3, the j =2 states are no longer metastable and could not be observed. The spectroscopic results were used to derive structural and dynamical information of the Xe-CH4 complex.

  6. Exciton–polaritons in van der Waals heterostructures embedded in tunable microcavities

    PubMed Central

    Dufferwiel, S.; Schwarz, S.; Withers, F.; Trichet, A. A. P.; Li, F.; Sich, M.; Del Pozo-Zamudio, O.; Clark, C.; Nalitov, A.; Solnyshkov, D. D.; Malpuech, G.; Novoselov, K. S.; Smith, J. M.; Skolnick, M. S.; Krizhanovskii, D. N.; Tartakovskii, A. I.

    2015-01-01

    Layered materials can be assembled vertically to fabricate a new class of van der Waals heterostructures a few atomic layers thick, compatible with a wide range of substrates and optoelectronic device geometries, enabling new strategies for control of light–matter coupling. Here, we incorporate molybdenum diselenide/hexagonal boron nitride (MoSe2/hBN) quantum wells in a tunable optical microcavity. Part-light–part-matter polariton eigenstates are observed as a result of the strong coupling between MoSe2 excitons and cavity photons, evidenced from a clear anticrossing between the neutral exciton and the cavity modes with a splitting of 20 meV for a single MoSe2 monolayer, enhanced to 29 meV in MoSe2/hBN/MoSe2 double-quantum wells. The splitting at resonance provides an estimate of the exciton radiative lifetime of 0.4 ps. Our results pave the way for room-temperature polaritonic devices based on multiple-quantum-well van der Waals heterostructures, where polariton condensation and electrical polariton injection through the incorporation of graphene contacts may be realized. PMID:26446783

  7. Density-functional description of polymer crystals: A comparative study of recent van der Waals functionals

    NASA Astrophysics Data System (ADS)

    Pham, Thinh H.; Ramprasad, Rampi; Nguyen, Huy-Viet

    2016-06-01

    Due to the lack of treatment of long-range dispersion energies, density functional theory with local and semilocal approximations of exchange-correlation energy is known to fail in describing van der Waals complexes, including polymer crystals. This limitation can be overcome by using a different class of functionals, called van der Waals density functional (vdW-DF), originally developed by Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)]. In this work, we performed a systematic study of structural properties of polymeric crystals using the original vdW-DF functional by Dion et al. and its variants and refinements. Our study shows that this class of functional outperforms the conventional LDA or PBE functionals and gives results with similar accuracy to that of empirical dispersion-corrected schemes such as DFT-D. This study suggests the use of vdW-DF2 functional — a revised version of vdW-DF functional — to obtain a high-fidelity prediction of structural and other properties of polymeric materials.

  8. Ab initio phonon dispersion in crystalline naphthalene using van der Waals density functionals

    NASA Astrophysics Data System (ADS)

    Brown-Altvater, Florian; Rangel, Tonatiuh; Neaton, Jeffrey B.

    2016-05-01

    Acene molecular crystals are of current interest in organic optoelectronics, both as active materials and for exploring and understanding new phenomena. Phonon scattering can be an important facilitator and dissipation mechanism in charge separation and carrier transport processes. Here, we carry out density functional theory (DFT) calculations of the structure and the full phonon dispersion of crystalline naphthalene, a well-characterized acene crystal for which detailed neutron-diffraction measurements, as well as infrared and Raman spectroscopy, are available. We evaluate the performance, relative to experiments, of DFT within the local density approximation (LDA); the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE); and a recent van der Waals-corrected nonlocal correlation (vdW-DF-cx) functional. We find that the vdW-DF-cx functional accurately predicts lattice parameters of naphthalene within 1%. Intermolecular and intramolecular phonon frequencies across the Brillouin zone are reproduced within 7.8% and 1%, respectively. As expected, LDA (PBE) underestimates (overestimates) the lattice parameters and overestimates (underestimates) phonon frequencies, demonstrating their shortcomings for predictive calculations of weakly bound materials. If the unit cell is fixed to the experimental lattice parameters, PBE is shown to lead to improved phonon frequencies. Our study provides a detailed understanding of the phonon spectrum of naphthalene, and highlights the importance of including van der Waals dispersion interactions in predictive calculations of lattice parameters and phonon frequencies of molecular crystals and related organic materials.

  9. Van der Waals force: a dominant factor for reactivity of graphene.

    PubMed

    Lee, Jong Hak; Avsar, Ahmet; Jung, Jeil; Tan, Jun You; Watanabe, K; Taniguchi, T; Natarajan, Srinivasan; Eda, Goki; Adam, Shaffique; Castro Neto, Antonio H; Özyilmaz, Barbaros

    2015-01-14

    Reactivity control of graphene is an important issue because chemical functionalization can modulate graphene's unique mechanical, optical, and electronic properties. Using systematic optical studies, we demonstrate that van der Waals interaction is the dominant factor for the chemical reactivity of graphene on two-dimensional (2D) heterostructures. A significant enhancement in the chemical stability of graphene is achieved by replacing the common SiO2 substrate with 2D crystals such as an additional graphene layer, WS2, MoS2, or h-BN. Our theoretical and experimental results show that its origin is a strong van der Waals interaction between the graphene layer and the 2D substrate. This results in a high resistive force on graphene toward geometric lattice deformation. We also demonstrate that the chemical reactivity of graphene can be controlled by the relative lattice orientation with respect to the substrates and thus can be used for a wide range of applications including hydrogen storage. PMID:25493357

  10. Key concepts from Gibbs that empowered Van der Waals, Korteweg and Kamerlingh Onnes

    NASA Astrophysics Data System (ADS)

    Levelt Sengers, Johanna

    2003-03-01

    Gibbs founded his theory of the equilibrium of heterogeneous systems (1873-1878) on the following pillars: thermodynamic stability; phase equilibrium from tangent planes rolling across thermodynamic energy surfaces; the chemical potential; degrees of freedom; the phase rule; and criticality. These concepts inspired major interdisciplinary research on mixture phase behavior in the Netherlands.(J. Levelt Sengers, How Fluids Unmix, Edita, Amsterdam (2002)) Mathematician Korteweg and physicist Van der Waals, at the University of Amsterdam, used Gibbs's geometric approach to produce the first formulation of the Helmholtz energy of binary fluid mixtures in 1891. Physicist Kamerlingh Onnes and his students at the University of Leiden studied binary mixtures experimentally, confirming Van der Waals's model, and built many 3-D models of thermodynamic surfaces. Misconceptions about criticality abounded in Europe from 1880 to 1908, provoking attacks by Kamerlingh Onnes. Between 1907 and 1913, Amsterdam chemist Bakhuis Roozeboom and his school produced an influential book series on binary and ternary, fluid and solid phase equilibria, including reacting systems.

  11. Hydrogenic Rydberg States of Molecular van der Waals Complexes: Resolved Rydberg Spectroscopy of DABCO-N2

    NASA Astrophysics Data System (ADS)

    Cockett, Martin C.; Watkins, Mark J.

    2004-01-01

    The complementary threshold ionization techniques of MATI and ZEKE spectroscopy have been used to reveal well-resolved, long-lived (>10 μs) hydrogenic Rydberg series (50≤n≤98) in a van der Waals complex formed between a polyatomic molecule and a diatomic molecule for the first time. The series are observed within 50 cm-1 of the adiabatic ionization threshold as well as two core-excited thresholds corresponding to excitation of up to two quanta in the van der Waals vibra­tional mode.

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

    SciTech Connect

    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{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

  13. 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

  14. 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

  15. Electronic Properties and Device Applications of van-der-Waals Thin Films

    NASA Astrophysics Data System (ADS)

    Renteria, Jacqueline de Dios

    Successful exfoliation of graphene and discoveries of its unique electrical and thermal properties have motivated searches for other quasi two-dimensional (2D) materials with interesting properties. The layered van der Waals materials can be cleaved mechanically or exfoliated chemically by breaking the relatively weak bonding between the layers. In this dissertation research I addressed a special group of inorganic van der Waals materials -- layered transition metal dichalcogenides (MX2, where M=Mo, W, Nb, Ta or Ti and X=S, Se or Te). The focus of the investigation was electronic properties of thin films of TaSe2 and MoS2 and their device applications. In the first part of the dissertation, I describe the fabrication and performance of all-metallic three-terminal devices with the TaSe2 thin-film conducting channel. The layers of 2H-TaSe2 were exfoliated mechanically from single crystals grown by the chemical vapor transport method. It was established that devices with nanometer-scale thickness channels exhibited strongly non-linear current-voltage characteristics, unusual optical response, and electrical gating at room temperature. It was found that the drain-source current in thin-film 2H-TaSe2--Ti/Au devices reproducibly shows an abrupt transition from a highly resistive to a conductive state, with the threshold tunable via the gate voltage. Such current-voltage characteristics can be used, in principle, for implementing radiation-hard all-metallic logic circuits. In the second part of the dissertation, I describe the fabrication, electrical testing and measurements of the low-frequency 1/f noise in three-terminal devices with the MoS2 thin-film channel (f is the frequency). Analysis of the experimental data allowed us to distinguish channel and contact noise contributions for both as fabricated and aged devices. The noise characteristics of MoS 2--Ti/Au devices are in agreement with the McWhorter model description. The latter is contrary to what is observed in

  16. Vibronic structure of the cyclopentadienyl radical and its nonrigid van der Waals cluster with nitrogen

    NASA Astrophysics Data System (ADS)

    Sun, S.; Bernstein, E. R.

    1995-09-01

    Fluorescence excitation and two color mass resolved excitation spectroscopy are employed to study the D1(2A2″)←D0(2E1″) vibronic transitions of the cyclopentadienyl radical (cpd) and its van der Waals cluster with nitrogen. The radical is created by photolysis of the cyclopentadiene dimer and cooled by expansion from a supersonic nozzle. The cpd(N2)1 cluster is generated in this cooling process. Mass resolved excitation spectra of cpd are obtained for the first 1200 cm-1 of the D1←D0 transition. The excitation spectrum of cpd(N2)1 shows a complicated structure for the origin transition. With the application of hole burning spectroscopy, we are able to assign all the cluster transitions to a single isomer. The features are assigned to a 55 cm-1 out-of-plane van der Waals mode stretch and contortional (rotational) motions of the N2 molecule with respect to the cpd radical. Empirical potential energy calculations are used to predict the properties of this cluster and yield the following results: (1) the N2 molecular axis is perpendicular to the cpd fivefold axis and parallel to the plane of the cpd ring with the two molecular centers of mass lying on the fivefold ring axis; (2) the binding energy of cpd(N2)1 is 434 cm-1; and (3) the rotational motion of the N2 molecule is essentially unhindered about the cpd fivefold axis. The molecular symmetry group D5h(MS) is applied to the nonrigid cluster, and optical selection rules exclude even↔odd transitions (Δn=0, ±2, ±4,... allowed) between the different contortional levels. Tentative assignments are given to the observed contortional features based on these considerations. The barrier to internal rotation is also small in the excited state. The results for the cpd(N2)1 van der Waals cluster are compared to those for the benzene (N2)1 and benzyl radical (N2)1 clusters.

  17. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

    DOE PAGESBeta

    Ganesh, P.; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A.; Kent, Paul R. C.

    2014-11-03

    In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based onmore » point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.« less

  18. Formation of van der Waals molecules in buffer-gas-cooled magnetic traps [corrected].

    PubMed

    Brahms, N; Tscherbul, T V; Zhang, P; Kłos, J; Sadeghpour, H R; Dalgarno, A; Doyle, J M; Walker, T G

    2010-07-16

    We predict that a large class of helium-containing cold polar molecules form readily in a cryogenic buffer gas, achieving densities as high as 10(12)  cm(-3). We explore the spin relaxation of these molecules in buffer-gas-loaded magnetic traps and identify a loss mechanism based on Landau-Zener transitions arising from the anisotropic hyperfine interaction. Our results show that the recently observed strong T(-6) thermal dependence of the spin-change rate of silver (Ag) trapped in dense (3)He is accounted for by the formation and spin change of Ag(3)He van der Waals molecules, thus providing indirect evidence for molecular formation in a buffer-gas trap. PMID:20867761

  19. Improving the Description of Nonmagnetic and Magnetic Molecular Crystals via the van der Waals Density Functional

    NASA Astrophysics Data System (ADS)

    Obata, Masao; Nakamura, Makoto; Hamada, Ikutaro; Oda, Tatsuki

    2015-02-01

    We have derived and implemented a stress tensor formulation for the van der Waals density functional (vdW-DF) with spin-polarization-dependent gradient correction (GC) recently proposed by the authors [J. Phys. Soc. Jpn. 82, 093701 (2013)] and applied it to nonmagnetic and magnetic molecular crystals under ambient condition. We found that the cell parameters of the molecular crystals obtained with vdW-DF show an overall improvement compared with those obtained using local density and generalized gradient approximations. In particular, the original vdW-DF with GC gives the equilibrium structural parameters of solid oxygen in the α-phase, which are in good agreement with the experiment.

  20. Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures

    PubMed Central

    Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M.; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J.; Li, Lain-Jong; Wallace, Robert M.; Datta, Suman; Robinson, Joshua A.

    2015-01-01

    Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2–WSe2–graphene and WSe2–MoS2–graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics. PMID:26088295

  1. Quantitative bond energetics in atomic-scale junctions with significant van der Waals character

    NASA Astrophysics Data System (ADS)

    Venkataraman, Latha; Aradhya, Sriharsha; Hybertsen, Mark

    2015-03-01

    A direct measurement of the potential energy surface that characterizes individual chemical bonds in complex materials has fundamental significance for many disciplines. Here, we demonstrate that the energy profile for metallic single-atom contacts and single-molecule junctions can be mapped by fitting ambient atomic force microscope measurements carried out in the near-equilibrium regime to a physical, but simple, functional form. In particular we are able to extract bond energies for metal-molecule link bonds in cases where the interaction has significant contribution from nonspecific interactions attributed to van der Waals (vdW) interactions at short length scale in addition to specific donor-acceptor bonds. Our approach significantly expands the quantitative information extracted from these measurements, allowing direct comparisons to density functional theory (DFT) calculations instead of relying on trends in bond rupture forces alone. Currently at Cornell University.

  2. A self-consistent GW approach to the van der Waals potential for a helium dimer.

    PubMed

    Shoji, Toru; Kuwahara, Riichi; Ono, Shota; Ohno, Kaoru

    2016-09-21

    van der Waals interaction between two helium (He) atoms is studied by calculating the total energy as a function of the He-He distance within the self-consistent GW approximation, which is expected to behave correctly in the long wavelength limit. In the Born-Oppenheimer (BO) approximation, the pair potential curve has its minimum value at 2.87 Å, which is somewhat larger than the local density approximation result, 2.40 Å, and is closer to previous quantum chemistry results. The expectation value for the interatomic distance, calculated by solving the Schrödinger equation for the two nuclei problem using the BO potential energy curve, is 30 Å, which is smaller but of the same order as previous experimental and theoretical results. PMID:27538378

  3. Probing interlayer interactions in WS2 -graphene van der Waals heterostructures

    NASA Astrophysics Data System (ADS)

    Chung, Ting Fung; Yuan, Long; Huang, Libai; Chen, Yong P.

    Two-dimensional crystals based van der Waals coupled heterostructures are of interest owing to their potential applications for flexible and transparent electronics and optoelectronics. The interaction between the 2D layered crystals at the interfaces of these heterostructures is crucial in determining the overall performance and is strongly affected by contamination and interfacial strain. We have fabricated heterostructures consisting of atomically thin exfoliated WS2 and chemical-vapor-deposited (CVD) graphene, and studied the interaction and coupling between the WS2 and graphene using atomic force microscopy (AFM), Raman spectroscopy and femtosecond transient absorption measurement (TAM). Information from Raman-active phonon modes allows us to estimate charge doping in graphene and interfacial strain on the crystals. Spatial imaging probed by TAM can be correlated to the heterostructure surface morphology measured by AFM and Raman maps of graphene and WS2, showing how the interlayer coupling alters exciton decay dynamics quantitatively.

  4. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections

    SciTech Connect

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-03-28

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μ{sub B} distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of −1.45 and 1.45 eV.

  5. Revisiting the adsorption of copper-phthalocyanine on Au(111) including van der Waals corrections.

    PubMed

    Lüder, Johann; Eriksson, Olle; Sanyal, Biplab; Brena, Barbara

    2014-03-28

    We have studied the adsorption of copper-phthalocyanine on Au(111) by means of van der Waals corrected density functional theory using the Tkatchenko-Scheffler method. We have compared the element and site resolved adsorption distances to recent experimental normal-incident X-ray standing wave measurements. The measured adsorption distances could be reproduced within a deviation of 1% for the Cu atom, 1% for the C atoms, and 2% for the N atoms. The molecule was found to have a magnetic moment of 1 μB distributed over the Cu and the N atoms of the pyrrole ring. Simulated scanning tunnel microscopy images based on the total and on the spin-resolved differential charge densities are provided for bias voltages of -1.45 and 1.45 eV. PMID:24697474

  6. Communication: Multiple-property-based diabatization for open-shell van der Waals molecules

    NASA Astrophysics Data System (ADS)

    Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C.

    2016-03-01

    We derive a new multiple-property-based diabatization algorithm. The transformation between adiabatic and diabatic representations is determined by requiring a set of properties in both representations to be related by a similarity transformation. This set of properties is determined in the adiabatic representation by rigorous electronic structure calculations. In the diabatic representation, the same properties are determined using model diabatic states defined as products of undistorted monomer wave functions. This diabatic model is generally applicable to van der Waals molecules in arbitrary electronic states. Application to locating seams of conical intersections and collisional transfer of electronic excitation energy is demonstrated for O2 - O2 in low-lying excited states. Property-based diabatization for this test system included all components of the electric quadrupole tensor, orbital angular momentum, and spin-orbit coupling.

  7. Quantum defect theory for the van der Waals plus dipole-dipole interaction

    NASA Astrophysics Data System (ADS)

    Wang, Gao-Ren; Xie, Ting; Huang, Yin; Zhang, Wei; Cong, Shu-Lin

    2012-12-01

    We investigate the scattering dynamics governed by the long-range van der Waals plus dipole-dipole interaction potential, -C6/R6-C3/R3, which describes the long-range interaction between two polar molecules in an electric field. In the spirit of quantum defect theory, a set of parameters which are nearly constants in the threshold regime is defined to characterize the scattering process. Using appropriate boundary conditions for the scattering wave functions and relevant parameters, we explore the quantum reflection by and quantum tunneling through the long-range potential. As a sample application, the reactive collision rates of 40K87Rb + 40K87Rb are calculated.

  8. Causality, universality, and effective field theory for van der Waals interactions

    NASA Astrophysics Data System (ADS)

    Elhatisari, Serdar; König, Sebastian; Lee, Dean; Hammer, H.-W.

    2013-05-01

    We analyze low-energy scattering for arbitrary short-range interactions plus an attractive 1/r6 tail. We derive the constraints of causality and unitarity and find that the van der Waals length scale dominates over parameters characterizing the short-distance physics of the interaction. This separation of scales suggests a separate universality class for physics characterizing interactions with an attractive 1/r6 tail. We argue that a similar universality class exists for any attractive potential 1/rα for α⩾2. We also discuss the extension to multichannel systems near a magnetic Feshbach resonance. We discuss the implications for effective field theory with attractive singular power-law tails.

  9. An application of the van der Waals density functional: Hydrogen bonding and stacking interactions between nucleobases.

    PubMed

    Cooper, Valentino R; Thonhauser, T; Langreth, David C

    2008-05-28

    We apply the van der Waals density functional (vdW-DF) to study hydrogen bonding and stacking interactions between nucleobases. The excellent agreement of our results with high level quantum chemical calculations highlights the value of the vdW-DF for first-principles investigations of biologically important molecules. Our results suggest that, in the case of hydrogen-bonded nucleobase pairs, dispersion interactions reduce the cost of propeller twists while having a negligible effect on buckling. Furthermore, the efficient scaling of DFT methods allowed for the easy optimization of separation distance between nucleobase stacks, indicating enhancements in the interaction energy of up to 3 kcalmol over previous fixed distance calculations. We anticipate that these results are significant for extending the vdW-DF method to model larger vdW complexes and biological molecules. PMID:18513005

  10. A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111).

    PubMed

    Mete, Ersen; Yılmaz, Ayşen; Danışman, Mehmet Fatih

    2016-05-14

    Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated with different molecules show a correlation with their dipole moments. The adsorption is favored for the isomers with dipole moments parallel to the surface. Of the two possible unit cell structures, (5 × 5) was found to be more stable than . PMID:27108565