Thermodynamically constrained correction to ab initio equations of state

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

French, Martin; Mattsson, Thomas R.

2014-07-07

We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence ofmore » the exchange-correlation functional used.« less

Density-functional energy gaps of solids demystified

NASA Astrophysics Data System (ADS)

Perdew, John P.; Ruzsinszky, Adrienn

2018-06-01

The fundamental energy gap of a solid is a ground-state second energy difference. Can one find the fundamental gap from the gap in the band structure of Kohn-Sham density functional theory? An argument of Williams and von Barth (WB), 1983, suggests that one can. In fact, self-consistent band-structure calculations within the local density approximation or the generalized gradient approximation (GGA) yield the fundamental gap within the same approximation for the energy. Such a calculation with the exact density functional would yield a band gap that also underestimates the fundamental gap, because the exact Kohn-Sham potential in a solid jumps up by an additive constant when one electron is added, and the WB argument does not take this effect into account. The WB argument has been extended recently to generalized Kohn-Sham theory, the simplest way to implement meta-GGAs and hybrid functionals self-consistently, with an exchange-correlation potential that is a non-multiplication operator. Since this operator is continuous, the band gap is again the fundamental gap within the same approximation, but, because the approximations are more realistic, so is the band gap. What approximations might be even more realistic?

Local thermodynamic mapping for effective liquid density-functional theory

NASA Technical Reports Server (NTRS)

Kyrlidis, Agathagelos; Brown, Robert A.

1992-01-01

The structural-mapping approximation introduced by Lutsko and Baus (1990) in the generalized effective-liquid approximation is extended to include a local thermodynamic mapping based on a spatially dependent effective density for approximating the solid phase in terms of the uniform liquid. This latter approximation, called the local generalized effective-liquid approximation (LGELA) yields excellent predictions for the free energy of hard-sphere solids and for the conditions of coexistence of a hard-sphere fcc solid with a liquid. Moreover, the predicted free energy remains single valued for calculations with more loosely packed crystalline structures, such as the diamond lattice. The spatial dependence of the weighted density makes the LGELA useful in the study of inhomogeneous solids.

Thermal radiative and thermodynamic properties of solid and liquid uranium and plutonium carbides in the visible-near-infrared range

NASA Astrophysics Data System (ADS)

Fisenko, Anatoliy I.; Lemberg, Vladimir F.

2016-09-01

The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these functions have not been established for plutonium carbide. The calculated values for the normal total emissivity of uranium and plutonium carbides at their melting temperatures is in good agreement with experimental data. The obtained results allow to calculate the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides for any size of samples. Based on the model of Hagen-Rubens and the Wiedemann-Franz law, a new method to determine the thermal conductivity of metals and carbides at the melting points is proposed.

Atomic kinetic energy, momentum distribution, and structure of solid neon at zero temperature

NASA Astrophysics Data System (ADS)

Cazorla, C.; Boronat, J.

2008-01-01

We report on the calculation of the ground-state atomic kinetic energy Ek and momentum distribution of solid Ne by means of the diffusion Monte Carlo method and Aziz HFD-B pair potential. This approach is shown to perform notably for this crystal since we obtain very good agreement with respect to experimental thermodynamic data. Additionally, we study the structural properties of solid Ne at densities near the equilibrium by estimating the radial pair-distribution function, Lindemann’s ratio, and atomic density profile around the positions of the perfect crystalline lattice. Our value for Ek at the equilibrium density is 41.51(6)K , which agrees perfectly with the recent prediction made by Timms , 41(2)K , based on their deep-inelastic neutron scattering experiments carried out over the temperature range 4-20K , and also with previous path integral Monte Carlo results obtained with the Lennard-Jones and Aziz HFD-C2 atomic pairwise interactions. The one-body density function of solid Ne is calculated accurately and found to fit perfectly, within statistical uncertainty, to a Gaussian curve. Furthermore, we analyze the degree of anharmonicity of solid Ne by calculating some of its microscopic ground-state properties within traditional harmonic approaches. We provide insightful comparison to solid He4 in terms of the Debye model in order to assess the relevance of anharmonic effects in Ne.

Contact angle of sessile drops in Lennard-Jones systems.

PubMed

Becker, Stefan; Urbassek, Herbert M; Horsch, Martin; Hasse, Hans

2014-11-18

Molecular dynamics simulations are used for studying the contact angle of nanoscale sessile drops on a planar solid wall in a system interacting via the truncated and shifted Lennard-Jones potential. The entire range between total wetting and dewetting is investigated by varying the solid-fluid dispersive interaction energy. The temperature is varied between the triple point and the critical temperature. A correlation is obtained for the contact angle in dependence of the temperature and the dispersive interaction energy. Size effects are studied by varying the number of fluid particles at otherwise constant conditions, using up to 150,000 particles. For particle numbers below 10,000, a decrease of the contact angle is found. This is attributed to a dependence of the solid-liquid surface tension on the droplet size. A convergence to a constant contact angle is observed for larger system sizes. The influence of the wall model is studied by varying the density of the wall. The effective solid-fluid dispersive interaction energy at a contact angle of θ = 90° is found to be independent of temperature and to decrease linearly with the solid density. A correlation is developed that describes the contact angle as a function of the dispersive interaction, the temperature, and the solid density. The density profile of the sessile drop and the surrounding vapor phase is described by a correlation combining a sigmoidal function and an oscillation term.

Recent developments in LIBXC - A comprehensive library of functionals for density functional theory

NASA Astrophysics Data System (ADS)

Lehtola, Susi; Steigemann, Conrad; Oliveira, Micael J. T.; Marques, Miguel A. L.

2018-01-01

LIBXC is a library of exchange-correlation functionals for density-functional theory. We are concerned with semi-local functionals (or the semi-local part of hybrid functionals), namely local-density approximations, generalized-gradient approximations, and meta-generalized-gradient approximations. Currently we include around 400 functionals for the exchange, correlation, and the kinetic energy, spanning more than 50 years of research. Moreover, LIBXC is by now used by more than 20 codes, not only from the atomic, molecular, and solid-state physics, but also from the quantum chemistry communities.

Controlled functionalization of carbonaceous fibers for asymmetric solid-state micro-supercapacitors with high volumetric energy density.

PubMed

Yu, Dingshan; Goh, Kunli; Zhang, Qiang; Wei, Li; Wang, Hong; Jiang, Wenchao; Chen, Yuan

2014-10-22

A 1.8 V asymmetric solid-state flexible micro-supercapacitor is designed with one MnO2 -coated reduced graphene oxide/single-walled carbon nanotube (rGO/SWCNT) composite fiber as positive electrode and one nitrogen-doped rGO/SWCNT fiber as negative electrode, which demonstrates ultrahigh volumetric energy density, comparable to some thin-film lithium batteries, along with high power density, long cycle life, and good flexibility. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding band gaps of solids in generalized Kohn-Sham theory.

PubMed

Perdew, John P; Yang, Weitao; Burke, Kieron; Yang, Zenghui; Gross, Eberhard K U; Scheffler, Matthias; Scuseria, Gustavo E; Henderson, Thomas M; Zhang, Igor Ying; Ruzsinszky, Adrienn; Peng, Haowei; Sun, Jianwei; Trushin, Egor; Görling, Andreas

2017-03-14

The fundamental energy gap of a periodic solid distinguishes insulators from metals and characterizes low-energy single-electron excitations. However, the gap in the band structure of the exact multiplicative Kohn-Sham (KS) potential substantially underestimates the fundamental gap, a major limitation of KS density-functional theory. Here, we give a simple proof of a theorem: In generalized KS theory (GKS), the band gap of an extended system equals the fundamental gap for the approximate functional if the GKS potential operator is continuous and the density change is delocalized when an electron or hole is added. Our theorem explains how GKS band gaps from metageneralized gradient approximations (meta-GGAs) and hybrid functionals can be more realistic than those from GGAs or even from the exact KS potential. The theorem also follows from earlier work. The band edges in the GKS one-electron spectrum are also related to measurable energies. A linear chain of hydrogen molecules, solid aluminum arsenide, and solid argon provide numerical illustrations.

Understanding band gaps of solids in generalized Kohn–Sham theory

PubMed Central

Perdew, John P.; Yang, Weitao; Burke, Kieron; Yang, Zenghui; Gross, Eberhard K. U.; Scheffler, Matthias; Scuseria, Gustavo E.; Henderson, Thomas M.; Zhang, Igor Ying; Ruzsinszky, Adrienn; Peng, Haowei; Sun, Jianwei; Trushin, Egor; Görling, Andreas

2017-01-01

The fundamental energy gap of a periodic solid distinguishes insulators from metals and characterizes low-energy single-electron excitations. However, the gap in the band structure of the exact multiplicative Kohn–Sham (KS) potential substantially underestimates the fundamental gap, a major limitation of KS density-functional theory. Here, we give a simple proof of a theorem: In generalized KS theory (GKS), the band gap of an extended system equals the fundamental gap for the approximate functional if the GKS potential operator is continuous and the density change is delocalized when an electron or hole is added. Our theorem explains how GKS band gaps from metageneralized gradient approximations (meta-GGAs) and hybrid functionals can be more realistic than those from GGAs or even from the exact KS potential. The theorem also follows from earlier work. The band edges in the GKS one-electron spectrum are also related to measurable energies. A linear chain of hydrogen molecules, solid aluminum arsenide, and solid argon provide numerical illustrations. PMID:28265085

Hydrogen slush density reference system

NASA Technical Reports Server (NTRS)

Weitzel, D. H.; Lowe, L. T.; Ellerbruch, D. A.; Cruz, J. E.; Sindt, C. F.

1971-01-01

A hydrogen slush density reference system was designed for calibration of field-type instruments and/or transfer standards. The device is based on the buoyancy principle of Archimedes. The solids are weighed in a low-mass container so arranged that solids and container are buoyed by triple-point liquid hydrogen during the weighing process. Several types of hydrogen slush density transducers were developed and tested for possible use as transfer standards. The most successful transducers found were those which depend on change in dielectric constant, after which the Clausius-Mossotti function is used to relate dielectric constant and density.

Highly Accurate Calculations of the Phase Diagram of Cold Lithium

NASA Astrophysics Data System (ADS)

Shulenburger, Luke; Baczewski, Andrew

The phase diagram of lithium is particularly complicated, exhibiting many different solid phases under the modest application of pressure. Experimental efforts to identify these phases using diamond anvil cells have been complemented by ab initio theory, primarily using density functional theory (DFT). Due to the multiplicity of crystal structures whose enthalpy is nearly degenerate and the uncertainty introduced by density functional approximations, we apply the highly accurate many-body diffusion Monte Carlo (DMC) method to the study of the solid phases at low temperature. These calculations span many different phases, including several with low symmetry, demonstrating the viability of DMC as a method for calculating phase diagrams for complex solids. Our results can be used as a benchmark to test the accuracy of various density functionals. This can strengthen confidence in DFT based predictions of more complex phenomena such as the anomalous melting behavior predicted for lithium at high pressures. Sandia National Laboratories is a multi-program 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 DE-AC04-94AL85000.

Ab initio approach to the ion stopping power at the plasma-solid interface

NASA Astrophysics Data System (ADS)

Bonitz, Michael; Schlünzen, Niclas; Wulff, Lasse; Joost, Jan-Philip; Balzer, Karsten

2016-10-01

The energy loss of ions in solids is of key relevance for many applications of plasmas, ranging from plasma technology to fusion. Standard approaches are based on density functional theory or SRIM simulations, however, the applicability range and accuracy of these results are difficult to assess, in particular, for low energies. Here we present an independent approach that is based on ab initio nonequilibrium Green functions theory, e.g. that allows to incorporate electronic correlations effects of the solid. We present the first application of this method to low-temperature plasmas, concentrating on proton and alpha-particle stopping in a graphene layer. In addition to the stopping power we present time-dependent results for the local electron density, the spectral function and the photoemission spectrum that is directly accessible in optical, UV or x-ray diagnostics. http://www.itap.uni-kiel.de/theo-physik/bonitz/.

Solid harmonic wavelet scattering for predictions of molecule properties

NASA Astrophysics Data System (ADS)

Eickenberg, Michael; Exarchakis, Georgios; Hirn, Matthew; Mallat, Stéphane; Thiry, Louis

2018-06-01

We present a machine learning algorithm for the prediction of molecule properties inspired by ideas from density functional theory (DFT). Using Gaussian-type orbital functions, we create surrogate electronic densities of the molecule from which we compute invariant "solid harmonic scattering coefficients" that account for different types of interactions at different scales. Multilinear regressions of various physical properties of molecules are computed from these invariant coefficients. Numerical experiments show that these regressions have near state-of-the-art performance, even with relatively few training examples. Predictions over small sets of scattering coefficients can reach a DFT precision while being interpretable.

Evaluate the ability of PVP to inhibit crystallization of amorphous solid dispersions by density functional theory and experimental verify.

PubMed

Wang, Bing; Wang, Dandan; Zhao, Shan; Huang, Xiaobin; Zhang, Jianbin; Lv, Yan; Liu, Xiaocen; Lv, Guojun; Ma, Xiaojun

2017-01-01

In this study, we used density functional theory (DFT) to predict polymer-drug interactions, and then evaluated the ability of poly (vinyl pyrrolidone) (PVP) to inhibit crystallization of amorphous solid dispersions by experimental-verification. Solid dispersions of PVP/resveratrol (Res) and PVP/griseofulvin (Gri) were adopted for evaluating the ability of PVP to inhibit crystallization. The density functional theory (DFT) with the B3LYP was used to calculate polymer-drug and drug-drug interactions. Fourier transform infrared spectroscopy (FTIR) was used to confirm hydrogen bonding interactions. Polymer-drug miscibility and drug crystallinity were characterized by the modulated differential scanning calorimetry (MDSC) and X-ray powder diffraction (XRD). The release profiles were studied to investigate the dissolution advantage. DFT results indicated that E PVP-Res >E Res-Res (E: represents hydrogen bonding energy). A strong interaction was formed between PVP and Res. In addition, Fourier transform infrared spectroscopy (FTIR) analysis showed hydrogen bonding formed between PVP and Res, but not between PVP and Gri. MDSC and XRD results suggested that 70-90wt% PVP/Res and PVP/Gri solid dispersions formed amorphous solid dispersions (ASDs). Under the accelerated testing condition, PVP/Res dispersions with higher miscibility quantified as 90/10wt% were more stable than PVP/Gri dispersions. The cumulative dissolution rate of 90wt% PVP/Res dispersions still kept high after 90days storage due to the strong interaction. However, the cumulative dissolution rate of PVP/Gri solid dispersions significantly dropped because of the recrystallization of Gri. Copyright © 2016 Elsevier B.V. All rights reserved.

Freezing of soft spheres: A critical test for weighted-density-functional theories

NASA Astrophysics Data System (ADS)

Laird, Brian B.; Kroll, D. M.

1990-10-01

We study the freezing properties of systems with inverse-power and Yukawa interactions (soft spheres), using recently developed weighted-density-functional theories. We find that the modified weighted-density-functional approximation (MWDA) of Denton and Ashcroft yields results for the liquid to face-centered-cubic (fcc) structure transition that represent a significant improvement over those of earlier ``second-order'' density-functional freezing theories; however, this theory, like the earlier ones, fails to predict any liquid to body-centered-cubic (bcc) transition, even under conditions where the computer simulations indicate that this should be the equilibrium solid structure. In addition, we show that both the modified effective-liquid approximation (MELA) of Baus [J. Phys. Condens. Matter 2, 2111 (1990)] and the generalized effective-liquid approximation of Lutsko and Baus [Phys. Rev. Lett. 64, 761 (1990)], while giving excellent results for the freezing of hard spheres, fail completely to predict freezing into either fcc or bcc solid phases for soft inverse-power potentials. We also give an alternate derivation of the MWDA that makes clearer its connection to earlier theories.

Semiclassical neutral atom as a reference system in density functional theory.

PubMed

Constantin, Lucian A; Fabiano, E; Laricchia, S; Della Sala, F

2011-05-06

We use the asymptotic expansions of the semiclassical neutral atom as a reference system in density functional theory to construct accurate generalized gradient approximations (GGAs) for the exchange-correlation and kinetic energies without any empiricism. These asymptotic functionals are among the most accurate GGAs for molecular systems, perform well for solid state, and overcome current GGA state of the art in frozen density embedding calculations. Our results also provide evidence for the conjointness conjecture between exchange and kinetic energies of atomic systems.

Structural and vibrational properties of solid nitromethane under high pressure by density functional theory.

PubMed

Liu, Hong; Zhao, Jijun; Wei, Dongqing; Gong, Zizheng

2006-03-28

The structural, vibrational, and electronic properties of solid nitromethane under hydrostatic pressure of up to 20 GPa have been studied using density functional theory. The changes of cell volume, the lattice constants, and the molecular geometry of solid nitromethane under hydrostatic loading are examined, and the bulk modulus B0 and its pressure derivative B0' are fitted from the volume-pressure relation. Our theoretical results are compared with available experiments. The change of electron band gap of nitromethane under high pressure is also discussed. Based on the optimized crystal structures, the vibrational frequencies for the internal and lattice modes of the nitromethane crystal at ambient and high pressures are computed, and the pressure-induced frequency shifts of these modes are discussed.

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework.

PubMed

Berger, Daniel; Logsdail, Andrew J; Oberhofer, Harald; Farrow, Matthew R; Catlow, C Richard A; Sherwood, Paul; Sokol, Alexey A; Blum, Volker; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capability by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO2(110).

Embedded-cluster calculations in a numeric atomic orbital density-functional theory framework

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

Berger, Daniel, E-mail: daniel.berger@ch.tum.de; Oberhofer, Harald; Reuter, Karsten

2014-07-14

We integrate the all-electron electronic structure code FHI-aims into the general ChemShell package for solid-state embedding quantum and molecular mechanical (QM/MM) calculations. A major undertaking in this integration is the implementation of pseudopotential functionality into FHI-aims to describe cations at the QM/MM boundary through effective core potentials and therewith prevent spurious overpolarization of the electronic density. Based on numeric atomic orbital basis sets, FHI-aims offers particularly efficient access to exact exchange and second order perturbation theory, rendering the established QM/MM setup an ideal tool for hybrid and double-hybrid level density functional theory calculations of solid systems. We illustrate this capabilitymore » by calculating the reduction potential of Fe in the Fe-substituted ZSM-5 zeolitic framework and the reaction energy profile for (photo-)catalytic water oxidation at TiO{sub 2}(110)« less

Density functional theory investigation of the LiIn 1-xGa xSe 2 solid solution

DOE PAGES

Wiggins, Brenden; Batista, Enrique; Burger, Arnold; ...

2016-06-07

Here, the electronic structure and optical properties of the LiIn 1-xGa xSe 2 (x=0, 0.25, 0.5, 0.75, 1) solid solution were studied by density functional theory (DFT) with pure functionals. The exchange-correlation is treated within the local density approximation (LDA) and generalized-gradient approximation (GGA). The electronic structures for each respective compound are discussed in detail. Calculations reveal that gallium incorporation can be used to tune the optical-electrical properties of the solid solution and correlates with the lattice parameter. The band gap trend of the LiIn 1-xGa xSe 2 system follows a nonlinear behavior between the LiInSe 2 and LiGaSe 2more » ternary boundaries. The bowing parameter is estimated to be on the order of 0.1- 0.3 eV at the point. Low-temperature optical absorption revealed a 30% change in the temperature dependence of the band gap for the intermediate compound LiIn 0.6Ga 0.4Se 2 compared to ternary boundaries and suggests the heat capacity to be another control element through strain.« less

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

PubMed

Boehme, Simon C; Azpiroz, Jon Mikel; Aulin, Yaroslav V; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Infante, Ivan; Houtepen, Arjan J

2015-05-13

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Measurements of the K -Shell Opacity of a Solid-Density Magnesium Plasma Heated by an X-Ray Free-Electron Laser

DOE PAGES

Preston, T. R.; Vinko, S. M.; Ciricosta, O.; ...

2017-08-25

We present measurements of the spectrally resolved x rays emitted from solid-density magnesium targets of varying sub-μm thicknesses isochorically heated by an x-ray laser. The data exhibit a largely thickness independent source function, allowing the extraction of a measure of the opacity to K-shell x rays within well-defined regimes of electron density and temperature, extremely close to local thermodynamic equilibrium conditions. The deduced opacities at the peak of the Kα transitions of the ions are consistent with those predicted by detailed atomic-kinetics calculations.

Revisiting ignited-quenched transition and the non-Newtonian rheology of a sheared dilute gas-solid suspension

NASA Astrophysics Data System (ADS)

Saha, Saikat; Alam, Meheboob

2017-12-01

The hydrodynamics and rheology of a sheared dilute gas-solid suspension, consisting of inelastic hard-spheres suspended in a gas, are analysed using anisotropic Maxwellian as the single particle distribution function. The closed-form solutions for granular temperature and three invariants of the second-moment tensor are obtained as functions of the Stokes number ($St$), the mean density ($\

Molecularly Engineered Azobenzene Derivatives for High Energy Density Solid-State Solar Thermal Fuels.

PubMed

Cho, Eugene N; Zhitomirsky, David; Han, Grace G D; Liu, Yun; Grossman, Jeffrey C

2017-03-15

Solar thermal fuels (STFs) harvest and store solar energy in a closed cycle system through conformational change of molecules and can release the energy in the form of heat on demand. With the aim of developing tunable and optimized STFs for solid-state applications, we designed three azobenzene derivatives functionalized with bulky aromatic groups (phenyl, biphenyl, and tert-butyl phenyl groups). In contrast to pristine azobenzene, which crystallizes and makes nonuniform films, the bulky azobenzene derivatives formed uniform amorphous films that can be charged and discharged with light and heat for many cycles. Thermal stability of the films, a critical metric for thermally triggerable STFs, was greatly increased by the bulky functionalization (up to 180 °C), and we were able to achieve record high energy density of 135 J/g for solid-state STFs, over a 30% improvement compared to previous solid-state reports. Furthermore, the chargeability in the solid state was improved, up to 80% charged from 40% charged in previous solid-state reports. Our results point toward molecular engineering as an effective method to increase energy storage in STFs, improve chargeability, and improve the thermal stability of the thin film.

Investigating tautomeric polymorphism in crystalline anthranilic acid using terahertz spectroscopy and solid-state density functional theory.

PubMed

Delaney, Sean P; Witko, Ewelina M; Smith, Tiffany M; Korter, Timothy M

2012-08-02

Terahertz spectroscopy is sensitive to the interactions between molecules in the solid-state and recently has emerged as a new analytical tool for investigating polymorphism. Here, this technique is applied for the first time to the phenomenon of tautomeric polymorphism where the crystal structures of anthranilic acid (2-aminobenzoic acid) have been investigated. Three polymorphs of anthranilic acid (denoted Forms I, II and III) were studied using terahertz spectroscopy and the vibrational modes and relative polymorph stabilities analyzed using solid-state density functional theory calculations augmented with London dispersion force corrections. Form I consists of both neutral and zwitterionic molecules and was found to be the most stable polymorph as compared to Forms II and III (both containing only neutral molecules). The simulations suggest that a balance between steric interactions and electrostatic forces is responsible for the favoring of the mixed neutral/zwitterion solid over the all neutral or all zwitterion crystalline arrangements.

Effective model hierarchies for dynamic and static classical density functional theories

NASA Astrophysics Data System (ADS)

Majaniemi, S.; Provatas, N.; Nonomura, M.

2010-09-01

The origin and methodology of deriving effective model hierarchies are presented with applications to solidification of crystalline solids. In particular, it is discussed how the form of the equations of motion and the effective parameters on larger scales can be obtained from the more microscopic models. It will be shown that tying together the dynamic structure of the projection operator formalism with static classical density functional theories can lead to incomplete (mass) transport properties even though the linearized hydrodynamics on large scales is correctly reproduced. To facilitate a more natural way of binding together the dynamics of the macrovariables and classical density functional theory, a dynamic generalization of density functional theory based on the nonequilibrium generating functional is suggested.

Morphology and linear-elastic moduli of random network solids.

PubMed

Nachtrab, Susan; Kapfer, Sebastian C; Arns, Christoph H; Madadi, Mahyar; Mecke, Klaus; Schröder-Turk, Gerd E

2011-06-17

The effective linear-elastic moduli of disordered network solids are analyzed by voxel-based finite element calculations. We analyze network solids given by Poisson-Voronoi processes and by the structure of collagen fiber networks imaged by confocal microscopy. The solid volume fraction ϕ is varied by adjusting the fiber radius, while keeping the structural mesh or pore size of the underlying network fixed. For intermediate ϕ, the bulk and shear modulus are approximated by empirical power-laws K(phi)proptophin and G(phi)proptophim with n≈1.4 and m≈1.7. The exponents for the collagen and the Poisson-Voronoi network solids are similar, and are close to the values n=1.22 and m=2.11 found in a previous voxel-based finite element study of Poisson-Voronoi systems with different boundary conditions. However, the exponents of these empirical power-laws are at odds with the analytic values of n=1 and m=2, valid for low-density cellular structures in the limit of thin beams. We propose a functional form for K(ϕ) that models the cross-over from a power-law at low densities to a porous solid at high densities; a fit of the data to this functional form yields the asymptotic exponent n≈1.00, as expected. Further, both the intensity of the Poisson-Voronoi process and the collagen concentration in the samples, both of which alter the typical pore or mesh size, affect the effective moduli only by the resulting change of the solid volume fraction. These findings suggest that a network solid with the structure of the collagen networks can be modeled in quantitative agreement by a Poisson-Voronoi process. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inelastic neutron scattering spectrum of cyclotrimethylenetrinitramine: a comparison with solid-state electronic structure calculations.

PubMed

Ciezak, Jennifer A; Trevino, S F

2006-04-20

Solid-state geometry optimizations and corresponding normal-mode analysis of the widely used energetic material cyclotrimethylenetrinitramine (RDX) were performed using density functional theory with both the generalized gradient approximation (BLYP and BP functionals) and the local density approximation (PWC and VWN functionals). The structural results were found to be in good agreement with experimental neutron diffraction data and previously reported calculations based on the isolated-molecule approximation. The vibrational inelastic neutron scattering (INS) spectrum of polycrystalline RDX was measured and compared with simulated INS constructed from the solid-state calculations. The vibrational frequencies calculated from the solid-state methods had average deviations of 10 cm(-1) or less, whereas previously published frequencies based on an isolated-molecule approximation had deviations of 65 cm(-1) or less, illustrating the importance of including crystalline forces. On the basis of the calculations and analysis, it was possible to assign the normal modes and symmetries, which agree well with previous assignments. Four possible "doorway modes" were found in the energy range defined by the lattice modes, which were all found to contain fundamental contributions from rotation of the nitro groups.

Ginzburg-Landau theory for the solid-liquid interface of bcc elements. II - Application to the classical one-component plasma, the Wigner crystal, and He-4

NASA Technical Reports Server (NTRS)

Zeng, X. C.; Stroud, D.

1989-01-01

The previously developed Ginzburg-Landau theory for calculating the crystal-melt interfacial tension of bcc elements to treat the classical one-component plasma (OCP), the charged fermion system, and the Bose crystal. For the OCP, a direct application of the theory of Shih et al. (1987) yields for the surface tension 0.0012(Z-squared e-squared/a-cubed), where Ze is the ionic charge and a is the radius of the ionic sphere. Bose crystal-melt interface is treated by a quantum extension of the classical density-functional theory, using the Feynman formalism to estimate the relevant correlation functions. The theory is applied to the metastable He-4 solid-superfluid interface at T = 0, with a resulting surface tension of 0.085 erg/sq cm, in reasonable agreement with the value extrapolated from the measured surface tension of the bcc solid in the range 1.46-1.76 K. These results suggest that the density-functional approach is a satisfactory mean-field theory for estimating the equilibrium properties of liquid-solid interfaces, given knowledge of the uniform phases.

Prediction of crosslink density of solid propellant binders. [curing of elastomers

NASA Technical Reports Server (NTRS)

Marsh, H. E., Jr.

1976-01-01

A quantitative theory is outlined which allows calculation of crosslink density of solid propellant binders from a small number of predetermined parameters such as the binder composition, the functionality distributions of the ingredients, and the extent of the curing reaction. The parameter which is partly dependent on process conditions is the extent of reaction. The proposed theoretical model is verified by independent measurement of effective chain concentration and sol and gel fractions in simple compositions prepared from model compounds. The model is shown to correlate tensile data with composition in the case of urethane-cured polyether and certain solid propellants. A formula for the branching coefficient is provided according to which if one knows the functionality distributions of the ingredients and the corresponding equivalent weights and can measure or predict the extent of reaction, he can calculate the branching coefficient of such a system for any desired composition.

Many-body perturbation theory using the density-functional concept: beyond the GW approximation.

PubMed

Bruneval, Fabien; Sottile, Francesco; Olevano, Valerio; Del Sole, Rodolfo; Reining, Lucia

2005-05-13

We propose an alternative formulation of many-body perturbation theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, which leads to excellent optical absorption and energy-loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-dependent density-functional theory. Numerical results for the band gap of bulk silicon and solid argon illustrate corrections beyond the GW approximation for the self-energy.

Density Functionals of Chemical Bonding

PubMed Central

Putz, Mihai V.

2008-01-01

The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

PubMed

Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

2015-05-20

A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids.

PubMed

Yu, Haoyu S; He, Xiao; Truhlar, Donald G

2016-03-08

Kohn-Sham density functional theory is widely used for applications of electronic structure theory in chemistry, materials science, and condensed-matter physics, but the accuracy depends on the quality of the exchange-correlation functional. Here, we present a new local exchange-correlation functional called MN15-L that predicts accurate results for a broad range of molecular and solid-state properties including main-group bond energies, transition metal bond energies, reaction barrier heights, noncovalent interactions, atomic excitation energies, ionization potentials, electron affinities, total atomic energies, hydrocarbon thermochemistry, and lattice constants of solids. The MN15-L functional has the same mathematical form as a previous meta-nonseparable gradient approximation exchange-correlation functional, MN12-L, but it is improved because we optimized it against a larger database, designated 2015A, and included smoothness restraints; the optimization has a much better representation of transition metals. The mean unsigned error on 422 chemical energies is 2.32 kcal/mol, which is the best among all tested functionals, with or without nonlocal exchange. The MN15-L functional also provides good results for test sets that are outside the training set. A key issue is that the functional is local (no nonlocal exchange or nonlocal correlation), which makes it relatively economical for treating large and complex systems and solids. Another key advantage is that medium-range correlation energy is built in so that one does not need to add damped dispersion by molecular mechanics in order to predict accurate noncovalent binding energies. We believe that the MN15-L functional should be useful for a wide variety of applications in chemistry, physics, materials science, and molecular biology.

Density functional theory in the solid state

PubMed Central

Hasnip, Philip J.; Refson, Keith; Probert, Matt I. J.; Yates, Jonathan R.; Clark, Stewart J.; Pickard, Chris J.

2014-01-01

Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program. PMID:24516184

Enhanced NMR Discrimination of Pharmaceutically Relevant Molecular Crystal Forms through Fragment-Based Ab Initio Chemical Shift Predictions.

PubMed

Hartman, Joshua D; Day, Graeme M; Beran, Gregory J O

2016-11-02

Chemical shift prediction plays an important role in the determination or validation of crystal structures with solid-state nuclear magnetic resonance (NMR) spectroscopy. One of the fundamental theoretical challenges lies in discriminating variations in chemical shifts resulting from different crystallographic environments. Fragment-based electronic structure methods provide an alternative to the widely used plane wave gauge-including projector augmented wave (GIPAW) density functional technique for chemical shift prediction. Fragment methods allow hybrid density functionals to be employed routinely in chemical shift prediction, and we have recently demonstrated appreciable improvements in the accuracy of the predicted shifts when using the hybrid PBE0 functional instead of generalized gradient approximation (GGA) functionals like PBE. Here, we investigate the solid-state 13 C and 15 N NMR spectra for multiple crystal forms of acetaminophen, phenobarbital, and testosterone. We demonstrate that the use of the hybrid density functional instead of a GGA provides both higher accuracy in the chemical shifts and increased discrimination among the different crystallographic environments. Finally, these results also provide compelling evidence for the transferability of the linear regression parameters mapping predicted chemical shieldings to chemical shifts that were derived in an earlier study.

Enhanced NMR Discrimination of Pharmaceutically Relevant Molecular Crystal Forms through Fragment-Based Ab Initio Chemical Shift Predictions

PubMed Central

2016-01-01

Chemical shift prediction plays an important role in the determination or validation of crystal structures with solid-state nuclear magnetic resonance (NMR) spectroscopy. One of the fundamental theoretical challenges lies in discriminating variations in chemical shifts resulting from different crystallographic environments. Fragment-based electronic structure methods provide an alternative to the widely used plane wave gauge-including projector augmented wave (GIPAW) density functional technique for chemical shift prediction. Fragment methods allow hybrid density functionals to be employed routinely in chemical shift prediction, and we have recently demonstrated appreciable improvements in the accuracy of the predicted shifts when using the hybrid PBE0 functional instead of generalized gradient approximation (GGA) functionals like PBE. Here, we investigate the solid-state 13C and 15N NMR spectra for multiple crystal forms of acetaminophen, phenobarbital, and testosterone. We demonstrate that the use of the hybrid density functional instead of a GGA provides both higher accuracy in the chemical shifts and increased discrimination among the different crystallographic environments. Finally, these results also provide compelling evidence for the transferability of the linear regression parameters mapping predicted chemical shieldings to chemical shifts that were derived in an earlier study. PMID:27829821

Density functional theory calculations of 95Mo NMR parameters in solid-state compounds.

PubMed

Cuny, Jérôme; Furet, Eric; Gautier, Régis; Le Pollès, Laurent; Pickard, Chris J; d'Espinose de Lacaillerie, Jean-Baptiste

2009-12-21

The application of periodic density functional theory-based methods to the calculation of (95)Mo electric field gradient (EFG) and chemical shift (CS) tensors in solid-state molybdenum compounds is presented. Calculations of EFG tensors are performed using the projector augmented-wave (PAW) method. Comparison of the results with those obtained using the augmented plane wave + local orbitals (APW+lo) method and with available experimental values shows the reliability of the approach for (95)Mo EFG tensor calculation. CS tensors are calculated using the recently developed gauge-including projector augmented-wave (GIPAW) method. This work is the first application of the GIPAW method to a 4d transition-metal nucleus. The effects of ultra-soft pseudo-potential parameters, exchange-correlation functionals and structural parameters are precisely examined. Comparison with experimental results allows the validation of this computational formalism.

A quantitative study of factors influencing lamellar eutectic morphology during solidification

NASA Technical Reports Server (NTRS)

Kaukler, W. F. S.

1981-01-01

The factors that influence the shape of the solid-liquid interface of a lamellar binary eutectic alloy are evaluated. Alloys of carbon tetrabromide and hexachloroethane which serve as a transparent analogue of lamellar metallic eutectics are used. The observed interface shapes are analyzed by computer-aided methods. The solid-liquid interfacial free energies of each of the individual phases comprising the eutectic system are measured as a function of composition using a 'grain boundary groove' technique. The solid-liquid interfacial free energy of the two phases are evaluated directly from the eutectic interface. The phase diagram for the system, the heat of fusion as a function of composition, and the density as a function of composition are measured. The shape of the eutectic interface is controlled mainly by the solid-liquid and solid-solid interfacial free energy relationships at the interface and by the temperature gradient present, rather than by interlamellar diffusion in the liquid at the interface, over the range of growth rates studied.

Geometric Modeling for Computer Vision

DTIC Science & Technology

1974-10-01

within a distance R of a locus X ,Y,Z; spatial uniqueness refers to the property that physical solids can not occupy the same space simultaneously. A...density functions W«p( X ,Y,Z). Unfortunately such density functions can no» be writtrn out for objects such as a typing chair or a plastic horse...be approximated by a surface function 2 = F( X ,Y). For example landscape may be represented by geodetic maps in such a 2-D fashion. By definition, a

Ground-state densities from the Rayleigh-Ritz variation principle and from density-functional theory.

PubMed

Kvaal, Simen; Helgaker, Trygve

2015-11-14

The relationship between the densities of ground-state wave functions (i.e., the minimizers of the Rayleigh-Ritz variation principle) and the ground-state densities in density-functional theory (i.e., the minimizers of the Hohenberg-Kohn variation principle) is studied within the framework of convex conjugation, in a generic setting covering molecular systems, solid-state systems, and more. Having introduced admissible density functionals as functionals that produce the exact ground-state energy for a given external potential by minimizing over densities in the Hohenberg-Kohn variation principle, necessary and sufficient conditions on such functionals are established to ensure that the Rayleigh-Ritz ground-state densities and the Hohenberg-Kohn ground-state densities are identical. We apply the results to molecular systems in the Born-Oppenheimer approximation. For any given potential v ∈ L(3/2)(ℝ(3)) + L(∞)(ℝ(3)), we establish a one-to-one correspondence between the mixed ground-state densities of the Rayleigh-Ritz variation principle and the mixed ground-state densities of the Hohenberg-Kohn variation principle when the Lieb density-matrix constrained-search universal density functional is taken as the admissible functional. A similar one-to-one correspondence is established between the pure ground-state densities of the Rayleigh-Ritz variation principle and the pure ground-state densities obtained using the Hohenberg-Kohn variation principle with the Levy-Lieb pure-state constrained-search functional. In other words, all physical ground-state densities (pure or mixed) are recovered with these functionals and no false densities (i.e., minimizing densities that are not physical) exist. The importance of topology (i.e., choice of Banach space of densities and potentials) is emphasized and illustrated. The relevance of these results for current-density-functional theory is examined.

Lunar Surface Material - Spacecraft Measurements of Density and Strength

NASA Technical Reports Server (NTRS)

Jaffe, L. D.

1969-01-01

The relation of the density of the lunar surface layer to depth is probably best determined from spacecraft measurements of the bearing capacity as a function of depth. A comparison of these values with laboratory measurements of the bearing capacity of low-cohesion particulate materials as a function of the percentage of solid indicates that the bulk density at the lunar surface is about 1.1 grams per cubic centimeter and that it increases nearly linearly to about 1.6 grams per cubic centimeter at a depth of 5 centimeters.

Density functional description of size-dependent effects at nucleation on neutral and charged nanoparticles

NASA Astrophysics Data System (ADS)

Shchekin, Alexander K.; Lebedeva, Tatiana S.

2017-03-01

A numerical study of size-dependent effects in the thermodynamics of a small droplet formed around a solid nanoparticle has been performed within the square-gradient density functional theory. The Lennard-Jones fluid with the Carnahan-Starling model for the hard-sphere contribution to intermolecular interaction in liquid and vapor phases and interfaces has been used for description of the condensate. The intermolecular forces between the solid core and condensate molecules have been taken into account with the help of the Lennard-Jones part of the total molecular potential of the core. The influence of the electric charge of the particle has been considered under assumption of the central Coulomb potential in the medium with dielectric permittivity depending on local condensate density. The condensate density profiles and equimolecular radii for equilibrium droplets at different values of the condensate chemical potential have been computed in the cases of an uncharged solid core with the molecular potential, a charged core without molecular potential, and a core with joint action of the Coulomb and molecular potentials. The appearance of stable equilibrium droplets even in the absence of the electric charge has been commented. As a next step, the capillary, disjoining pressure, and electrostatic contributions to the condensate chemical potential have been considered and compared with the predictions of classical thermodynamics in a wide range of values of the droplet and the particle equimolecular radii. With the help of the found dependence of the condensate chemical potential in droplet on the droplet size, the activation barrier for nucleation on uncharged and charged particles has been computed as a function of the vapor supersaturation. Finally, the work of droplet formation and the work of wetting the particle have been found as functions of the droplet size.

An extrapolation scheme for solid-state NMR chemical shift calculations

NASA Astrophysics Data System (ADS)

Nakajima, Takahito

2017-06-01

Conventional quantum chemical and solid-state physical approaches include several problems to accurately calculate solid-state nuclear magnetic resonance (NMR) properties. We propose a reliable computational scheme for solid-state NMR chemical shifts using an extrapolation scheme that retains the advantages of these approaches but reduces their disadvantages. Our scheme can satisfactorily yield solid-state NMR magnetic shielding constants. The estimated values have only a small dependence on the low-level density functional theory calculation with the extrapolation scheme. Thus, our approach is efficient because the rough calculation can be performed in the extrapolation scheme.

Quantum electronic stress: density-functional-theory formulation and physical manifestation.

PubMed

Hu, Hao; Liu, Miao; Wang, Z F; Zhu, Junyi; Wu, Dangxin; Ding, Hepeng; Liu, Zheng; Liu, Feng

2012-08-03

The concept of quantum electronic stress (QES) is introduced and formulated within density functional theory to elucidate extrinsic electronic effects on the stress state of solids and thin films in the absence of lattice strain. A formal expression of QES (σ(QE)) is derived in relation to deformation potential of electronic states (Ξ) and variation of electron density (Δn), σ(QE) = ΞΔn as a quantum analog of classical Hooke's law. Two distinct QES manifestations are demonstrated quantitatively by density functional theory calculations: (1) in the form of bulk stress induced by charge carriers and (2) in the form of surface stress induced by quantum confinement. Implications of QES in some physical phenomena are discussed to underlie its importance.

Separation and determination of citrinin in corn using HPLC fluorescence detection assisted by molecularly imprinted solid phase extraction clean-up

USDA-ARS?s Scientific Manuscript database

A liquid chromatography based method to detect citrinin in corn was developed using molecularly imprinted solid phase extraction (MISPE) sample clean-up. Molecularly imprinted polymers were synthesized using 1,4-dihydroxy-2-naphthoic acid as the template and an amine functional monomer. Density func...

Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by 17O solid-state NMR and density functional theory.

PubMed

Gupta, Rupal; Stringer, John; Struppe, Jochem; Rehder, Dieter; Polenova, Tatyana

2018-07-01

Electronic and structural properties of short-lived metal-peroxido complexes, which are key intermediates in many enzymatic reactions, are not fully understood. While detected in various enzymes, their catalytic properties remain elusive because of their transient nature, making them difficult to study spectroscopically. We integrated 17 O solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases. 17 O chemical shift and quadrupolar tensors, measured by solid-state NMR spectroscopy, probe the electronic structure of the peroxido ligand and its interaction with the metal. DFT analysis reveals the unusually large chemical shift anisotropy arising from the metal orbitals contributing towards the magnetic shielding of the ligand. The results illustrate the power of an integrated approach for studies of oxygen centers in enzyme reaction intermediates. Copyright © 2018 Elsevier Inc. All rights reserved.

Pressure cell for investigations of solid-liquid interfaces by neutron reflectivity.

PubMed

Kreuzer, Martin; Kaltofen, Thomas; Steitz, Roland; Zehnder, Beat H; Dahint, Reiner

2011-02-01

We describe an apparatus for measuring scattering length density and structure of molecular layers at planar solid-liquid interfaces under high hydrostatic pressure conditions. The device is designed for in situ characterizations utilizing neutron reflectometry in the pressure range 0.1-100 MPa at temperatures between 5 and 60 °C. The pressure cell is constructed such that stratified molecular layers on crystalline substrates of silicon, quartz, or sapphire with a surface area of 28 cm(2) can be investigated against noncorrosive liquid phases. The large substrate surface area enables reflectivity to be measured down to 10(-5) (without background correction) and thus facilitates determination of the scattering length density profile across the interface as a function of applied load. Our current interest is on the stability of oligolamellar lipid coatings on silicon surfaces against aqueous phases as a function of applied hydrostatic pressure and temperature but the device can also be employed to probe the structure of any other solid-liquid interface.

Absorption, scattering, and radiation force efficiencies in the longitudinal wave scattering by a small viscoelastic particle in an isotropic solid.

PubMed

Lopes, J H; Leão-Neto, J P; Silva, G T

2017-11-01

Analytical expressions of the absorption, scattering, and elastic radiation force efficiency factors are derived for the longitudinal plane wave scattering by a small viscoelastic particle in a lossless solid matrix. The particle is assumed to be much smaller than the incident wavelength, i.e., the so-called long-wavelength (Rayleigh) approximation. The efficiencies are dimensionless quantities that represent the absorbed and scattering powers and the elastic radiation force on the particle. In the quadrupole approximation, they are expressed in terms of contrast functions (bulk and shear moduli, and density) between the particle and solid matrix. The results for a high-density polyethylene particle embedded in an aluminum matrix agree with those obtained with the partial wave expansion method. Additionally, the connection between the elastic radiation force and forward scattering function is established through the optical theorem. The present results should be useful for ultrasound characterization of particulate composites, and the development of implanted devices activated by radiation force.

The phase diagram of water at negative pressures: virtual ices.

PubMed

Conde, M M; Vega, C; Tribello, G A; Slater, B

2009-07-21

The phase diagram of water at negative pressures as obtained from computer simulations for two models of water, TIP4P/2005 and TIP5P is presented. Several solid structures with lower densities than ice Ih, so-called virtual ices, were considered as possible candidates to occupy the negative pressure region of the phase diagram of water. In particular the empty hydrate structures sI, sII, and sH and another, recently proposed, low-density ice structure. The relative stabilities of these structures at 0 K was determined using empirical water potentials and density functional theory calculations. By performing free energy calculations and Gibbs-Duhem integration the phase diagram of TIP4P/2005 was determined at negative pressures. The empty hydrates sII and sH appear to be the stable solid phases of water at negative pressures. The phase boundary between ice Ih and sII clathrate occurs at moderate negative pressures, while at large negative pressures sH becomes the most stable phase. This behavior is in reasonable agreement with what is observed in density functional theory calculations.

Anharmonic, dimensionality and size effects in phonon transport

NASA Astrophysics Data System (ADS)

Thomas, Iorwerth O.; Srivastava, G. P.

2017-12-01

We have developed and employed a numerically efficient semi- ab initio theory, based on density-functional and relaxation-time schemes, to examine anharmonic, dimensionality and size effects in phonon transport in three- and two-dimensional solids of different crystal symmetries. Our method uses third- and fourth-order terms in crystal Hamiltonian expressed in terms of a temperature-dependent Grüneisen’s constant. All input to numerical calculations are generated from phonon calculations based on the density-functional perturbation theory. It is found that four-phonon processes make important and measurable contribution to lattice thermal resistivity above the Debye temperature. From our numerical results for bulk Si, bulk Ge, bulk MoS2 and monolayer MoS2 we find that the sample length dependence of phonon conductivity is significantly stronger in low-dimensional solids.

Nanoionic devices: Interface nanoarchitechtonics for physical property tuning and enhancement

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Terabe, Kazuya; Yang, Rui; Aono, Masakazu

2016-11-01

Nanoionic devices have been developed to generate novel functions overcoming limitations of conventional materials synthesis and semiconductor technology. Various physical properties can be tuned and enhanced by local ion transport near the solid/solid interface. Two electronic carrier doping methods can be used to achieve extremely high-density electronic carriers: one is electrostatic carrier doping using an electric double layer (EDL); the other is electrochemical carrier doping using a redox reaction. Atomistic restructuring near the solid/solid interface driven by a DC voltage, namely, interface nanoarchitechtonics, has huge potential. For instance, the use of EDL enables high-density carrier doping in potential superconductors, which can hardly accept chemical doping, in order to achieve room-temperature superconductivity. Optical bandgap and photoluminescence can be controlled for various applications including smart windows and biosensors. In situ tuning of magnetic properties is promising for low-power-consumption spintronics. Synaptic plasticity in the human brain is achieved in neuromorphic devices.

Some effects of electron channeling on electron energy loss spectroscopy.

PubMed

Kirkland, Earl J

2005-02-01

As an electron beam (of order 100 keV) travels through a crystalline solid it can be channeled down a zone axis of the crystal to form a channeling peak centered on the atomic columns. The channeling peak can be similar in size to the outer atomic orbitals. Electron energy loss spectroscopy (EELS) measures the losses that the electron experiences as it passes through the solid yielding information about the unoccupied density of states in the solid. The interaction matrix element for this process typically produces dipole selection rules for small angle scattering. In this paper, a theoretical calculation of the EELS cross section in the presence of strong channeling is performed for the silicon L23 edge. The presence of channeling is found to alter both the intensity and selection rules for this EELS signal as a function of depth in the solid. At some depths in the specimen small but significant non-dipole transition components can be produced, which may influence measurements of the density of states in solids.

Weavable, Conductive Yarn-Based NiCo//Zn Textile Battery with High Energy Density and Rate Capability.

PubMed

Huang, Yan; Ip, Wing Shan; Lau, Yuen Ying; Sun, Jinfeng; Zeng, Jie; Yeung, Nga Sze Sea; Ng, Wing Sum; Li, Hongfei; Pei, Zengxia; Xue, Qi; Wang, Yukun; Yu, Jie; Hu, Hong; Zhi, Chunyi

2017-09-26

With intrinsic safety and much higher energy densities than supercapacitors, rechargeable nickel/cobalt-zinc-based textile batteries are promising power sources for next generation personalized wearable electronics. However, high-performance wearable nickel/cobalt-zinc-based batteries are rarely reported because there is a lack of industrially weavable and knittable highly conductive yarns. Here, we use scalably produced highly conductive yarns uniformly covered with zinc (as anode) and nickel cobalt hydroxide nanosheets (as cathode) to fabricate rechargeable yarn batteries. They possess a battery level capacity and energy density, as well as a supercapacitor level power density. They deliver high specific capacity of 5 mAh cm -3 and energy densities of 0.12 mWh cm -2 and 8 mWh cm -3 (based on the whole solid battery). They exhibit ultrahigh rate capabilities of 232 C (liquid electrolyte) and 116 C (solid electrolyte), which endows the batteries excellent power densities of 32.8 mW cm -2 and 2.2 W cm -3 (based on the whole solid battery). These are among the highest values reported so far. A wrist band battery is further constructed by using a large conductive cloth woven from the conductive yarns by a commercial weaving machine. It powers various electronic devices successfully, enabling dual functions of wearability and energy storage.

Kinetic theory of heterogeneous nucleation; effect of nonuniform density in the nuclei.

PubMed

Berim, Gersh O; Ruckenstein, Eli

2011-03-01

The heterogeneous nucleation of a liquid from a vapor in contact with a planar solid surface or a solid surface with cavities is examined on the basis of the kinetic theory of nucleation developed by Nowakowski and Ruckenstein [J. Phys. Chem. 96 (1992) 2313] which is extended to nonuniform fluid density distribution (FDD) in the nucleus. The latter is determined under the assumption that at each moment the FDD in the nucleus is provided by the density functional theory (DFT) for a nanodrop. As a result of this assumption, the theory does not require to consider that the contact angle which the nucleus makes with the solid surface and the density of the nucleus are independent parameters since they are provided by the DFT. For all considered cases, the nucleation rate is higher in the cavities than on a planar surface and increases with increasing strength of the fluid-solid interactions and decreasing cavity radius. The difference is small at high supersaturations (small critical nuclei), but becomes larger at low supersaturations when the critical nucleus has a size comparable with the size of the cavity. The nonuniformity of the FDD in the nucleus decreases the nucleation rate when compared to the uniform FDD. Copyright © 2010 Elsevier Inc. All rights reserved.

The solid-state terahertz spectrum of MDMA (Ecstasy) - A unique test for molecular modeling assignments

NASA Astrophysics Data System (ADS)

Allis, Damian G.; Hakey, Patrick M.; Korter, Timothy M.

2008-10-01

The terahertz (THz, far-infrared) spectrum of 3,4-methylene-dioxymethamphetamine hydrochloride (Ecstasy) is simulated using solid-state density functional theory. While a previously reported isolated-molecule calculation is noteworthy for the precision of its solid-state THz reproduction, the solid-state calculation predicts that the isolated-molecule modes account for only half of the spectral features in the THz region, with the remaining structure arising from lattice vibrations that cannot be predicted without solid-state molecular modeling. The molecular origins of the internal mode contributions to the solid-state THz spectrum, as well as the proper consideration of the protonation state of the molecule, are also considered.

A general representation scheme for crystalline solids based on Voronoi-tessellation real feature values and atomic property data

PubMed Central

Jalem, Randy; Nakayama, Masanobu; Noda, Yusuke; Le, Tam; Takeuchi, Ichiro; Tateyama, Yoshitaka; Yamazaki, Hisatsugu

2018-01-01

Abstract Increasing attention has been paid to materials informatics approaches that promise efficient and fast discovery and optimization of functional inorganic materials. Technical breakthrough is urgently requested to advance this field and efforts have been made in the development of materials descriptors to encode or represent characteristics of crystalline solids, such as chemical composition, crystal structure, electronic structure, etc. We propose a general representation scheme for crystalline solids that lifts restrictions on atom ordering, cell periodicity, and system cell size based on structural descriptors of directly binned Voronoi-tessellation real feature values and atomic/chemical descriptors based on the electronegativity of elements in the crystal. Comparison was made vs. radial distribution function (RDF) feature vector, in terms of predictive accuracy on density functional theory (DFT) material properties: cohesive energy (CE), density (d), electronic band gap (BG), and decomposition energy (Ed). It was confirmed that the proposed feature vector from Voronoi real value binning generally outperforms the RDF-based one for the prediction of aforementioned properties. Together with electronegativity-based features, Voronoi-tessellation features from a given crystal structure that are derived from second-nearest neighbor information contribute significantly towards prediction. PMID:29707064

A general representation scheme for crystalline solids based on Voronoi-tessellation real feature values and atomic property data.

PubMed

Jalem, Randy; Nakayama, Masanobu; Noda, Yusuke; Le, Tam; Takeuchi, Ichiro; Tateyama, Yoshitaka; Yamazaki, Hisatsugu

2018-01-01

Increasing attention has been paid to materials informatics approaches that promise efficient and fast discovery and optimization of functional inorganic materials. Technical breakthrough is urgently requested to advance this field and efforts have been made in the development of materials descriptors to encode or represent characteristics of crystalline solids, such as chemical composition, crystal structure, electronic structure, etc. We propose a general representation scheme for crystalline solids that lifts restrictions on atom ordering, cell periodicity, and system cell size based on structural descriptors of directly binned Voronoi-tessellation real feature values and atomic/chemical descriptors based on the electronegativity of elements in the crystal. Comparison was made vs. radial distribution function (RDF) feature vector, in terms of predictive accuracy on density functional theory (DFT) material properties: cohesive energy (CE), density ( d ), electronic band gap (BG), and decomposition energy (Ed). It was confirmed that the proposed feature vector from Voronoi real value binning generally outperforms the RDF-based one for the prediction of aforementioned properties. Together with electronegativity-based features, Voronoi-tessellation features from a given crystal structure that are derived from second-nearest neighbor information contribute significantly towards prediction.

Influence of the aggregate state on band structure and optical properties of C60 computed with different methods

NASA Astrophysics Data System (ADS)

Pal, Amrita; Arabnejad, Saeid; Yamashita, Koichi; Manzhos, Sergei

2018-05-01

C60 and C60 based molecules are efficient acceptors and electron transport layers for planar perovskite solar cells. While properties of these molecules are well studied by ab initio methods, those of solid C60, specifically its optical absorption properties, are not. We present a combined density functional theory-Density Functional Tight Binding (DFTB) study of the effect of solid state packing on the band structure and optical absorption of C60. The valence and conduction band edge energies of solid C60 differ on the order of 0.1 eV from single molecule frontier orbital energies. We show that calculations of optical properties using linear response time dependent-DFT(B) or the imaginary part of the dielectric constant (dipole approximation) can result in unrealistically large redshifts in the presence of intermolecular interactions compared to available experimental data. We show that optical spectra computed from the frequency-dependent real polarizability can better reproduce the effect of C60 aggregation on optical absorption, specifically with a generalized gradient approximation functional, and may be more suited to study effects of molecular aggregation.

First-principles simulations of heat transport

NASA Astrophysics Data System (ADS)

Puligheddu, Marcello; Gygi, Francois; Galli, Giulia

2017-11-01

Advances in understanding heat transport in solids were recently reported by both experiment and theory. However an efficient and predictive quantum simulation framework to investigate thermal properties of solids, with the same complexity as classical simulations, has not yet been developed. Here we present a method to compute the thermal conductivity of solids by performing ab initio molecular dynamics at close to equilibrium conditions, which only requires calculations of first-principles trajectories and atomic forces, thus avoiding direct computation of heat currents and energy densities. In addition the method requires much shorter sequential simulation times than ordinary molecular dynamics techniques, making it applicable within density functional theory. We discuss results for a representative oxide, MgO, at different temperatures and for ordered and nanostructured morphologies, showing the performance of the method in different conditions.

Computational designing and screening of solid materials for CO2capture

NASA Astrophysics Data System (ADS)

Duan, Yuhua

In this presentation, we will update our progress on computational designing and screening of solid materials for CO2 capture. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO2 sorbent candidates from the vast array of possible solid materials have been proposed and validated at NETL. The advantage of this method is that it identifies the thermodynamic properties of the CO2 capture reaction as a function of temperature and pressure without any experimental input beyond crystallographic structural information of the solid phases involved. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the solids of interest, we were able to identify only those solid materials for which lower capture energy costs are expected at the desired working conditions. In addition, we present a simulation scheme to increase and decrease the turnover temperature (Tt) of solid capturing CO2 reaction by mixing other solids. Our results also show that some solid sorbents can serve as bi-functional materials: CO2 sorbent and CO oxidation catalyst. Such dual functionality could be used for removing both CO and CO2 after water-gas-shift to obtain pure H2.

Hybrid density functional study of band alignment in ZnO-GaN and ZnO-(Ga(1-x)Zn(x))(N(1-x)O(x))-GaN heterostructures.

PubMed

Wang, Zhenhai; Zhao, Mingwen; Wang, Xiaopeng; Xi, Yan; He, Xiujie; Liu, Xiangdong; Yan, Shishen

2012-12-05

The band alignment in ZnO-GaN and related heterostructures is crucial for uses in solar harvesting technology. Here, we report our density functional calculations of the band alignment and optical properties of ZnO-GaN and ZnO-(Ga(1-x)Zn(x))(N(1-x)O(x))-GaN heterostructures using a Heyd-Scuseria-Ernzerhof (HSE) hybrid functional. We found that the conventional GGA functionals underestimate not only the band gap but also the band offset of these heterostructures. Using the hybrid functional calculations, we show that the (Ga(1-x)Zn(x))(N(1-x)O(x)) solid solution has a direct band gap of about 2.608 eV, in good agreement with the experimental data. More importantly, this solid solution forms type-II band alignment with the host materials. A GaN-(Ga(1-x)Zn(x))(N(1-x)O(x))-ZnO core-shell solar cell model is presented to improve the visible light absorption ability and carrier collection efficiency.

The comparison of approaches to the solid-state NMR-based structural refinement of vitamin B1 hydrochloride and of its monohydrate

NASA Astrophysics Data System (ADS)

Czernek, Jiří; Pawlak, Tomasz; Potrzebowski, Marek J.; Brus, Jiří

2013-01-01

The 13C and 15N CPMAS SSNMR measurements were accompanied by the proper theoretical description of the solid-phase environment, as provided by the density functional theory in the pseudopotential plane-wave scheme, and employed in refining the atomic coordinates of the crystal structures of thiamine chloride hydrochloride and of its monohydrate. Thus, using the DFT functionals PBE, PW91 and RPBE, the SSNMR-consistent solid-phase structures of these compounds are derived from the geometrical optimization, which is followed by an assessment of the fits of the GIPAW-predicted values of the chemical shielding parameters to their experimental counterparts.

Invertibility of retarded response functions for Laplace transformable potentials: Application to one-body reduced density matrix functional theory.

PubMed

Giesbertz, K J H

2015-08-07

A theorem for the invertibility of arbitrary response functions is presented under the following conditions: the time dependence of the potentials should be Laplace transformable and the initial state should be a ground state, though it might be degenerate. This theorem provides a rigorous foundation for all density-functional-like theories in the time-dependent linear response regime. Especially for time-dependent one-body reduced density matrix (1RDM) functional theory, this is an important step forward, since a solid foundation has currently been lacking. The theorem is equally valid for static response functions in the non-degenerate case, so can be used to characterize the uniqueness of the potential in the ground state version of the corresponding density-functional-like theory. Such a classification of the uniqueness of the non-local potential in ground state 1RDM functional theory has been lacking for decades. With the aid of presented invertibility theorem presented here, a complete classification of the non-uniqueness of the non-local potential in 1RDM functional theory can be given for the first time.

Using Wannier functions to improve solid band gap predictions in density functional theory

DOE PAGES

Ma, Jie; Wang, Lin-Wang

2016-04-26

Enforcing a straight-line condition of the total energy upon removal/addition of fractional electrons on eigen states has been successfully applied to atoms and molecules for calculating ionization potentials and electron affinities, but fails for solids due to the extended nature of the eigen orbitals. Here we have extended the straight-line condition to the removal/addition of fractional electrons on Wannier functions constructed within the occupied/unoccupied subspaces. It removes the self-interaction energies of those Wannier functions, and yields accurate band gaps for solids compared to experiments. It does not have any adjustable parameters and the computational cost is at the DFT level.more » This method can also work for molecules, providing eigen energies in good agreement with experimental ionization potentials and electron affinities. Our approach can be viewed as an alternative approach of the standard LDA+U procedure.« less

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

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

Peng, Haowei; Yang, Zeng-Hui; Perdew, John P.

A “best-of-both-worlds” van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short- and intermediate-range interactions with the long-range vdW interaction from r VV 10 , the revised Vydrov–van Voorhis nonlocal correlation functional. The resultant SCAN + r VV 10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies andmore » lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co(0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.« less

Versatile van der Waals Density Functional Based on a Meta-Generalized Gradient Approximation

DOE PAGES

Peng, Haowei; Yang, Zeng-Hui; Perdew, John P.; ...

2016-10-12

A “best-of-both-worlds” van der Waals (vdW) density functional is constructed, seamlessly supplementing the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation for short- and intermediate-range interactions with the long-range vdW interaction from r VV 10 , the revised Vydrov–van Voorhis nonlocal correlation functional. The resultant SCAN + r VV 10 is the only vdW density functional to date that yields excellent interlayer binding energies and spacings, as well as intralayer lattice constants in 28 layered materials. Its versatility for various kinds of bonding is further demonstrated by its good performance for 22 interactions between molecules; the cohesive energies andmore » lattice constants of 50 solids; the adsorption energy and distance of a benzene molecule on coinage-metal surfaces; the binding energy curves for graphene on Cu(111), Ni(111), and Co(0001) surfaces; and the rare-gas solids. We argue that a good semilocal approximation should (as SCAN does) capture the intermediate-range vdW through its exchange term. We have found an effective range of the vdW interaction between 8 and 16 Å for systems considered here, suggesting that this interaction is negligibly small at the larger distances where it reaches its asymptotic power-law decay.« less

Application of London-type dispersion corrections to the solid-state density functional theory simulation of the terahertz spectra of crystalline pharmaceuticals.

PubMed

King, Matthew D; Buchanan, William D; Korter, Timothy M

2011-03-14

The effects of applying an empirical dispersion correction to solid-state density functional theory methods were evaluated in the simulation of the crystal structure and low-frequency (10 to 90 cm(-1)) terahertz spectrum of the non-steroidal anti-inflammatory drug, naproxen. The naproxen molecular crystal is bound largely by weak London force interactions, as well as by more prominent interactions such as hydrogen bonding, and thus serves as a good model for the assessment of the pair-wise dispersion correction term in systems influenced by intermolecular interactions of various strengths. Modifications to the dispersion parameters were tested in both fully optimized unit cell dimensions and those determined by X-ray crystallography, with subsequent simulations of the THz spectrum being performed. Use of the unmodified PBE density functional leads to an unrealistic expansion of the unit cell volume and the poor representation of the THz spectrum. Inclusion of a modified dispersion correction enabled a high-quality simulation of the THz spectrum and crystal structure of naproxen to be achieved without the need for artificially constraining the unit cell dimensions.

Coarse-grained discrete particle simulations of particle segregation in rotating fluidized beds in vortex chambers [Discrete particle simulations of particle segregation in rotating fluidized beds in vortex chambers

DOE PAGES

Verma, Vikrant; Li, Tingwen; De Wilde, Juray

2017-05-26

Vortex chambers allow the generation of rotating fluidized beds, offering high-G intensified gas-solid contact, gas-solids separation and solids-solids segregation. Focusing on binary particle mixtures and fixing the density and diameter of the heavy/large particles, transient batch CFD-coarse-grained DPM simulations were carried out with varying densities or sizes of the light/small particles to evaluate to what extent combining these three functionalities is possible within a vortex chamber of given design. Both the rate and quality of segregation were analyzed. Within a relatively wide density and size range, fast and efficient segregation takes place, with an inner and slower rotating bed ofmore » the lighter/small particles forming within the outer and faster rotating bed of the heavier/large particles. Simulations show that the contamination of the outer bed with lighter particles occurs more easily than contamination of the inner bed with heavier particles and increases with decreasing difference in size or density of the particles. Bubbling in the inner bed is observed with an inner bed of very low density or small particles. Porosity plots show that vortex chambers with a sufficient number of gas inlet slots have to be used to guarantee a uniform gas distribution and particle bed. Lastly, the flexibility of particle segregation in vortex chambers with respect to the gas flow rate is demonstrated.« less

Coarse-grained discrete particle simulations of particle segregation in rotating fluidized beds in vortex chambers [Discrete particle simulations of particle segregation in rotating fluidized beds in vortex chambers

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

Verma, Vikrant; Li, Tingwen; De Wilde, Juray

Vortex chambers allow the generation of rotating fluidized beds, offering high-G intensified gas-solid contact, gas-solids separation and solids-solids segregation. Focusing on binary particle mixtures and fixing the density and diameter of the heavy/large particles, transient batch CFD-coarse-grained DPM simulations were carried out with varying densities or sizes of the light/small particles to evaluate to what extent combining these three functionalities is possible within a vortex chamber of given design. Both the rate and quality of segregation were analyzed. Within a relatively wide density and size range, fast and efficient segregation takes place, with an inner and slower rotating bed ofmore » the lighter/small particles forming within the outer and faster rotating bed of the heavier/large particles. Simulations show that the contamination of the outer bed with lighter particles occurs more easily than contamination of the inner bed with heavier particles and increases with decreasing difference in size or density of the particles. Bubbling in the inner bed is observed with an inner bed of very low density or small particles. Porosity plots show that vortex chambers with a sufficient number of gas inlet slots have to be used to guarantee a uniform gas distribution and particle bed. Lastly, the flexibility of particle segregation in vortex chambers with respect to the gas flow rate is demonstrated.« less

The anelastic Ericksen problem: universal eigenstrains and deformations in compressible isotropic elastic solids.

PubMed

Yavari, Arash; Goriely, Alain

2016-12-01

The elastic Ericksen problem consists of finding deformations in isotropic hyperelastic solids that can be maintained for arbitrary strain-energy density functions. In the compressible case, Ericksen showed that only homogeneous deformations are possible. Here, we solve the anelastic version of the same problem, that is, we determine both the deformations and the eigenstrains such that a solution to the anelastic problem exists for arbitrary strain-energy density functions. Anelasticity is described by finite eigenstrains. In a nonlinear solid, these eigenstrains can be modelled by a Riemannian material manifold whose metric depends on their distribution. In this framework, we show that the natural generalization of the concept of homogeneous deformations is the notion of covariantly homogeneous deformations -deformations with covariantly constant deformation gradients. We prove that these deformations are the only universal deformations and that they put severe restrictions on possible universal eigenstrains . We show that, in a simply-connected body, for any distribution of universal eigenstrains the material manifold is a symmetric Riemannian manifold and that in dimensions 2 and 3 the universal eigenstrains are zero-stress.

The anelastic Ericksen problem: universal eigenstrains and deformations in compressible isotropic elastic solids

PubMed Central

2016-01-01

The elastic Ericksen problem consists of finding deformations in isotropic hyperelastic solids that can be maintained for arbitrary strain-energy density functions. In the compressible case, Ericksen showed that only homogeneous deformations are possible. Here, we solve the anelastic version of the same problem, that is, we determine both the deformations and the eigenstrains such that a solution to the anelastic problem exists for arbitrary strain-energy density functions. Anelasticity is described by finite eigenstrains. In a nonlinear solid, these eigenstrains can be modelled by a Riemannian material manifold whose metric depends on their distribution. In this framework, we show that the natural generalization of the concept of homogeneous deformations is the notion of covariantly homogeneous deformations—deformations with covariantly constant deformation gradients. We prove that these deformations are the only universal deformations and that they put severe restrictions on possible universal eigenstrains. We show that, in a simply-connected body, for any distribution of universal eigenstrains the material manifold is a symmetric Riemannian manifold and that in dimensions 2 and 3 the universal eigenstrains are zero-stress. PMID:28119554

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo

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

Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.

We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, amore » finding in stark contrast to DAC data.« less

Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo

DOE PAGES

Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.

2014-10-01

We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, amore » finding in stark contrast to DAC data.« less

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

Nonlocal and Nonadiabatic Effects in the Charge-Density Response of Solids: A Time-Dependent Density-Functional Approach

NASA Astrophysics Data System (ADS)

Panholzer, Martin; Gatti, Matteo; Reining, Lucia

2018-04-01

The charge-density response of extended materials is usually dominated by the collective oscillation of electrons, the plasmons. Beyond this feature, however, intriguing many-body effects are observed. They cannot be described by one of the most widely used approaches for the calculation of dielectric functions, which is time-dependent density functional theory (TDDFT) in the adiabatic local density approximation (ALDA). Here, we propose an approximation to the TDDFT exchange-correlation kernel which is nonadiabatic and nonlocal. It is extracted from correlated calculations in the homogeneous electron gas, where we have tabulated it for a wide range of wave vectors and frequencies. A simple mean density approximation allows one to use it in inhomogeneous materials where the density varies on a scale of 1.6 rs or faster. This kernel contains effects that are completely absent in the ALDA; in particular, it correctly describes the double plasmon in the dynamic structure factor of sodium, and it shows the characteristic low-energy peak that appears in systems with low electronic density. It also leads to an overall quantitative improvement of spectra.

Nonlocal and Nonadiabatic Effects in the Charge-Density Response of Solids: A Time-Dependent Density-Functional Approach.

PubMed

Panholzer, Martin; Gatti, Matteo; Reining, Lucia

2018-04-20

The charge-density response of extended materials is usually dominated by the collective oscillation of electrons, the plasmons. Beyond this feature, however, intriguing many-body effects are observed. They cannot be described by one of the most widely used approaches for the calculation of dielectric functions, which is time-dependent density functional theory (TDDFT) in the adiabatic local density approximation (ALDA). Here, we propose an approximation to the TDDFT exchange-correlation kernel which is nonadiabatic and nonlocal. It is extracted from correlated calculations in the homogeneous electron gas, where we have tabulated it for a wide range of wave vectors and frequencies. A simple mean density approximation allows one to use it in inhomogeneous materials where the density varies on a scale of 1.6 r_{s} or faster. This kernel contains effects that are completely absent in the ALDA; in particular, it correctly describes the double plasmon in the dynamic structure factor of sodium, and it shows the characteristic low-energy peak that appears in systems with low electronic density. It also leads to an overall quantitative improvement of spectra.

New Density Functional Approach for Solid-Liquid-Vapor Transitions in Pure Materials

NASA Astrophysics Data System (ADS)

Kocher, Gabriel; Provatas, Nikolas

2015-04-01

A new phase field crystal (PFC) type theory is presented, which accounts for the full spectrum of solid-liquid-vapor phase transitions within the framework of a single density order parameter. Its equilibrium properties show the most quantitative features to date in PFC modeling of pure substances, and full consistency with thermodynamics in pressure-volume-temperature space is demonstrated. A method to control either the volume or the pressure of the system is also introduced. Nonequilibrium simulations show that 2- and 3-phase growth of solid, vapor, and liquid can be achieved, while our formalism also allows for a full range of pressure-induced transformations. This model opens up a new window for the study of pressure driven interactions of condensed phases with vapor, an experimentally relevant paradigm previously missing from phase field crystal theories.

Positive segregation as a function of buoyancy force during steel ingot solidification.

PubMed

Radovic, Zarko; Jaukovic, Nada; Lalovic, Milisav; Tadic, Nebojsa

2008-12-01

We analyze theoretically and experimentally solute redistribution in the dendritic solidification process and positive segregation during solidification of steel ingots. Positive segregation is mainly caused by liquid flow in the mushy zone. Changes in the liquid steel velocity are caused by the temperature gradient and by the increase in the solid fraction during solidification. The effects of buoyancy and of the change in the solid fraction on segregation intensity are analyzed. The relationships between the density change, liquid fraction and the steel composition are considered. Such elements as W, Ni, Mo and Cr decrease the effect of the density variations, i.e. they show smaller tendency to segregate. Based on the modeling and experimental results, coefficients are provided controlling the effects of chemical composition, secondary dendrite arm spacing and the solid fraction.

Structure, Elastic Constants and XRD Spectra of Extended Solids under High Pressure

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

Batyrev, I. G.; Coleman, S. P.; Ciezak-Jenkins, J. A.

We present results of evolutionary simulations based on density functional calculations of a potentially new type of energetic materials called extended solids: P-N and N-H. High-density structures with covalent bonds generated using variable and fixed concentration methods were analysed in terms of thermo-dynamical stability and agreement with experimental X-ray diffraction (XRD) spectra. X-ray diffraction spectra were calculated using a virtual diffraction algorithm that computes kinematic diffraction intensity in three-dimensional reciprocal space before being reduced to a two-theta line profile. Calculated XRD patterns were used to search for the structure of extended solids present at experimental pressures by optimizing data accordingmore » to experimental XRD peak position, peak intensity and theoretically calculated enthalpy. Elastic constants has been calculated for thermodynamically stable structures of P-N system.« less

Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

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

Dutta, Saikat; Wu, Kevin C.-W., E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw; Kao, Hsien-Ming, E-mail: hmkao@cc.ncu.edu.tw, E-mail: kevinwu@ntu.edu.tw

This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and {sup 13}C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion ofmore » fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.« less

Evidence of two-stage melting of Wigner solids

NASA Astrophysics Data System (ADS)

Knighton, Talbot; Wu, Zhe; Huang, Jian; Serafin, Alessandro; Xia, J. S.; Pfeiffer, L. N.; West, K. W.

2018-02-01

Ultralow carrier concentrations of two-dimensional holes down to p =1 ×109cm-2 are realized. Remarkable insulating states are found below a critical density of pc=4 ×109cm-2 or rs≈40 . Sensitive dc V-I measurement as a function of temperature and electric field reveals a two-stage phase transition supporting the melting of a Wigner solid as a two-stage first-order transition.

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

NASA Astrophysics Data System (ADS)

Xiao, Ruijuan; Li, Hong; Chen, Liquan

2015-09-01

Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

Electronic structure and optical properties of CdSxSe1-x solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

NASA Astrophysics Data System (ADS)

Murphy, M. W.; Yiu, Y. M.; Ward, M. J.; Liu, L.; Hu, Y.; Zapien, J. A.; Liu, Yingkai; Sham, T. K.

2014-11-01

The electronic structure and optical properties of a series of iso-electronic and iso-structural CdSxSe1-x solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

The Structure of Liquid and Amorphous Hafnia.

PubMed

Gallington, Leighanne C; Ghadar, Yasaman; Skinner, Lawrie B; Weber, J K Richard; Ushakov, Sergey V; Navrotsky, Alexandra; Vazquez-Mayagoitia, Alvaro; Neuefeind, Joerg C; Stan, Marius; Low, John J; Benmore, Chris J

2017-11-10

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf-O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that show density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf-Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf-Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.

The Structure of Liquid and Amorphous Hafnia

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

Gallington, Leighanne; Ghadar, Yasaman; Skinner, Lawrie

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that showmore » density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.« less

The Structure of Liquid and Amorphous Hafnia

DOE PAGES

Gallington, Leighanne; Ghadar, Yasaman; Skinner, Lawrie; ...

2017-11-10

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that showmore » density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO 6,7 polyhedra resembling that observed in the monoclinic phase.« less

NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations

NASA Astrophysics Data System (ADS)

de Wijs, G. A.; Laskowski, R.; Blaha, P.; Havenith, R. W. A.; Kresse, G.; Marsman, M.

2017-02-01

We present a benchmark of the density functional linear response calculation of NMR shieldings within the gauge-including projector-augmented-wave method against all-electron augmented-plane-wave+local-orbital and uncontracted Gaussian basis set results for NMR shieldings in molecular and solid state systems. In general, excellent agreement between the aforementioned methods is obtained. Scalar relativistic effects are shown to be quite large for nuclei in molecules in the deshielded limit. The small component makes up a substantial part of the relativistic corrections.

NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations.

PubMed

de Wijs, G A; Laskowski, R; Blaha, P; Havenith, R W A; Kresse, G; Marsman, M

2017-02-14

We present a benchmark of the density functional linear response calculation of NMR shieldings within the gauge-including projector-augmented-wave method against all-electron augmented-plane-wave+local-orbital and uncontracted Gaussian basis set results for NMR shieldings in molecular and solid state systems. In general, excellent agreement between the aforementioned methods is obtained. Scalar relativistic effects are shown to be quite large for nuclei in molecules in the deshielded limit. The small component makes up a substantial part of the relativistic corrections.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Analysis of radiometric signal in sedimentating suspension flow in open channel

NASA Astrophysics Data System (ADS)

Zych, Marcin; Hanus, Robert; Petryka, Leszek; Świsulski, Dariusz; Doktor, Marek; Mastej, Wojciech

2015-05-01

The article discusses issues related to the estimation of the sedimentating solid particles average flow velocity in an open channel using radiometric methods. Due to the composition of the compound, which formed water and diatomite, received data have a very weak signal to noise ratio. In the process analysis the known determining of the solid phase transportation time delay the classical cross-correlation function is the most reliable method. The use of advanced frequency analysis based on mutual spectral density function and wavelet transform of recorded signals allows a reduction of the noise contribution.

Utsu aftershock productivity law explained from geometric operations on the permanent static stress field of mainshocks

NASA Astrophysics Data System (ADS)

Mignan, Arnaud

2018-03-01

The aftershock productivity law is an exponential function of the form K ∝ exp(αM), with K being the number of aftershocks triggered by a given mainshock of magnitude M and α ≈ ln(10) being the productivity parameter. This law remains empirical in nature although it has also been retrieved in static stress simulations. Here, we parameterize this law using the solid seismicity postulate (SSP), the basis of a geometrical theory of seismicity where seismicity patterns are described by mathematical expressions obtained from geometric operations on a permanent static stress field. We first test the SSP that relates seismicity density to a static stress step function. We show that it yields a power exponent q = 1.96 ± 0.01 for the power-law spatial linear density distribution of aftershocks, once uniform noise is added to the static stress field, in agreement with observations. We then recover the exponential function of the productivity law with a break in scaling obtained between small and large M, with α = 1.5ln(10) and ln(10), respectively, in agreement with results from previous static stress simulations. Possible biases of aftershock selection, proven to exist in epidemic-type aftershock sequence (ETAS) simulations, may explain the lack of break in scaling observed in seismicity catalogues. The existence of the theoretical kink, however, remains to be proven. Finally, we describe how to estimate the solid seismicity parameters (activation density δ+, aftershock solid envelope r∗ and background stress amplitude range Δo∗) for large M values.

Effect of solid surface charge on the binding behaviour of a metal-binding peptide

PubMed Central

Donatan, Senem; Sarikaya, Mehmet; Tamerler, Candan; Urgen, Mustafa

2012-01-01

Over the last decade, solid-binding peptides have been increasingly used as molecular building blocks coupling bio- and nanotechnology. Despite considerable research being invested in this field, the effects of many surface-related parameters that define the binding of peptide to solids are still unknown. In the quest to control biological molecules at solid interfaces and, thereby, tailoring the binding characteristics of the peptides, the use of surface charge of the solid surface may probably play an important role, which then can be used as a potential tuning parameter of peptide adsorption. Here, we report quantitative investigation on the viscoelastic properties and binding kinetics of an engineered gold-binding peptide, 3RGBP1, adsorbed onto the gold surface at different surface charge densities. The experiments were performed in aqueous solutions using an electrochemical dissipative quartz crystal microbalance system. Hydrodynamic mass, hydration state and surface coverage of the adsorbed peptide films were determined as a function of surface charge density of the gold metal substrate. Under each charged condition, binding of 3rGBP1 displayed quantitative differences in terms of adsorbed peptide amount, surface coverage ratio and hydration state. Based on the intrinsically disordered structure of the peptide, we propose a possible mechanism for binding of the peptide that can be used for tuning surface adsorption in further studies. Controlled alteration of peptide binding on solid surfaces, as shown here, may provide novel methods for surface functionalization used for bioenabled processing and fabrication of future micro- and nanodevices. PMID:22491974

Modeling of nanoscale liquid mixture transport by density functional hydrodynamics

NASA Astrophysics Data System (ADS)

Dinariev, Oleg Yu.; Evseev, Nikolay V.

2017-06-01

Modeling of multiphase compositional hydrodynamics at nanoscale is performed by means of density functional hydrodynamics (DFH). DFH is the method based on density functional theory and continuum mechanics. This method has been developed by the authors over 20 years and used for modeling in various multiphase hydrodynamic applications. In this paper, DFH was further extended to encompass phenomena inherent in liquids at nanoscale. The new DFH extension is based on the introduction of external potentials for chemical components. These potentials are localized in the vicinity of solid surfaces and take account of the van der Waals forces. A set of numerical examples, including disjoining pressure, film precursors, anomalous rheology, liquid in contact with heterogeneous surface, capillary condensation, and forward and reverse osmosis, is presented to demonstrate modeling capabilities.

Lattice dynamics calculations based on density-functional perturbation theory in real space

NASA Astrophysics Data System (ADS)

Shang, Honghui; Carbogno, Christian; Rinke, Patrick; Scheffler, Matthias

2017-06-01

A real-space formalism for density-functional perturbation theory (DFPT) is derived and applied for the computation of harmonic vibrational properties in molecules and solids. The practical implementation using numeric atom-centered orbitals as basis functions is demonstrated exemplarily for the all-electron Fritz Haber Institute ab initio molecular simulations (FHI-aims) package. The convergence of the calculations with respect to numerical parameters is carefully investigated and a systematic comparison with finite-difference approaches is performed both for finite (molecules) and extended (periodic) systems. Finally, the scaling tests and scalability tests on massively parallel computer systems demonstrate the computational efficiency.

Multiphase aluminum equations of state via density functional theory

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

Sjostrom, Travis; Crockett, Scott; Rudin, Sven

2016-10-03

We have performed density functional theory (DFT) based calculations for aluminum in extreme conditions of both pressure and temperature, up to five times compressed ambient density, and over 1 000 000 K in temperature. In order to cover such a domain, DFT methods including phonon calculations, quantum molecular dynamics, and orbital-free DFT are employed. Our results are then used to construct a SESAME equation of state for the aluminum 1100 alloy, encompassing the fcc, hcp, and bcc solid phases as well as the liquid regime. We also provide extensive comparison with experiment, and based on this we also provide amore » slightly modified equation of state for the aluminum 6061 alloy.« less

(Nbx, Zr1-x)4AlC3 MAX Phase Solid Solutions: Processing, Mechanical Properties, and Density Functional Theory Calculations.

PubMed

Lapauw, Thomas; Tytko, Darius; Vanmeensel, Kim; Huang, Shuigen; Choi, Pyuck-Pa; Raabe, Dierk; Caspi, El'ad N; Ozeri, Offir; To Baben, Moritz; Schneider, Jochen M; Lambrinou, Konstantina; Vleugels, Jozef

2016-06-06

The solubility of zirconium (Zr) in the Nb4AlC3 host lattice was investigated by combining the experimental synthesis of (Nbx, Zr1-x)4AlC3 solid solutions with density functional theory calculations. High-purity solid solutions were prepared by reactive hot pressing of NbH0.89, ZrH2, Al, and C starting powder mixtures. The crystal structure of the produced solid solutions was determined using X-ray and neutron diffraction. The limited Zr solubility (maximum of 18.5% of the Nb content in the host lattice) in Nb4AlC3 observed experimentally is consistent with the calculated minimum in the energy of mixing. The lattice parameters and microstructure were evaluated over the entire solubility range, while the chemical composition of (Nb0.85, Zr0.15)4AlC3 was mapped using atom probe tomography. The hardness, Young's modulus, and fracture toughness at room temperature as well as the high-temperature flexural strength and E-modulus of (Nb0.85, Zr0.15)4AlC3 were investigated and compared to those of pure Nb4AlC3. Quite remarkably, an appreciable increase in fracture toughness was observed from 6.6 ± 0.1 MPa/m(1/2) for pure Nb4AlC3 to 10.1 ± 0.3 MPa/m(1/2) for the (Nb0.85, Zr0.15)4AlC3 solid solution.

Stability of mechanical joints in launching vehicles: Local and global stationary values of energy density

NASA Astrophysics Data System (ADS)

Chue, Ching-Hwei

A method was developed for predicting the behavior of mechanical joints in launch vehicles with particular emphasis placed on how the combined effects of loading, geometry, and materials could be optimized in terms of structure instability and/or integrity. What was considered to be essential is the fluctuation of the volume energy density with time in the structure. The peaks and valleys of the volume energy density function will be associated with failure by fracture and/or yielding while the distance between their local and global stationary values govern the structure instability. The Solid Rocket Booster (SRB) of the space shuttle was analyzed under axisymmetric and non-axisymmetric loadings. A semi-analytical finite element program was developed for solving the case of non-axisymmetric loading. Following a dynamic stress analysis, contours of the volume energy density in the structure were obtained as a function of time. The magnitudes and locations of these stationary values were then calculated locally and globally and related to possible failure by fracture. In the case of axisymmetric flight, the local and global instability behavior do not change appreciably. Fluctuations in the energy density and the dynamic stability length parameter become appreciable when the non-axisymmetric loads are considered. The magnitude of the energy in the shell structure is sensitive to alterations in the gas pressure induced by the solid propellant.

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

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Nonlinear electronic excitations in crystalline solids using meta-generalized gradient approximation and hybrid functional in time-dependent density functional theory

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

Sato, Shunsuke A.; Taniguchi, Yasutaka; Department of Medical and General Sciences, Nihon Institute of Medical Science, 1276 Shimogawara, Moroyama-Machi, Iruma-Gun, Saitama 350-0435

2015-12-14

We develop methods to calculate electron dynamics in crystalline solids in real-time time-dependent density functional theory employing exchange-correlation potentials which reproduce band gap energies of dielectrics; a meta-generalized gradient approximation was proposed by Tran and Blaha [Phys. Rev. Lett. 102, 226401 (2009)] (TBm-BJ) and a hybrid functional was proposed by Heyd, Scuseria, and Ernzerhof [J. Chem. Phys. 118, 8207 (2003)] (HSE). In time evolution calculations employing the TB-mBJ potential, we have found it necessary to adopt the predictor-corrector step for a stable time evolution. We have developed a method to evaluate electronic excitation energy without referring to the energy functionalmore » which is unknown for the TB-mBJ potential. For the HSE functional, we have developed a method for the operation of the Fock-like term in Fourier space to facilitate efficient use of massive parallel computers equipped with graphic processing units. We compare electronic excitations in silicon and germanium induced by femtosecond laser pulses using the TB-mBJ, HSE, and a simple local density approximation (LDA). At low laser intensities, electronic excitations are found to be sensitive to the band gap energy: they are close to each other using TB-mBJ and HSE and are much smaller in LDA. At high laser intensities close to the damage threshold, electronic excitation energies do not differ much among the three cases.« less

The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering

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

Wei, Xialu; Rechtin, Jack; Olevsky, Eugene

Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries (ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals that the functionally graded structure can eliminate themore » delamination effect at the electrode–electrolyte interface and, therefore, retains better performance.« less

The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering

DOE PAGES

Wei, Xialu; Rechtin, Jack; Olevsky, Eugene

2017-09-14

Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries (ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals that the functionally graded structure can eliminate themore » delamination effect at the electrode–electrolyte interface and, therefore, retains better performance.« less

Conformal Electroplating of Azobenzene-Based Solar Thermal Fuels onto Large-Area and Fiber Geometries.

PubMed

Zhitomirsky, David; Grossman, Jeffrey C

2016-10-05

There is tremendous growth in fields where small functional molecules and colloidal nanomaterials are integrated into thin films for solid-state device applications. Many of these materials are synthesized in solution and there often exists a significant barrier to transition them into the solid state in an efficient manner. Here, we develop a methodology employing an electrodepositable copolymer consisting of small functional molecules for applications in solar energy harvesting and storage. We employ azobenzene solar thermal fuel polymers and functionalize them to enable deposition from low concentration solutions in methanol, resulting in uniform and large-area thin films. This approach enables conformal deposition on a variety of conducting substrates that can be either flat or structured depending on the application. Our approach further enables control over film growth via electrodepsition conditions and results in highly uniform films of hundreds of nanometers to microns in thickness. We demonstrate that this method enables superior retention of solar thermal fuel properties, with energy densities of ∼90 J/g, chargeability in the solid state, and exceptional materials utilization compared to other solid-state processing approaches. This novel approach is applicable to systems such as photon upconversion, photovoltaics, photosensing, light emission, and beyond, where small functional molecules enable solid-state applications.

Solid-state NMR studies of form I of atorvastatin calcium.

PubMed

Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

2012-03-22

Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

Nanopatterning of Surfaces with Monometallic and Heterobimetallic 1D Coordination Polymers: A Molecular Tectonics Approach at the Solid/Liquid Interface.

PubMed

El Garah, Mohamed; Marets, Nicolas; Mauro, Matteo; Aliprandi, Alessandro; Bonacchi, Sara; De Cola, Luisa; Ciesielski, Artur; Bulach, Véronique; Hosseini, Mir Wais; Samorì, Paolo

2015-07-08

The self-assembly of multiple molecular components into complex supramolecular architectures is ubiquitous in nature and constitutes one of the most powerful strategies to fabricate multifunctional nanomaterials making use of the bottom-up approach. When spatial confinement in two dimensions on a solid substrate is employed, this approach can be exploited to generate periodically ordered structures from suitably designed molecular tectons. In this study we demonstrate that physisorbed directional periodic arrays of monometallic or heterobimetallic coordination polymers can be generated on a highly oriented pyrolitic graphite surface by combinations of a suitably designed directional organic tecton or metallatecton based on a porphyrin or nickel(II) metalloporphyrin backbone bearing both a pyridyl unit and a terpyridyl unit acting as coordinating sites for CoCl2. The periodic architectures were visualized at the solid/liquid interface with a submolecular resolution by scanning tunneling microscopy and corroborated by combined density functional and time-dependent density functional theory calculations. The capacity to nanopattern the surface for the first time with two distinct metallic centers exhibiting different electronic and optical properties is a key step toward the bottom-up construction of robust multicomponent and, thus, multifunctional molecular nanostructures and nanodevices.

Structural, Electronic and Dynamical Properties of Curium Monopnictides: Density Functional Calculations

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Upadhyay, Deepak; Som, Narayan; Pillai, Sharad B.; Shinde, Satyam; Jha, Prafulla K.

2017-03-01

The structural, electronic, dynamical and thermodynamical properties of CmX (X = N, P, As, Sb, and Bi) compounds are studied using first principles calculations within density functional theory. The Perdew-Burke-Ernzerhof spin polarized generalized gradient approximation and Perdew-Wang (PW) spin polarized local density approximation as the exchange correlational functionals are used in these calculations. There is a good agreement between the present and previously reported data. The calculated electronic density of states suggests that the curium monopnictides are metallic in nature, which is consistent with earlier studies. The significant values of magnetic moment suggest their magnetic nature. The phonon dispersion curves and phonon density of states are also calculated, which depict the dynamical stability of these compounds. There is a significant separation between the optical and acoustical phonon branches. The temperature dependence of the thermodynamical functions are also calculated and discussed. Internal energy and vibrational contribution to the Helmholtz free energy increases and decreases, respectively, with temperature. The entropy increases with temperature. The specific heat at constant volume and Debye temperature obey Debye theory. The temperature variation of the considered thermodynamical functions is in line with those of other crystalline solids.

X-ray electron density investigation of chemical bonding in van der Waals materials

NASA Astrophysics Data System (ADS)

Kasai, Hidetaka; Tolborg, Kasper; Sist, Mattia; Zhang, Jiawei; Hathwar, Venkatesha R.; Filsø, Mette Ø.; Cenedese, Simone; Sugimoto, Kunihisa; Overgaard, Jacob; Nishibori, Eiji; Iversen, Bo B.

2018-03-01

Van der Waals (vdW) solids have attracted great attention ever since the discovery of graphene, with the essential feature being the weak chemical bonding across the vdW gap. The nature of these weak interactions is decisive for many extraordinary properties, but it is a strong challenge for current theory to accurately model long-range electron correlations. Here we use synchrotron X-ray diffraction data to precisely determine the electron density in the archetypal vdW solid, TiS2, and compare the results with density functional theory calculations. Quantitative agreement is observed for the chemical bonding description in the covalent TiS2 slabs, but significant differences are identified for the interactions across the gap, with experiment revealing more electron deformation than theory. The present data provide an experimental benchmark for testing theoretical models of weak chemical bonding.

Experimental and theoretical investigations of functionalized boron nitride as electrode materials for Li-ion batteries

DOE PAGES

Zhang, Fan; Nemeth, Karoly; Bareno, Javier; ...

2016-03-03

The feasibility of synthesizing functionalized h-BN (FBN) via the reaction between molten LiOH and solid h-BN is studied for the first time and its first ever application as an electrode material in Li-ion batteries is evaluated. Density functional theory (DFT) calculations are performed to provide mechanistic understanding of the possible electrochemical reactions derived from the FBN. Various materials characterizations reveal that the melt-solid reaction can lead to exfoliation and functionalization of h-BN simultaneously, while electrochemical analysis proves that the FBN can reversibly store charges through surface redox reactions with good cycle stability and coulombic efficiency. As a result, the DFTmore » calculations have provided physical insights into the observed electrochemical properties derived from the FBN.« less

Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts.

PubMed

Huang, Bing; Xiao, Li; Lu, Juntao; Zhuang, Lin

2016-05-17

A new property is reported that accurately quantifies and spatially describes the chemical reactivity of solid surfaces. The core idea is to create a reactivity weight function peaking at the Fermi level, thereby determining a weighted summation of the density of states of a solid surface. When such a weight function is defined as the derivative of the Fermi-Dirac distribution function at a certain non-zero temperature, the resulting property is the finite-temperature chemical softness, termed Fermi softness (SF ), which turns out to be an accurate descriptor of the surface reactivity. The spatial image of SF maps the reactive domain of a heterogeneous surface and even portrays morphological details of the reactive sites. SF analyses reveal that the reactive zones on a Pt3 Y(111) surface are the platinum sites rather than the seemingly active yttrium sites, and the reactivity of the S-dimer edge of MoS2 is spatially anisotropic. Our finding is of fundamental and technological significance to heterogeneous catalysis and industrial processes demanding rational design of solid catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three-particle correlation functions of quasi-two-dimensional one-component and binary colloid suspensions.

PubMed

Ho, Hau My; Lin, Binhua; Rice, Stuart A

2006-11-14

We report the results of experimental determinations of the triplet correlation functions of quasi-two-dimensional one-component and binary colloid suspensions in which the colloid-colloid interaction is short ranged. The suspensions studied range in density from modestly dilute to solid. The triplet correlation function of the one-component colloid system reveals extensive ordering deep in the liquid phase. At the same density the ordering of the larger diameter component in a binary colloid system is greatly diminished by a very small amount of the smaller diameter component. The possible utilization of information contained in the triplet correlation function in the theory of melting of a quasi-two-dimensional system is briefly discussed.

Functionally Graded Bismuth Oxide/Zirconia Bilayer Electrolytes for High-Performance Intermediate-Temperature Solid Oxide Fuel Cells (IT-SOFCs).

PubMed

Joh, Dong Woo; Park, Jeong Hwa; Kim, Doyeub; Wachsman, Eric D; Lee, Kang Taek

2017-03-15

A functionally graded Bi 1.6 Er 0.4 O 3 (ESB)/Y 0.16 Zr 0.84 O 1.92 (YSZ) bilayer electrolyte is successfully developed via a cost-effective screen printing process using nanoscale ESB powders on the tape-cast NiO-YSZ anode support. Because of the highly enhanced oxygen incorporation process at the cathode/electrolyte interface, a novel bilayer solid oxide fuel cell (SOFC) yields extremely high power density of ∼2.1 W cm -2 at 700 °C, which is a 2.4 times increase compared to that of the YSZ single electrolyte SOFC.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications.

PubMed

Huang, Chun; Zhang, Jin; Young, Neil P; Snaith, Henry J; Grant, Patrick S

2016-05-10

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices.

Chemically interconnected light-weight 3D-carbon nanotube solid network

DOE PAGES

Ozden, Sehmus; Tsafack, Thierry; Owuor, Peter S.; ...

2017-03-31

Owing to the weak physical interactions such as van der Waals and π-π interactions, which hold nanotubes together in carbon nanotube (CNT) bulk structures, the tubes can easily slide on each other. In creating covalent interconnection between individual carbon nanotube (CNT) structures we saw remarkable improvements in the properties of their three-dimensional (3D) bulk structures. The creation of such nanoengineered 3D solid structures with improved properties and low-density remains one of the fundamental challenges in real-world applications. We also report the scalable synthesis of low-density 3D macroscopic structure made of covalently interconnected nanotubes using free-radical polymerization method after functionalized CNTsmore » with allylamine monomers. The resulted interconnected highly porous solid structure exhibits higher mechanical properties, larger surface area and greater porosity than non-crosslinked nanotube structures. To gain further insights into the deformation mechanisms of nanotubes, fully atomistic reactive molecular dynamics simulations are used. Here we demonstrate one such utility in CO 2 uptake, whose interconnected solid structure performed better than non-interconnected structures.« less

Performance of the strongly constrained and appropriately normed density functional for solid-state materials

DOE PAGES

Isaacs, Eric B.; Wolverton, Chris

2018-06-22

Constructed to satisfy 17 known exact constraints for a semilocal density functional, the strongly constrained and appropriately normed (SCAN) meta-generalized-gradient-approximation functional has shown early promise for accurately describing the electronic structure of molecules and solids. One open question is how well SCAN predicts the formation energy, a key quantity for describing the thermodynamic stability of solid-state compounds. To answer this question, we perform an extensive benchmark of SCAN by computing the formation energies for a diverse group of nearly 1000 crystalline compounds for which experimental values are known. Due to an enhanced exchange interaction in the covalent bonding regime, SCANmore » substantially decreases the formation energy errors for strongly bound compounds, by approximately 50% to 110 meV/atom, as compared to the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE). However, for intermetallic compounds, SCAN performs moderately worse than PBE with an increase in formation energy error of approximately 20%, stemming from SCAN's distinct behavior in the weak bonding regime. The formation energy errors can be further reduced via elemental chemical potential fitting. We find that SCAN leads to significantly more accurate predicted crystal volumes, moderately enhanced magnetism, and mildly improved band gaps as compared to PBE. Altogether, SCAN represents a significant improvement in accurately describing the thermodynamics of strongly bound compounds.« less

Performance of the strongly constrained and appropriately normed density functional for solid-state materials

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

Isaacs, Eric B.; Wolverton, Chris

Constructed to satisfy 17 known exact constraints for a semilocal density functional, the strongly constrained and appropriately normed (SCAN) meta-generalized-gradient-approximation functional has shown early promise for accurately describing the electronic structure of molecules and solids. One open question is how well SCAN predicts the formation energy, a key quantity for describing the thermodynamic stability of solid-state compounds. To answer this question, we perform an extensive benchmark of SCAN by computing the formation energies for a diverse group of nearly 1000 crystalline compounds for which experimental values are known. Due to an enhanced exchange interaction in the covalent bonding regime, SCANmore » substantially decreases the formation energy errors for strongly bound compounds, by approximately 50% to 110 meV/atom, as compared to the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE). However, for intermetallic compounds, SCAN performs moderately worse than PBE with an increase in formation energy error of approximately 20%, stemming from SCAN's distinct behavior in the weak bonding regime. The formation energy errors can be further reduced via elemental chemical potential fitting. We find that SCAN leads to significantly more accurate predicted crystal volumes, moderately enhanced magnetism, and mildly improved band gaps as compared to PBE. Altogether, SCAN represents a significant improvement in accurately describing the thermodynamics of strongly bound compounds.« less

Differentiability of energy functionals in spin-density-functional theory

NASA Astrophysics Data System (ADS)

Gál, Tamás

2007-06-01

Recently, nonuniqueness of external electrostatic and magnetic fields yielding a given many-electron ground state has been pointed out [K. Capelle and G. Vignale, Phys. Rev. Lett. 86, 5546 (2001); H. Eschrig and W. E. Pickett, Solid State Commun. 118, 123 (2001)], implying the nondifferentiability of the ground-state energy functional of spin-density-functional theory (SDFT), on the basis of which the applicability of widely used DFT methods in SDFT has been put into question and the need for a critical reexamination of those applications has been concluded. Here it is shown, for collinear magnetic fields, that the nonuniqueness of the external potentials in SDFT does not imply the nonexistence of number-conserving functional derivatives as well, with the use of which therefore problems arising from the nondifferentiability are avoided.

Application of continuous normal-lognormal bivariate density functions in a sensitivity analysis of municipal solid waste landfill.

PubMed

Petrovic, Igor; Hip, Ivan; Fredlund, Murray D

2016-09-01

The variability of untreated municipal solid waste (MSW) shear strength parameters, namely cohesion and shear friction angle, with respect to waste stability problems, is of primary concern due to the strong heterogeneity of MSW. A large number of municipal solid waste (MSW) shear strength parameters (friction angle and cohesion) were collected from published literature and analyzed. The basic statistical analysis has shown that the central tendency of both shear strength parameters fits reasonably well within the ranges of recommended values proposed by different authors. In addition, it was established that the correlation between shear friction angle and cohesion is not strong but it still remained significant. Through use of a distribution fitting method it was found that the shear friction angle could be adjusted to a normal probability density function while cohesion follows the log-normal density function. The continuous normal-lognormal bivariate density function was therefore selected as an adequate model to ascertain rational boundary values ("confidence interval") for MSW shear strength parameters. It was concluded that a curve with a 70% confidence level generates a "confidence interval" within the reasonable limits. With respect to the decomposition stage of the waste material, three different ranges of appropriate shear strength parameters were indicated. Defined parameters were then used as input parameters for an Alternative Point Estimated Method (APEM) stability analysis on a real case scenario of the Jakusevec landfill. The Jakusevec landfill is the disposal site of the capital of Croatia - Zagreb. The analysis shows that in the case of a dry landfill the most significant factor influencing the safety factor was the shear friction angle of old, decomposed waste material, while in the case of a landfill with significant leachate level the most significant factor influencing the safety factor was the cohesion of old, decomposed waste material. The analysis also showed that a satisfactory level of performance with a small probability of failure was produced for the standard practice design of waste landfills as well as an analysis scenario immediately after the landfill closure. Copyright © 2015 Elsevier Ltd. All rights reserved.

A robust molecular probe for Ångstrom-scale analytics in liquids

PubMed Central

Nirmalraj, Peter; Thompson, Damien; Dimitrakopoulos, Christos; Gotsmann, Bernd; Dumcenco, Dumitru; Kis, Andras; Riel, Heike

2016-01-01

Traditionally, nanomaterial profiling using a single-molecule-terminated scanning probe is performed at the vacuum–solid interface often at a few Kelvin, but is not a notion immediately associated with liquid–solid interface at room temperature. Here, using a scanning tunnelling probe functionalized with a single C60 molecule stabilized in a high-density liquid, we resolve low-dimensional surface defects, atomic interfaces and capture Ångstrom-level bond-length variations in single-layer graphene and MoS2. Atom-by-atom controllable imaging contrast is demonstrated at room temperature and the electronic structure of the C60–metal probe complex within the encompassing liquid molecules is clarified using density functional theory. Our findings demonstrates that operating a robust single-molecular probe is not restricted to ultra-high vacuum and cryogenic settings. Hence the scope of high-precision analytics can be extended towards resolving sub-molecular features of organic elements and gauging ambient compatibility of emerging layered materials with atomic-scale sensitivity under experimentally less stringent conditions. PMID:27516157

Role of Dynamically Frustrated Bond Disorder in a Li + Superionic Solid Electrolyte

DOE PAGES

Adelstein, Nicole; Wood, Brandon C.

2016-09-16

Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li + solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li + mobility, and are enabled thermallymore » by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li 3InBr 6 by temporarily stabilizing configurations favorable for migrating Li +. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.« less

Phase diagram of two-dimensional hard ellipses.

PubMed

Bautista-Carbajal, Gustavo; Odriozola, Gerardo

2014-05-28

We report the phase diagram of two-dimensional hard ellipses as obtained from replica exchange Monte Carlo simulations. The replica exchange is implemented by expanding the isobaric ensemble in pressure. The phase diagram shows four regions: isotropic, nematic, plastic, and solid (letting aside the hexatic phase at the isotropic-plastic two-step transition [E. P. Bernard and W. Krauth, Phys. Rev. Lett. 107, 155704 (2011)]). At low anisotropies, the isotropic fluid turns into a plastic phase which in turn yields a solid for increasing pressure (area fraction). Intermediate anisotropies lead to a single first order transition (isotropic-solid). Finally, large anisotropies yield an isotropic-nematic transition at low pressures and a high-pressure nematic-solid transition. We obtain continuous isotropic-nematic transitions. For the transitions involving quasi-long-range positional ordering, i.e., isotropic-plastic, isotropic-solid, and nematic-solid, we observe bimodal probability density functions. This supports first order transition scenarios.

Characterization of oxygen defects in diamond by means of density functional theory calculations

NASA Astrophysics Data System (ADS)

Thiering, Gergő; Gali, Adam

2016-09-01

Point defects in diamond are of high interest as candidates for realizing solid state quantum bits, bioimaging agents, or ultrasensitive electric or magnetic field sensors. Various artificial diamond synthesis methods should introduce oxygen contamination in diamond, however, the incorporation of oxygen into diamond crystal and the nature of oxygen-related point defects are largely unknown. Oxygen may be potentially interesting as a source of quantum bits or it may interact with other point defects which are well established solid state qubits. Here we employ plane-wave supercell calculations within density functional theory, in order to characterize the electronic and magneto-optical properties of various oxygen-related defects. Besides the trivial single interstitial and substitutional oxygen defects we also consider their complexes with vacancies and hydrogen atoms. We find that oxygen defects are mostly electrically active and introduce highly correlated orbitals that pose a challenge for density functional theory modeling. Nevertheless, we are able to identify the fingerprints of substitutional oxygen defect, the oxygen-vacancy and oxygen-vacancy-hydrogen complexes in the electron paramagnetic resonance spectrum. We demonstrate that first principles calculations can predict the motional averaging of the electron paramagnetic resonance spectrum of defects that are subject to Jahn-Teller distortion. We show that the high-spin neutral oxygen-vacancy defect exhibits very fast nonradiative decay from its optical excited state that might hinder applying it as a qubit.

Speckle tracking and speckle content based composite strain imaging for solid and fluid filled lesions.

PubMed

Rabbi, Md Shifat-E; Hasan, Md Kamrul

2017-02-01

Strain imaging though for solid lesions provides an effective way for determining their pathologic condition by displaying the tissue stiffness contrast, for fluid filled lesions such an imaging is yet an open problem. In this paper, we propose a novel speckle content based strain imaging technique for visualization and classification of fluid filled lesions in elastography after automatic identification of the presence of fluid filled lesions. Speckle content based strain, defined as a function of speckle density based on the relationship between strain and speckle density, gives an indirect strain value for fluid filled lesions. To measure the speckle density of the fluid filled lesions, two new criteria based on oscillation count of the windowed radio frequency signal and local variance of the normalized B-mode image are used. An improved speckle tracking technique is also proposed for strain imaging of the solid lesions and background. A wavelet-based integration technique is then proposed for combining the strain images from these two techniques for visualizing both the solid and fluid filled lesions from a common framework. The final output of our algorithm is a high quality composite strain image which can effectively visualize both solid and fluid filled breast lesions in addition to the speckle content of the fluid filled lesions for their discrimination. The performance of our algorithm is evaluated using the in vivo patient data and compared with recently reported techniques. The results show that both the solid and fluid filled lesions can be better visualized using our technique and the fluid filled lesions can be classified with good accuracy. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of solid distribution on elastic properties of open-cell cellular solids using numerical and experimental methods.

PubMed

Zargarian, A; Esfahanian, M; Kadkhodapour, J; Ziaei-Rad, S

2014-09-01

Effect of solid distribution between edges and vertices of three-dimensional cellular solid with an open-cell structure was investigated both numerically and experimentally. Finite element analysis (FEA) with continuum elements and appropriate periodic boundary condition was employed to calculate the elastic properties of cellular solids using tetrakaidecahedral (Kelvin) unit cell. Relative densities between 0.01 and 0.1 and various values of solid fractions were considered. In order to validate the numerical model, three scaffolds with the relative density of 0.08, but different amounts of solid in vertices, were fabricated via 3-D printing technique. Good agreement was observed between numerical simulation and experimental results. Results of numerical simulation showed that, at low relative densities (<0.03), Young׳s modulus increased by shifting materials away from edges to vertices at first and then decreased after reaching a critical point. However, for the high values of relative density, Young׳s modulus increased monotonically. Mechanisms of such a behavior were discussed in detail. Results also indicated that Poisson׳s ratio decreased by increasing relative density and solid fraction in vertices. By fitting a curve to the data obtained from the numerical simulation and considering the relative density and solid fraction in vertices, empirical relations were derived for Young׳s modulus and Poisson׳s ratio. Copyright © 2014 Elsevier Ltd. All rights reserved.

Structure determination and characterization of two rare-earth molybdenum borate compounds: LnMoBO(6) (Ln = La, Ce).

PubMed

Zhao, Dan; Cheng, Wen-Dan; Zhang, Hao; Hang, Shu-Ping; Fang, Ming

2008-07-28

The structural, optical, and electronic properties of two rare-earth molybdenum borate compounds, LnMoBO(6) (Ln = La, Ce), have been investigated by means of single-crystal X-ray diffraction, elemental analyses, and spectral measurements, as well as calculations of energy band structures, density of states, and optical response functions by the density functional method. The title compounds, which crystallize in monoclinic space group P2(1)/c, possess a similar network of interconnected [Ce(2)(MoO(4))(2)](2+) chains and [BO(2)](-) wavy chains. Novel 1D molybdenum oxide chains are contained in their three-dimensional (3D) networks. The calculated results of crystal energy band structure by the density functional theory (DFT) method show that the solid-state compound LaMoBO(6) is a semiconductor with indirect band gaps.

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

NASA Astrophysics Data System (ADS)

Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Arias, T. A.; Hennig, Richard G.

2014-02-01

Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the SN2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the SN2 reaction.

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

Ozden, Sehmus; Tsafack, Thierry; Owuor, Peter S.

Owing to the weak physical interactions such as van der Waals and π-π interactions, which hold nanotubes together in carbon nanotube (CNT) bulk structures, the tubes can easily slide on each other. In creating covalent interconnection between individual carbon nanotube (CNT) structures we saw remarkable improvements in the properties of their three-dimensional (3D) bulk structures. The creation of such nanoengineered 3D solid structures with improved properties and low-density remains one of the fundamental challenges in real-world applications. We also report the scalable synthesis of low-density 3D macroscopic structure made of covalently interconnected nanotubes using free-radical polymerization method after functionalized CNTsmore » with allylamine monomers. The resulted interconnected highly porous solid structure exhibits higher mechanical properties, larger surface area and greater porosity than non-crosslinked nanotube structures. To gain further insights into the deformation mechanisms of nanotubes, fully atomistic reactive molecular dynamics simulations are used. Here we demonstrate one such utility in CO 2 uptake, whose interconnected solid structure performed better than non-interconnected structures.« less

Importance of oxygen in the metal-free catalytic growth of single-walled carbon nanotubes from SiO(x) by a vapor-solid-solid mechanism.

PubMed

Liu, Bilu; Tang, Dai-Ming; Sun, Chenghua; Liu, Chang; Ren, Wencai; Li, Feng; Yu, Wan-Jing; Yin, Li-Chang; Zhang, Lili; Jiang, Chuanbin; Cheng, Hui-Ming

2011-01-19

To understand in-depth the nature of the catalyst and the growth mechanism of single-walled carbon nanotubes (SWCNTs) on a newly developed silica catalyst, we performed this combined experimental and theoretical study. In situ transmission electron microscopy (TEM) observations revealed that the active catalyst for the SWCNT growth is solid and amorphous SiO(x) nanoparticles (NPs), suggesting a vapor-solid-solid growth mechanism. From in situ TEM and chemical vapor deposition growth experiments, we found that oxygen plays a crucial role in SWCNT growth in addition to the well-known catalyst size effect. Density functional theory calculations showed that oxygen atoms can enhance the capture of -CH(x) and consequently facilitate the growth of SWCNTs on oxygen-containing SiO(x) NPs.

Solid H2 in the interstellar medium

NASA Astrophysics Data System (ADS)

Füglistaler, A.; Pfenniger, D.

2018-06-01

Context. Condensation of H2 in the interstellar medium (ISM) has long been seen as a possibility, either by deposition on dust grains or thanks to a phase transition combined with self-gravity. H2 condensation might explain the observed low efficiency of star formation and might help to hide baryons in spiral galaxies. Aims: Our aim is to quantify the solid fraction of H2 in the ISM due to a phase transition including self-gravity for different densities and temperatures in order to use the results in more complex simulations of the ISM as subgrid physics. Methods: We used molecular dynamics simulations of fluids at different temperatures and densities to study the formation of solids. Once the simulations reached a steady state, we calculated the solid mass fraction, energy increase, and timescales. By determining the power laws measured over several orders of magnitude, we extrapolated to lower densities the higher density fluids that can be simulated with current computers. Results: The solid fraction and energy increase of fluids in a phase transition are above 0.1 and do not follow a power law. Fluids out of a phase transition are still forming a small amount of solids due to chance encounters of molecules. The solid mass fraction and energy increase of these fluids are linearly dependent on density and can easily be extrapolated. The timescale is below one second, the condensation can be considered instantaneous. Conclusions: The presence of solid H2 grains has important dynamic implications on the ISM as they may be the building blocks for larger solid bodies when gravity is included. We provide the solid mass fraction, energy increase, and timescales for high density fluids and extrapolation laws for lower densities.

Modelling of the Thermo-Physical and Physical Properties for Solidification of Al-Alloys

NASA Astrophysics Data System (ADS)

Saunders, N.; Li, X.; Miodownik, A. P.; Schillé, J.-P.

The thermo-physical and physical properties of the liquid and solid phases are critical components in casting simulations. Such properties include the fraction solid transformed, enthalpy release, thermal conductivity, volume and density, all as a function of temperature. Due to the difficulty in experimentally determining such properties at solidification temperatures, little information exists for multi-component alloys. As part of the development of a new computer program for modelling of materials properties (JMatPro) extensive work has been carried out on the development of sound, physically based models for these properties. Wide ranging results will presented for Al-based alloys, which will include more detailed information concerning the density change of the liquid that intrinsically occurs during solidification due to its change in composition.

The role of surface ligands in determining the electronic properties of quantum dot solids and their impact on photovoltaic figure of merits.

PubMed

Goswami, Prasenjit N; Mandal, Debranjan; Rath, Arup K

2018-01-18

Surface chemistry plays a crucial role in determining the electronic properties of quantum dot solids and may well be the key to mitigate loss processes involved in quantum dot solar cells. Surface ligands help to maintain the shape and size of the individual dots in solid films, to preserve the clean energy band gap of the individual particles and to control charge carrier conduction across solid films, in turn regulating their performance in photovoltaic applications. In this report, we show that the changes in size, shape and functional groups of small chain organic ligands enable us to modulate mobility, dielectric constant and carrier doping density of lead sulfide quantum dot solids. Furthermore, we correlate these results with performance, stability and recombination processes in the respective photovoltaic devices. Our results highlight the critical role of surface chemistry in the electronic properties of quantum dots. The role of the size, functionality and the surface coverage of the ligands in determining charge transport properties and the stability of quantum dot solids have been discussed. Our findings, when applied in designing new ligands with higher mobility and improved passivation of quantum dot solids, can have important implications for the development of high-performance quantum dot solar cells.

Application of Van Der Waals Density Functional Theory to Study Physical Properties of Energetic Materials

NASA Astrophysics Data System (ADS)

Conroy, M. W.; Budzevich, M. M.; Lin, Y.; Oleynik, I. I.; White, C. T.

2009-12-01

An empirical correction to account for van der Waals interactions based on the work of Neumann and Perrin [J. Phys. Chem. B 109, 15531 (2005)] was applied to density functional theory calculations of energetic molecular crystals. The calculated equilibrium unit-cell volumes of FOX-7, β-HMX, solid nitromethane, PETN-I, α-RDX, and TATB show a significant improvement in the agreement with experimental results. Hydrostatic-compression simulations of β-HMX, PETN-I, and α-RDX were also performed. The isothermal equations of state calculated from the results show increased agreement with experiment in the pressure intervals studied.

Combining Nuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations to Characterize Carvedilol Polymorphs.

PubMed

Rezende, Carlos A; San Gil, Rosane A S; Borré, Leandro B; Pires, José Ricardo; Vaiss, Viviane S; Resende, Jackson A L C; Leitão, Alexandre A; De Alencastro, Ricardo B; Leal, Katia Z

2016-09-01

The experiments of carvedilol form II, form III, and hydrate by (13)C and (15)N cross-polarization magic-angle spinning (CP MAS) are reported. The GIPAW (gauge-including projector-augmented wave) method from DFT (density functional theory) calculations was used to simulate (13)C and (15)N chemical shifts. A very good agreement was found for the comparison between the global results of experimental and calculated nuclear magnetic resonance (NMR) chemical shifts for carvedilol polymorphs. This work aims a comprehensive understanding of carvedilol crystalline forms employing solution and solid-state NMR as well as DFT calculations. Copyright © 2016. Published by Elsevier Inc.

Quantum Stress: Density Functional Theory Formulation and Physical Manifestation

NASA Astrophysics Data System (ADS)

Hu, Hao; Liu, Feng

2012-02-01

The concept of ``quantum stress (QS)'' is introduced and formulated within density functional theory (DFT), to underlie extrinsic electronic effects on the stress state of solids and thin films in the absence of lattice strain. An explicit expression of QS (σ^Q) is derived in relation to the deformation potential of electronic states (ξ) and the variation of electron density (δn), σ^Q=ξ(δn), as a quantum analog of classical Hook's law. Two distinct QS manifestations are demonstrated quantitatively by DFT calculations: (1) in the form of bulk stress induced by charge carriers; and (2) in the form of surface stress induced by quantum confinement. QS has broad implications in physical phenomena and technological applications that are based on coupling of electronic structure with lattice strain.

Recent progress in density functional theory

NASA Astrophysics Data System (ADS)

Truhlar, Donald

2014-03-01

Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.

Profile structures of the voltage-sensor domain and the voltage-gated K+-channel vectorially oriented in a single phospholipid bilayer membrane at the solid-vapor and solid-liquid interfaces determined by x-ray interferometry

PubMed Central

Gupta, S.; Liu, J.; Strzalka, J.; Blasie, J. K.

2011-01-01

One subunit of the prokaryotic voltage-gated potassium ion channel from Aeropyrum pernix (KvAP) is comprised of six transmembrane α helices, of which S1–S4 form the voltage-sensor domain (VSD) and S5 and S6 contribute to the pore domain (PD) of the functional homotetramer. However, the mechanism of electromechanical coupling interconverting the closed-to-open (i.e., nonconducting-to-K+-conducting) states remains undetermined. Here, we have vectorially oriented the detergent (OG)-solubilized VSD in single monolayers by two independent approaches, namely “directed-assembly” and “self-assembly,” to achieve a high in-plane density. Both utilize Ni coordination chemistry to tether the protein to an alkylated inorganic surface via its C-terminal His6 tag. Subsequently, the detergent is replaced by phospholipid (POPC) via exchange, intended to reconstitute a phospholipid bilayer environment for the protein. X-ray interferometry, in which interference with a multilayer reference structure is used to both enhance and phase the specular x-ray reflectivity from the tethered single membrane, was used to determine directly the electron density profile structures of the VSD protein solvated by detergent versus phospholipid, and with either a moist He (moderate hydration) or bulk aqueous buffer (high hydration) environment to preserve a native structure conformation. Difference electron density profiles, with respect to the multilayer substrate itself, for the VSD-OG monolayer and VSD-POPC membranes at both the solid-vapor and solid-liquid interfaces, reveal the profile structures of the VSD protein dominating these profiles and further indicate a successful reconstitution of a lipid bilayer environment. The self-assembly approach was similarly extended to the intact full-length KvAP channel for comparison. The spatial extent and asymmetry in the profile structures of both proteins confirm their unidirectional vectorial orientation within the reconstituted membrane and indicate retention of the protein’s folded three-dimensional tertiary structure upon completion of membrane bilayer reconstitution. Moreover, the resulting high in-plane density of vectorially oriented protein within a fully hydrated single phospholipid bilayer membrane at the solid-liquid interface will enable investigation of their conformational states as a function of the transmembrane electric potential. PMID:22060407

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

Stability and ionic mobility in argyrodite-related lithium-ion solid electrolytes.

PubMed

Chen, Hao Min; Maohua, Chen; Adams, Stefan

2015-07-07

In the search for fast lithium-ion conducting solids for the development of safe rechargeable all-solid-state batteries with high energy density, thiophosphates and related compounds have been demonstrated to be particularly promising both because of their record ionic conductivities and their typically low charge transfer resistances. In this work we explore a wide range of known and predicted thiophosphates with a particular focus on the cubic argyrodite phase with a robust three-dimensional network of ion migration pathways. Structural and hydrolysis stability are calculated employing density functional method in combination with a generally applicable method of predicting the relevant critical reaction. The activation energy for ion migration in these argyrodites is then calculated using the empirical bond valence pathway method developed in our group, while bandgaps of selected argyrodites are calculated as a basis for assessing the electrochemical window. Findings for the lithium compounds are also compared to those of previously known copper argyrodites and hypothetical sodium argyrodites. Therefrom, guidelines for experimental work are derived to yield phases with the optimum balance between chemical stability and ionic conductivity in the search for practical lithium and sodium solid electrolyte materials.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications

PubMed Central

Huang, Chun; Zhang, Jin; Young, Neil P.; Snaith, Henry J.; Grant, Patrick S.

2016-01-01

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices. PMID:27161379

Using Solution- and Solid-State S K-edge X-ray Absorption Spectroscopy with Density Functional Theory to Evaluate M–S Bonding for MS42- (M = Cr, Mo, W) Dianions

PubMed Central

Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Daly, Scott R.; Kozimor, Stosh A.; MacInnes, Molly M.; Martin, Richard L.; Scott, Brian L.

2014-01-01

Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions. PMID:25311904

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

PubMed

Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

2014-12-14

Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

Solid-state diffusion in amorphous zirconolite

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

Yang, C.; Dove, M. T.; Trachenko, K.

2014-11-14

We discuss how structural disorder and amorphization affect solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffusion constants, but does not change the activation energy in the density range considered. We also findmore » that atomic species in zirconolite are affected differently by amorphization and density change. Our microscopic insights are relevant for understanding how solid-state diffusion changes due to disorder and for building predictive models of operation of materials to be used to encapsulate nuclear waste.« less

Cationic flocculants carrying hydrophobic functionalities: applications for solid/liquid separation.

PubMed

Schwarz, S; Jaeger, W; Paulke, B-R; Bratskaya, S; Smolka, N; Bohrisch, J

2007-07-26

The flocculation behaviors of three series of polycations with narrow molecular weight distributions carrying hydrophobic substituents on their backbones [poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride), poly(N-vinylbenzyl-N,N-dimethyl-N-butylammonium chloride), and poly(N-vinylbenzylpyridinium chloride)] were investigated in dispersions of monodisperse polystyrene latexes and kaolin. Apparently, the charge density of the polycations decreases with increasing substituent hydrophobicity and increasing molecular weight of the polyelectrolytes. The necessary amount of flocculant for phase separation in dispersions with high substrate surface charge densities increases with increasing hydrophobicity of the polyelectrolyte. Nevertheless, the introduction of hydrophobic functionalities is beneficial, resulting in a substantial broadening of the range between the minimum and maximum amounts of flocculant necessary for efficient flocculation (flocculation window). An increase in ionic strength supports this effect. When the substrate has a low charge density, the hydrophobic interactions play a much more significant role in the flocculation process. Here, the minimum efficient doses remained the same for all three polyelectrolytes investigated, but the width of the flocculation window increased as the polycation hydrophobicity and the molecular weight increased. The necessary amount of flocculant increased with an increase in particle size at constant solid content of the dispersion, as well as with a decreasing number of particles at a constant particle size.

Transparent, flexible supercapacitors from nano-engineered carbon films.

PubMed

Jung, Hyun Young; Karimi, Majid B; Hahm, Myung Gwan; Ajayan, Pulickel M; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Transparent, flexible supercapacitors from nano-engineered carbon films

PubMed Central

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications. PMID:23105970

Transparent, flexible supercapacitors from nano-engineered carbon films

NASA Astrophysics Data System (ADS)

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-10-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Analysis of noise from reusable solid rocket motor firings

NASA Astrophysics Data System (ADS)

Jerome, Trevor W.; Gee, Kent L.; Neilsen, Tracianne B.

2012-10-01

As part of investigations into the design of next-generation launch vehicles, near and far-field data were collected during horizontal static firings of reusable solid rocket motors. Spatial variation of overall and one-third octave band pressure levels at sideline and polar arc arrays is analyzed. Spectra at individual microphone locations were analyzed. Positively-skewed pressure waveforms were observed in the probability density functions. Extreme skewness in the first-order estimate of the time derivative was found as a result of the presence of significant acoustic shocks.

Periodic subsystem density-functional theory

NASA Astrophysics Data System (ADS)

Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

2014-11-01

By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn-Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn-Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.

Periodic subsystem density-functional theory.

PubMed

Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

2014-11-07

By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn-Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn-Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.

Periodic subsystem density-functional theory

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

Genova, Alessandro; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu; Ceresoli, Davide

2014-11-07

By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dualmore » approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.« less

Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Wu, Tao

We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the substrate after completion of polymerization, we show the grafting density of the polymers grafted to flexible substrates can be tuned as a function of Deltax.

Ionic and electronic transport properties in dense plasmas by orbital-free density functional theory

DOE PAGES

Sjostrom, Travis; Daligault, Jérôme

2015-12-09

We validate the application of our recent orbital-free density functional theory (DFT) approach, [Phys. Rev. Lett. 113, 155006 (2014)], for the calculation of ionic and electronic transport properties of dense plasmas. To this end, we calculate the self-diffusion coefficient, the viscosity coefficient, the electrical and thermal conductivities, and the reflectivity coefficient of hydrogen and aluminum plasmas. Very good agreement is found with orbital-based Kohn-Sham DFT calculations at lower temperatures. Because the computational costs of the method do not increase with temperature, we can produce results at much higher temperatures than is accessible by the Kohn-Sham method. Our results for warmmore » dense aluminum at solid density are inconsistent with the recent experimental results reported by Sperling et al. [Phys. Rev. Lett. 115, 115001 (2015)].« less

Obtaining macroscopic quantities for the contact line problem from Density Functional Theory using asymptotic methods

NASA Astrophysics Data System (ADS)

Sibley, David; Nold, Andreas; Kalliadasis, Serafim

2015-11-01

Density Functional Theory (DFT), a statistical mechanics of fluids approach, captures microscopic details of the fluid density structure in the vicinity of contact lines, as seen in computations in our recent study. Contact lines describe the location where interfaces between two fluids meet solid substrates, and have stimulated a wealth of research due to both their ubiquity in nature and technological applications and also due to their rich multiscale behaviour. Whilst progress can be made computationally to capture the microscopic to mesoscopic structure from DFT, complete analytical results to fully bridge to the macroscale are lacking. In this work, we describe our efforts to bring asymptotic methods to DFT to obtain results for contact angles and other macroscopic quantities in various parameter regimes. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.

Nature of isomerism of solid isothiourea salts, inhibitors of nitric oxide synthases, as studied by 1H-14N nuclear quadrupole double resonance, X-ray, and density functional theory/quantum theory of atoms in molecules.

PubMed

Latosińska, J N; Latosińska, M; Seliger, J; Žagar, V; Maurin, J K; Kazimierczuk, Z

2012-02-09

Isothioureas, inhibitors of nitric oxide synthases, have been studied experimentally in solid state by nuclear quadrupole double resonance (NQDR) and X-ray methods and theoretically by the quantum theory of atoms in molecules/density functional theory. Resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each molecule. The crystal packings of (S)-3,4-dichlorobenzyl-N-methylisothiouronium chloride with the disordered chlorine positions in benzene ring and (S)-butyloisothiouronium bromide have been resolved in X-ray diffraction studies. (14)N NQDR spectra have been found good indicators of isomer type and strength of intra- or intermolecular N-H···X (X = Cl, Br) interactions. From among all salts studied, only for (S)-2,3,4,5,6-pentabromobenzylisothiouronium chloride are both nitrogen sites equivalent, which has been explained by the slow exchange. This unique structural feature can be a key factor in the high biological activity of (S)-2,3,4,5,6-pentabromobenzylisothiouronium salts.

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

Song, Jong-Won; Hirao, Kimihiko

Long-range corrected density functional theory (LC-DFT) attracts many chemists’ attentions as a quantum chemical method to be applied to large molecular system and its property calculations. However, the expensive time cost to evaluate the long-range HF exchange is a big obstacle to be overcome to be applied to the large molecular systems and the solid state materials. Upon this problem, we propose a linear-scaling method of the HF exchange integration, in particular, for the LC-DFT hybrid functional.

Theoretical analysis for the specific heat and thermal parameters of solid C60

NASA Astrophysics Data System (ADS)

Soto, J. R.; Calles, A.; Castro, J. J.

1997-08-01

We present the results of a theoretical analysis for the thermal parameters and phonon contribution to the specific heat in solid C60. The phonon contribution to the specific heat is calculated through the solution of the corresponding dynamical matrix, for different points in the Brillouin zone, and the construccion of the partial and generalized phonon density of states. The force constants are obtained from a first principle calculation, using a SCF Hartree-Fock wave function from the Gaussian 92 program. The thermal parameters reported are the effective temperatures and vibrational amplitudes as a function of temperature. Using this model we present a parametization scheme in order to reproduce the general behaviour of the experimental specific heat for these materials.

Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery

PubMed Central

Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

2016-01-01

α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm−2. At 1.0 V of cell voltage, a current density of 324 mA cm−2 is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm−2, and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte. PMID:27646032

Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery.

PubMed

Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

2016-09-20

α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm(-2). At 1.0 V of cell voltage, a current density of 324 mA cm(-2) is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm(-2), and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

Structural, elastic, electronic and dynamical properties of OsB and ReB: Density functional calculations

NASA Astrophysics Data System (ADS)

Li, Yanling; Zeng, Zhi; Lin, Haiqing

2010-06-01

The structural, elastic, electronic and dynamical properties of ReB and OsB are investigated by first-principles calculations based on density functional theory. It turns out that ReB and OsB are metallic ultra-incompressible solids with small elastic anisotropy and high hardness. The change of c/ a ratio in OsB indicates that there is a structural phase transition at about 31 GPa. Phonon spectra calculations show that both OsB and ReB are stable dynamically and there are abnormal phonon dispersions along special directions in Brillouin zone. OsB and ReB do not show superconductivity due to very weak electron-phonon interactions in them.

Data for the synthesis of resorcinol-formaldehyde aerogels in acidic and basic media.

PubMed

Molina-Campos, Daniel F; Fonseca-Correa, Rafael A; Vargas-Delgadillo, Diana P; Giraldo, Liliana; Moreno-Piraján, Juan Carlos

2017-06-01

The aim of this research is to synthesise carbon aerogels and to compare the differences in their textural, morphological and chemical properties when synthesised in basic and acidic media, and with two different types of pretreatment carbonization and activation with CO 2 . Four samples are prepared and characterised using TGA-DTA, SEM, DRX, isotherm determination of N 2 adsorption-desorption at -196 °C and immersion calorimetry. The data for pore distribution are reported using non-local density functional theory and quenched solid density functional theory. Finally, with the immersion calorimetry data, the consistency between the results using this technique and those obtained using the nitrogen isotherms is analysed.

Structural and electronic properties of M-MOF-74 (M = Mg, Co or Mn)

NASA Astrophysics Data System (ADS)

de Oliveira, Aline; de Lima, Guilherme Ferreira; De Abreu, Heitor Avelino

2018-01-01

The Metal-Organic Frameworks M-MOF-74 (M = Mg, Co or Mn) were investigated through Density Functional Theory calculations. Structural parameters and band gap energies were determined in agreement with experimental data, with errors under 2%. The methods Electron Localization Function and Quantum Theory of Atoms in Molecules were applied to the analyses of the electronic density topology of the three solids. These methodologies indicated that the bonds between the metallic cations and the oxygen atoms are predominantly ionic while the other ones are predominantly covalent. Furthermore, non-conventional hydrogen bonds were identified to Mg-MOF-74 and Co-MOF-74, which were not observed to Mn-MOF-74.

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

PubMed

Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

2011-11-23

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

Some Fundamental Issues in Ground-State Density Functional Theory: A Guide for the Perplexed.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Constantin, Lucian A; Sun, Jianwei; Csonka, Gábor I

2009-04-14

Some fundamental issues in ground-state density functional theory are discussed without equations: (1) The standard Hohenberg-Kohn and Kohn-Sham theorems were proven for a Hamiltonian that is not quite exact for real atoms, molecules, and solids. (2) The density functional for the exchange-correlation energy, which must be approximated, arises from the tendency of electrons to avoid one another as they move through the electron density. (3) In the absence of a magnetic field, either spin densities or total electron density can be used, although the former choice is better for approximations. (4) "Spin contamination" of the determinant of Kohn-Sham orbitals for an open-shell system is not wrong but right. (5) Only to the extent that symmetries of the interacting wave function are reflected in the spin densities should those symmetries be respected by the Kohn-Sham noninteracting or determinantal wave function. Functionals below the highest level of approximations should however sometimes break even those symmetries, for good physical reasons. (6) Simple and commonly used semilocal (lower-level) approximations for the exchange-correlation energy as a functional of the density can be accurate for closed systems near equilibrium and yet fail for open systems of fluctuating electron number. (7) The exact Kohn-Sham noninteracting state need not be a single determinant, but common approximations can fail when it is not. (8) Over an open system of fluctuating electron number, connected to another such system by stretched bonds, semilocal approximations make the exchange-correlation energy and hole-density sum rule too negative. (9) The gap in the exact Kohn-Sham band structure of a crystal underestimates the real fundamental gap but may approximate the first exciton energy in the large-gap limit. (10) Density functional theory is not really a mean-field theory, although it looks like one. The exact functional includes strong correlation, and semilocal approximations often overestimate the strength of static correlation through their semilocal exchange contributions. (11) Only under rare conditions can excited states arise directly from a ground-state theory.

Efficient chemical potential evaluation with kinetic Monte Carlo method and non-uniform external potential: Lennard-Jones fluid, liquid, and solid

NASA Astrophysics Data System (ADS)

Ustinov, E. A.

2017-07-01

The aim of this paper is to present a method of a direct evaluation of the chemical potential of fluid, liquid, and solid with kinetic Monte Carlo simulation. The method is illustrated with the 12-6 Lennard-Jones (LJ) system over a wide range of density and temperature. A distinctive feature of the methodology used in the present study is imposing an external potential on the elongated simulation box to split the system into two equilibrium phases, one of which is substantially diluted. This technique provides a reliable direct evaluation of the chemical potential of the whole non-uniform system (including that of the uniformly distributed dense phase in the central zone of the box), which, for example, is impossible in simulation of the uniform crystalline phase. The parameters of the vapor-liquid, liquid-solid, and fluid-solid transitions have been reliably determined. The chemical potential and the pressure are defined as thermodynamically consistent functions of density and temperature separately for the liquid and the solid (FCC) phases. It has been shown that in two-phase systems separated by a flat interface, the crystal melting always occurs at equilibrium conditions. It is also proved that in the limit of zero temperature, the specific heat capacity of an LJ crystal at constant volume is exactly 3Rg (where Rg is the gas constant) without resorting to harmonic oscillators.

Solid lipid nanoparticles as a vehicle for brain-targeted drug delivery: two new strategies of functionalization with apolipoprotein E

NASA Astrophysics Data System (ADS)

Rute Neves, Ana; Fontes Queiroz, Joana; Weksler, Babette; Romero, Ignacio A.; Couraud, Pierre-Olivier; Reis, Salette

2015-12-01

Nanotechnology can be an important tool to improve the permeability of some drugs for the blood-brain barrier. In this work we created a new system to enter the brain by functionalizing solid lipid nanoparticles with apolipoprotein E, aiming to enhance their binding to low-density lipoprotein receptors on the blood-brain barrier endothelial cells. Solid lipid nanoparticles were successfully functionalized with apolipoprotein E using two distinct strategies that took advantage of the strong interaction between biotin and avidin. Transmission electron microscopy images revealed spherical nanoparticles, and dynamic light scattering gave a Z-average under 200 nm, a polydispersity index below 0.2, and a zeta potential between -10 mV and -15 mV. The functionalization of solid lipid nanoparticles with apolipoprotein E was demonstrated by infrared spectroscopy and fluorimetric assays. In vitro cytotoxic effects were evaluated by MTT and LDH assays in the human cerebral microvascular endothelial cells (hCMEC/D3) cell line, a human blood-brain barrier model, and revealed no toxicity up to 1.5 mg ml-1 over 4 h of incubation. The brain permeability was evaluated in transwell devices with hCMEC/D3 monolayers, and a 1.5-fold increment in barrier transit was verified for functionalized nanoparticles when compared with non-functionalized ones. The results suggested that these novel apolipoprotein E-functionalized nanoparticles resulted in dynamic stable systems capable of being used for an improved and specialized brain delivery of drugs through the blood-brain barrier.

The mechanics and design of a lightweight three-dimensional graphene assembly

PubMed Central

Qin, Zhao; Jung, Gang Seob; Kang, Min Jeong; Buehler, Markus J.

2017-01-01

Recent advances in three-dimensional (3D) graphene assembly have shown how we can make solid porous materials that are lighter than air. It is plausible that these solid materials can be mechanically strong enough for applications under extreme conditions, such as being a substitute for helium in filling up an unpowered flight balloon. However, knowledge of the elastic modulus and strength of the porous graphene assembly as functions of its structure has not been available, preventing evaluation of its feasibility. We combine bottom-up computational modeling with experiments based on 3D-printed models to investigate the mechanics of porous 3D graphene materials, resulting in new designs of carbon materials. Our study reveals that although the 3D graphene assembly has an exceptionally high strength at relatively high density (given the fact that it has a density of 4.6% that of mild steel and is 10 times as strong as mild steel), its mechanical properties decrease with density much faster than those of polymer foams. Our results provide critical densities below which the 3D graphene assembly starts to lose its mechanical advantage over most polymeric cellular materials. PMID:28070559

Pressureless sintered beta prime-Si3N4 solid solution: Fabrication, microstructure, and strength

NASA Technical Reports Server (NTRS)

Dutta, S.

1977-01-01

Si3N4, AlN, and Al2O3 were used as basic constituents in a study of the pressureless sintering of beta prime-Si3N4 solid solution as a function of temperature. Y2O3-SiO2 additions were used to promote liquid-phase sintering. The sintered specimens were characterized with respect to density, microstructure, strength, oxidation, and thermal shock resistance. Density greater than 98 percent of theoretical was achieved by pressureless sintering at 1750 C. The microstructure consisted essentially of fine-grained beta prime-Si3N4 solid solution as the major phase. Modulus of rupture strengths up to 483 MPa were achieved at moderate temperature (1000 C), but decreased to 228 MPa at 1380 C. This substantial strength loss was attributed to a glassy grain boundary phase formed during cooling from the sintering temperature. The best oxidation resistance was exhibited by a composition containing 3 mol % Y2O3-SiO2 additives. Water quench thermal shock resistance was equivalent to that of reaction sintered silicon nitride but lower than hot-pressed silicon nitride.

Microscopic description of a drop on a solid surface.

PubMed

Ruckenstein, Eli; Berim, Gersh O

2010-06-14

Two approaches recently suggested for the treatment of macro- or nanodrops on smooth or rough, planar or curved, solid surfaces, based on fluid-fluid and fluid-solid interaction potentials are reviewed. The first one employs the minimization of the total potential energy of a drop by assuming that the drop has a well defined profile and a constant liquid density in its entire volume with the exception of the monolayer nearest to the surface where the density has a different value. As a result, a differential equation for the drop profile as well as the necessary boundary conditions are derived which involve the parameters of the interaction potentials and do not contain such macroscopic characteristics as the surface tensions. As a consequence, the macroscopic and microscopic contact angles which the drop profile makes with the surface can be calculated. The macroscopic angle is obtained via the extrapolation of the circular part of the drop profile valid at some distance from the surface up to the solid surface. The microscopic angle is formed at the intersection of the real profile (which is not circular near the surface) with the surface. The theory provides a relation between these two angles. The ranges of the microscopic parameters of the interaction potentials for which (i) the drop can have any height (volume), (ii) the drop can have a restricted height but unrestricted volume, and (iii) a drop cannot be formed on the surface were identified. The theory was also extended to the description of a drop on a rough surface. The second approach is based on a nonlocal density functional theory (DFT), which accounts for the inhomogeneity of the liquid density and temperature effects, features which are missing in the first approach. Although the computational difficulties restrict its application to drops of only several nanometers, the theory can be applied indirectly to macrodrops by calculating the surface tensions and using the Young equation to determine the contact angle. Employing the canonical ensemble version of the DFT, nanodrops on smooth and rough solid surfaces could be investigated and their characteristics, such as the drop profile, contact angle, as well as the fluid density distribution inside the drop can be determined as functions of the parameters of the interaction potentials and temperature. It was found that the contact angle of the drop has a simple (quasi)universal dependence on the energy parameter epsilon(fs) of the fluid-solid interaction potential and temperature. The main feature of this dependence is the existence of a fixed value theta(0) of the contact angle theta which separates the solid substrates (characterized by the energy parameter epsilon(fs) of the fluid-solid interaction potential) into two classes with respect to their temperature dependence. For theta>theta(0) the contact angle monotonously increases and for theta

Balancing Cell Migration with Matrix Degradation Enhances Gene Delivery to Cells Cultured Three-Dimensionally Within Hydrogels

PubMed Central

Shepard, Jaclyn A.; Huang, Alyssa; Shikanova, Ariella; Shea, Lonnie D.

2010-01-01

In regenerative medicine, hydrogels are employed to fill defects and support the infiltration of cells that can ultimately regenerate tissue. Gene delivery within hydrogels targeting infiltrating cells has the potential to promote tissue formation, but the delivery efficiency of nonviral vectors within hydrogels is low hindering their applicability in tissue regeneration. To improve their functionality, we have conducted a mechanistic study to investigate the contribution of cell migration and matrix degradation on gene delivery. In this report, lipoplexes were entrapped within hydrogels based on poly(ethylene glycol) (PEG) crosslinked with peptides containing matrix metalloproteinase degradable sequences. The mesh size of these hydrogels is substantially less than the size of the entrapped lipoplexes, which can function to retain vectors. Cell migration and transfection were simultaneously measured within hydrogels with varying density of cell adhesion sites (Arg-Gly-Asp peptides) and solids content. Increasing RGD density increased expression levels up to 100-fold, while greater solids content sustained expression levels for 16 days. Increasing RGD density and decreasing solids content increased cell migration, which indicates expression levels increase with increased cell migration. Initially exposing cells to vector resulted in transient expression that declined after 2 days, verifying the requirement of migration to sustain expression. Transfected cells were predominantly located within the population of migrating cells for hydrogels that supported cell migration. Although the small mesh size retained at least 70% of the lipoplexes in the absence of cells after 32 days, the presence of cells decreased retention to 10% after 16 days. These results indicate that vectors retained within hydrogels contact migrating cells, and that persistent cell migration can maintain elevated expression levels. Thus matrix degradation and cell migration are fundamental design parameters for maximizing gene delivery from hydrogels. PMID:20450944

Ammonium nitrate-polymer glasses: a new concept for phase and thermal stabilization of ammonium nitrate.

PubMed

Lang, Anthony J; Vyazovkin, Sergey

2008-09-11

Dissolving of ammonium nitrate in highly polar polymers such as poly(vinylpyrrolidone) and/or poly(acrylamide) can result in the formation of single-phase glassy solid materials, in which NH 4 (+) and NO 3 (-) are separated through an ion-dipole interaction with the polymer matrix. Below the glass transition temperature of the polymer matrix the resulting materials remain phase and thermally stable as demonstrated through the absence of decomposition as well as the solid-solid transitions and melting of ammonium nitrate. The structure of the materials is explored by Fourier transform infrared spectroscopy and density functional calculations. Differential scanning calorimetry, thermogravimetry, and isoconversional kinetic analysis are applied to characterize the thermal behavior of the materials.

First-principles quantum-mechanical investigations of biomass conversion at the liquid-solid interfaces

NASA Astrophysics Data System (ADS)

Dang, Hongli; Xue, Wenhua; Liu, Yingdi; Jentoft, Friederike; Resasco, Daniel; Wang, Sanwu

2014-03-01

We report first-principles density-functional calculations and ab initio molecular dynamics (MD) simulations for the reactions involving furfural, which is an important intermediate in biomass conversion, at the catalytic liquid-solid interfaces. The different dynamic processes of furfural at the water-Cu(111) and water-Pd(111) interfaces suggest different catalytic reaction mechanisms for the conversion of furfural. Simulations for the dynamic processes with and without hydrogen demonstrate the importance of the liquid-solid interface as well as the presence of hydrogen in possible catalytic reactions including hydrogenation and decarbonylation of furfural. Supported by DOE (DE-SC0004600). This research used the supercomputer resources of the XSEDE, the NERSC Center, and the Tandy Supercomputing Center.

Calculation of NMR chemical shifts in organic solids: accounting for motional effects.

PubMed

Dumez, Jean-Nicolas; Pickard, Chris J

2009-03-14

NMR chemical shifts were calculated from first principles for well defined crystalline organic solids. These density functional theory calculations were carried out within the plane-wave pseudopotential framework, in which truly extended systems are implicitly considered. The influence of motional effects was assessed by averaging over vibrational modes or over snapshots taken from ab initio molecular dynamics simulations. It is observed that the zero-point correction to chemical shifts can be significant, and that thermal effects are particularly noticeable for shielding anisotropies and for a temperature-dependent chemical shift. This study provides insight into the development of highly accurate first principles calculations of chemical shifts in solids, highlighting the role of motional effects on well defined systems.

Flexible Asymmetric Supercapacitor Based on Functionalized Reduced Graphene Oxide Aerogels with Wide Working Potential Window.

PubMed

Bora, Anindita; Mohan, Kiranjyoti; Doley, Simanta; Dolui, Swapan Kumar

2018-03-07

Flexible energy storage devices are in great demand since the advent of flexible electronics. Until now, flexible supercapacitors based on graphene analogues usually have had low operating potential windows. To this end, two dissimilar electrode materials with complementary potential ranges are employed to obtain an optimum cell voltage of 1.8 V. A low-temperature organic sol-gel method is used to prepare two different types of functionalized reduced graphene oxide aerogels (rGOA) where Ag nanorod functionalized rGOA acts as a negative electrode while polyaniline nanotube functionalized rGOA acts as a positive electrode. Both materials comprehensively exploit their unique properties to produce a device that has high energy and power densities. An assembled all-solid-state asymmetric supercapacitor gives a high energy density of 52.85 W h kg -1 and power density of 31.5 kW kg -1 with excellent cycling and temperature stability. The device also performs extraordinarily well under different bending conditions, suggesting its potential to meet the requirements for flexible electronics.

IR spectra and properties of solid acetone, an interstellar and cometary molecule

NASA Astrophysics Data System (ADS)

Hudson, Reggie L.; Gerakines, Perry A.; Ferrante, Robert F.

2018-03-01

Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of 13C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73% error in previous work is identified and corrected.

Local structure analysis on (La,Ba)(Ga,Mg)O3-δ by the pair distribution function method using a neutron source and density functional theory calculations

NASA Astrophysics Data System (ADS)

Kitamura, Naoto; Vogel, Sven C.; Idemoto, Yasushi

2013-06-01

In this work, we focused on La0.95Ba0.05Ga0.8Mg0.2O3-δ with the perovskite structure, and investigated the local structure around the oxygen vacancy by pair distribution function (PDF) method and density functional theory (DFT) calculation. By comparing the G(r) simulated based on the DFT calculation and the experimentally-observed G(r), it was suggested that the oxygen vacancy was trapped by Ba2+ at the La3+ site at least at room temperature. Such a defect association may be one of the reasons why the La0.95Ba0.05Ga0.8Mg0.2O3-δ showed lower oxide-ion conductivity than (La,Sr)(Ga,Mg)O3-δ which was widely-used as an electrolyte of the solid oxide fuel cell.

Self-consistent hybrid functionals for solids: a fully-automated implementation

NASA Astrophysics Data System (ADS)

Erba, A.

2017-08-01

A fully-automated algorithm for the determination of the system-specific optimal fraction of exact exchange in self-consistent hybrid functionals of the density-functional-theory is illustrated, as implemented into the public Crystal program. The exchange fraction of this new class of functionals is self-consistently updated proportionally to the inverse of the dielectric response of the system within an iterative procedure (Skone et al 2014 Phys. Rev. B 89, 195112). Each iteration of the present scheme, in turn, implies convergence of a self-consistent-field (SCF) and a coupled-perturbed-Hartree-Fock/Kohn-Sham (CPHF/KS) procedure. The present implementation, beside improving the user-friendliness of self-consistent hybrids, exploits the unperturbed and electric-field perturbed density matrices from previous iterations as guesses for subsequent SCF and CPHF/KS iterations, which is documented to reduce the overall computational cost of the whole process by a factor of 2.

Lattice distortion in hcp rare gas solids

NASA Astrophysics Data System (ADS)

Grechnev, A.; Tretyak, S. M.; Freiman, Yu. A.

2010-04-01

The lattice distortion parameter δ ≡c/a-√8/3 has been calculated as a function of molar volume for the hcp phases of He, Ar, Kr, and Xe. Results from both semi-empirical potentials and density functional theory are presented. Our study shows that δ is negative for helium in the entire pressure range. For Ar, Kr, and Xe δ changes sign from negative to positive as the pressure increases, growing rapidly in magnitude at higher pressures.

Revisiting HgCl 2: A solution- and solid-state 199Hg NMR and ZORA-DFT computational study

NASA Astrophysics Data System (ADS)

Taylor, R. E.; Carver, Colin T.; Larsen, Ross E.; Dmitrenko, Olga; Bai, Shi; Dybowski, C.

2009-07-01

The 199Hg chemical-shift tensor of solid HgCl 2 was determined from spectra of polycrystalline materials, using static and magic-angle spinning (MAS) techniques at multiple spinning frequencies and field strengths. The chemical-shift tensor of solid HgCl 2 is axially symmetric ( η = 0) within experimental error. The 199Hg chemical-shift anisotropy (CSA) of HgCl 2 in a frozen solution in dimethylsulfoxide (DMSO) is significantly smaller than that of the solid, implying that the local electronic structure in the solid is different from that of the material in solution. The experimental chemical-shift results (solution and solid state) are compared with those predicted by density functional theory (DFT) calculations using the zeroth-order regular approximation (ZORA) to account for relativistic effects. 199Hg spin-lattice relaxation of HgCl 2 dissolved in DMSO is dominated by a CSA mechanism, but a second contribution to relaxation arises from ligand exchange. Relaxation in the solid state is independent of temperature, suggesting relaxation by paramagnetic impurities or defects.

Computational Characterization of Impact Induced Multi-Scale Dissipation in Reactive Solid Composites

DTIC Science & Technology

2016-07-01

Predicted variation in (a) hot-spot number density , (b) hot-spot volume fraction, and (c) hot-spot specific surface area for each ensemble with piston speed...packing density , characterized by its effective solid volume fraction φs,0, affects hot-spot statistics for pressure dominated waves corresponding to...distribution in solid volume fraction within each ensemble was nearly Gaussian, and its standard deviation decreased with increasing density . Analysis of

Fundamental gaps with approximate density functionals: The derivative discontinuity revealed from ensemble considerations

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

Kraisler, Eli; Kronik, Leeor

2014-05-14

The fundamental gap is a central quantity in the electronic structure of matter. Unfortunately, the fundamental gap is not generally equal to the Kohn-Sham gap of density functional theory (DFT), even in principle. The two gaps differ precisely by the derivative discontinuity, namely, an abrupt change in slope of the exchange-correlation energy as a function of electron number, expected across an integer-electron point. Popular approximate functionals are thought to be devoid of a derivative discontinuity, strongly compromising their performance for prediction of spectroscopic properties. Here we show that, in fact, all exchange-correlation functionals possess a derivative discontinuity, which arises naturallymore » from the application of ensemble considerations within DFT, without any empiricism. This derivative discontinuity can be expressed in closed form using only quantities obtained in the course of a standard DFT calculation of the neutral system. For small, finite systems, addition of this derivative discontinuity indeed results in a greatly improved prediction for the fundamental gap, even when based on the most simple approximate exchange-correlation density functional – the local density approximation (LDA). For solids, the same scheme is exact in principle, but when applied to LDA it results in a vanishing derivative discontinuity correction. This failure is shown to be directly related to the failure of LDA in predicting fundamental gaps from total energy differences in extended systems.« less

Directional Forces by Momentumless Excitation and Order-to-Order Transition in Peierls-Distorted Solids: The Case of GeTe

NASA Astrophysics Data System (ADS)

Chen, Nian-Ke; Li, Xian-Bin; Bang, Junhyeok; Wang, Xue-Peng; Han, Dong; West, Damien; Zhang, Shangbai; Sun, Hong-Bo

2018-05-01

Time-dependent density-functional theory molecular dynamics reveals an unexpected effect of optical excitation in the experimentally observed rhombohedral-to-cubic transition of GeTe. The excitation induces coherent forces along [001], which may be attributed to the unique energy landscape of Peierls-distorted solids. The forces drive the A1 g optical phonon mode in which Ge and Te move out of phase. Upon damping of the A1 g mode, phase transition takes place, which involves no atomic diffusion, defect formation, or the nucleation and growth of the cubic phase.

Design principles for radiation-resistant solid solutions

NASA Astrophysics Data System (ADS)

Schuler, Thomas; Trinkle, Dallas R.; Bellon, Pascal; Averback, Robert

2017-05-01

We develop a multiscale approach to quantify the increase in the recombined fraction of point defects under irradiation resulting from dilute solute additions to a solid solution. This methodology provides design principles for radiation-resistant materials. Using an existing database of solute diffusivities, we identify Sb as one of the most efficient solutes for this purpose in a Cu matrix. We perform density-functional-theory calculations to obtain binding and migration energies of Sb atoms, vacancies, and self-interstitial atoms in various configurations. The computed data informs the self-consistent mean-field formalism to calculate transport coefficients, allowing us to make quantitative predictions of the recombined fraction of point defects as a function of temperature and irradiation rate using homogeneous rate equations. We identify two different mechanisms according to which solutes lead to an increase in the recombined fraction of point defects; at low temperature, solutes slow down vacancies (kinetic effect), while at high temperature, solutes stabilize vacancies in the solid solution (thermodynamic effect). Extension to other metallic matrices and solutes are discussed.

Electronic functions of solid-to-liquid interfaces of organic semiconductor crystals and ionic liquid

NASA Astrophysics Data System (ADS)

Takeya, J.

2008-10-01

The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.

Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes

NASA Astrophysics Data System (ADS)

Ahmad, Zeeshan; Viswanathan, Venkatasubramanian

2017-08-01

We generalize the conditions for stable electrodeposition at isotropic solid-solid interfaces using a kinetic model which incorporates the effects of stresses and surface tension at the interface. We develop a stability diagram that shows two regimes of stability: a previously known pressure-driven mechanism and a new density-driven stability mechanism that is governed by the relative density of metal in the two phases. We show that inorganic solids and solid polymers generally do not lead to stable electrodeposition, and provide design guidelines for achieving stable electrodeposition.

Monte Carlo simulation of hard spheres near random closest packing using spherical boundary conditions

NASA Astrophysics Data System (ADS)

Tobochnik, Jan; Chapin, Phillip M.

1988-05-01

Monte Carlo simulations were performed for hard disks on the surface of an ordinary sphere and hard spheres on the surface of a four-dimensional hypersphere. Starting from the low density fluid the density was increased to obtain metastable amorphous states at densities higher than previously achieved. Above the freezing density the inverse pressure decreases linearly with density, reaching zero at packing fractions equal to 68% for hard spheres and 84% for hard disks. Using these new estimates for random closest packing and coefficients from the virial series we obtain an equation of state which fits all the data up to random closest packing. Usually, the radial distribution function showed the typical split second peak characteristic of amorphous solids and glasses. High density systems which lacked this split second peak and showed other sharp peaks were interpreted as signaling the onset of crystal nucleation.

Thermo-mechanical characterization of silicone foams

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

Rangaswamy, Partha; Smith, Nickolaus A.; Cady, Carl M.

Cellular solids such as elastomeric foams are used in many structural applications to absorb and dissipate energy, due to their light weight (low density) and high energy absorption capability. In this paper we will discuss foams derived from S5370, a silicone foam formulation developed by Dow Corning. In the application presented, the foam is consolidated into a cushion component of constant thickness but variable density. A mechanical material model developed by Lewis (2013), predicts material response, in part, as a function of relative density. To determine the required parameters for this model we have obtained the mechanical response in compressionmore » for ambient, cold and hot temperatures. The variable density cushion provided samples sufficient samples so that the effect of sample initial density on the mechanical response could be studied. The mechanical response data showed extreme sensitivity to relative density. We also observed at strains corresponding to 1 MPa a linear relationship between strain and initial density for all temperatures. Samples taken from parts with a history of thermal cycling demonstrated a stiffening response that was a function of temperature, with the trend of more stiffness as temperature increased above ambient. This observation is in agreement with the entropic effects on the thermo-mechanical behavior of silicone polymers. In this study, we present the experimental methods necessary for the development of a material model, the testing protocol, analysis of test data, and a discussion of load (stress) and gap (strain) as a function of sample initial densities and temperatures« less

Linear-scaling density-functional simulations of charged point defects in Al2O3 using hierarchical sparse matrix algebra.

PubMed

Hine, N D M; Haynes, P D; Mostofi, A A; Payne, M C

2010-09-21

We present calculations of formation energies of defects in an ionic solid (Al(2)O(3)) extrapolated to the dilute limit, corresponding to a simulation cell of infinite size. The large-scale calculations required for this extrapolation are enabled by developments in the approach to parallel sparse matrix algebra operations, which are central to linear-scaling density-functional theory calculations. The computational cost of manipulating sparse matrices, whose sizes are determined by the large number of basis functions present, is greatly improved with this new approach. We present details of the sparse algebra scheme implemented in the ONETEP code using hierarchical sparsity patterns, and demonstrate its use in calculations on a wide range of systems, involving thousands of atoms on hundreds to thousands of parallel processes.

Quasi-particle energy spectra in local reduced density matrix functional theory.

PubMed

Lathiotakis, Nektarios N; Helbig, Nicole; Rubio, Angel; Gidopoulos, Nikitas I

2014-10-28

Recently, we introduced [N. N. Lathiotakis, N. Helbig, A. Rubio, and N. I. Gidopoulos, Phys. Rev. A 90, 032511 (2014)] local reduced density matrix functional theory (local RDMFT), a theoretical scheme capable of incorporating static correlation effects in Kohn-Sham equations. Here, we apply local RDMFT to molecular systems of relatively large size, as a demonstration of its computational efficiency and its accuracy in predicting single-electron properties from the eigenvalue spectrum of the single-particle Hamiltonian with a local effective potential. We present encouraging results on the photoelectron spectrum of molecular systems and the relative stability of C20 isotopes. In addition, we propose a modelling of the fractional occupancies as functions of the orbital energies that further improves the efficiency of the method useful in applications to large systems and solids.

A new approach to determine the density of liquids and solids without measuring mass and volume: introducing the solidensimeter

NASA Astrophysics Data System (ADS)

Kiriktaş, Halit; Şahin, Mehmet; Eslek, Sinan; Kiriktaş, İrem

2018-05-01

This study aims to design a mechanism with which the density of any solid or liquid can be determined without measuring its mass and volume in order to help students comprehend the concept of density more easily. The solidensimeter comprises of two scaled and nested glass containers (graduated cylinder or beaker) and sufficient water. In this method, the density measurement was made using the Archimedes’ principle stating that an object fully submerged in a liquid displaces the same amount of liquid as its volume, while an object partially submerged or floating displaces the same amount of liquid as its mass. Using this method, the density of any solids or liquids can be determined using a simple mathematical ratio. At the end of the process a mechanism that helps students to comprehend the density topic more easily was designed. The system is easy-to-design, uses low-cost equipment and enables one to determine the density of any solid or liquid without measuring its mass and volume.

Self-organized Sr leads to solid state twinning in nano-scaled eutectic Si phase

PubMed Central

Albu, M.; Pal, A.; Gspan, C.; Picu, R. C.; Hofer, F.; Kothleitner, G.

2016-01-01

A new mechanism for twin nucleation in the eutectic Al-Si alloy with trace Sr impurities is proposed. Observations made by sub-angstrom resolution scanning transmission electron microscopy and X-ray probing proved the presence of <110> Sr columns located preferentially at twin boundaries. Density functional theory simulations indicate that Sr atoms bind in the Si lattice only along the <110> direction, with preferential positions at first and second nearest neighbors for interstitial and substitutional Sr, respectively. Density functional theory total energy calculations confirm that twin nucleation at Sr columns is energetically favorable. Hence, twins may nucleate in Si precipitates after solidification, which provides a different perspective to the currently accepted mechanism which suggests twin formation during precipitate growth. PMID:27527789

Self-organized Sr leads to solid state twinning in nano-scaled eutectic Si phase

NASA Astrophysics Data System (ADS)

Albu, M.; Pal, A.; Gspan, C.; Picu, R. C.; Hofer, F.; Kothleitner, G.

2016-08-01

A new mechanism for twin nucleation in the eutectic Al-Si alloy with trace Sr impurities is proposed. Observations made by sub-angstrom resolution scanning transmission electron microscopy and X-ray probing proved the presence of <110> Sr columns located preferentially at twin boundaries. Density functional theory simulations indicate that Sr atoms bind in the Si lattice only along the <110> direction, with preferential positions at first and second nearest neighbors for interstitial and substitutional Sr, respectively. Density functional theory total energy calculations confirm that twin nucleation at Sr columns is energetically favorable. Hence, twins may nucleate in Si precipitates after solidification, which provides a different perspective to the currently accepted mechanism which suggests twin formation during precipitate growth.

Thermodynamic functions, freezing transition, and phase diagram of dense carbon-oxygen mixtures in white dwarfs

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

Iyetomi, H.; Ogata, S.; Ichimaru, S.

1989-07-01

Equations of state for dense carbon-oxygen (C-O) binary-ionic mixtures (BIM's) appropriate to the interiors of white dwarfs are investigated through Monte Carlo simulations, by solution of relevant integral equations andvariational calculations in the density-functional formalism. It is thereby shown that the internal energies of the C-O BIM solids and fluids both obey precisely the linear mixing formulas. We then present an accurate calculation of the phase diagram associated with freezing transitions in such BIM materials, resulting in a novel prediction of an azeotropic diagram. Discontinuities of the mass density across the azeotropic phase boundaries areevaluated numerically for application to amore » study of white-dwarf evolution.« less

Extended screened exchange functional derived from transcorrelated density functional theory.

PubMed

Umezawa, Naoto

2017-09-14

We propose a new formulation of the correlation energy functional derived from the transcorrelated method in use in density functional theory (TC-DFT). An effective Hamiltonian, H TC , is introduced by a similarity transformation of a many-body Hamiltonian, H, with respect to a complex function F: H TC =1FHF. It is proved that an expectation value of H TC for a normalized single Slater determinant, D n , corresponds to the total energy: E[n] = ⟨Ψ n |H|Ψ n ⟩/⟨Ψ n |Ψ n ⟩ = ⟨D n |H TC |D n ⟩ under the two assumptions: (1) The electron density nr associated with a trial wave function Ψ n = D n F is v-representable and (2) Ψ n and D n give rise to the same electron density nr. This formulation, therefore, provides an alternative expression of the total energy that is useful for the development of novel correlation energy functionals. By substituting a specific function for F, we successfully derived a model correlation energy functional, which resembles the functional form of the screened exchange method. The proposed functional, named the extended screened exchange (ESX) functional, is described within two-body integrals and is parametrized for a numerically exact correlation energy of the homogeneous electron gas. The ESX functional does not contain any ingredients of (semi-)local functionals and thus is totally free from self-interactions. The computational cost for solving the self-consistent-field equation is comparable to that of the Hartree-Fock method. We apply the ESX functional to electronic structure calculations for a solid silicon, H - ion, and small atoms. The results demonstrate that the TC-DFT formulation is promising for the systematic improvement of the correlation energy functional.

Compression selective solid-state chemistry

NASA Astrophysics Data System (ADS)

Hu, Anguang

Compression selective solid-state chemistry refers to mechanically induced selective reactions of solids under thermomechanical extreme conditions. Advanced quantum solid-state chemistry simulations, based on density functional theory with localized basis functions, were performed to provide a remarkable insight into bonding pathways of high-pressure chemical reactions in all agreement with experiments. These pathways clearly demonstrate reaction mechanisms in unprecedented structural details, showing not only the chemical identity of reactive intermediates but also how atoms move along the reaction coordinate associated with a specific vibrational mode, directed by induced chemical stress occurred during bond breaking and forming. It indicates that chemical bonds in solids can break and form precisely under compression as we wish. This can be realized through strongly coupling of mechanical work to an initiation vibrational mode when all other modes can be suppressed under compression, resulting in ultrafast reactions to take place isothermally in a few femtoseconds. Thermodynamically, such reactions correspond to an entropy minimum process on an isotherm where the compression can force thermal expansion coefficient equal to zero. Combining a significantly brief reaction process with specific mode selectivity, both statistical laws and quantum uncertainty principle can be bypassed to precisely break chemical bonds, establishing fundamental principles of compression selective solid-state chemistry. Naturally this leads to understand the ''alchemy'' to purify, grow, and perfect certain materials such as emerging novel disruptive energetics.

Sensitivity of combustion and ignition characteristics of the solid-fuel charge of the microelectromechanical system of a microthruster to macrokinetic and design parameters

NASA Astrophysics Data System (ADS)

Futko, S. I.; Ermolaeva, E. M.; Dobrego, K. V.; Bondarenko, V. P.; Dolgii, L. N.

2012-07-01

We have developed a sensitivity analysis permitting effective estimation of the change in the impulse responses of a microthrusters and in the ignition characteristics of the solid-fuel charge caused by the variation of the basic macrokinetic parameters of the mixed fuel and the design parameters of the microthruster's combustion chamber. On the basis of the proposed sensitivity analysis, we have estimated the spread of both the propulsive force and impulse and the induction period and self-ignition temperature depending on the macrokinetic parameters of combustion (pre-exponential factor, activation energy, density, and heat content) of the solid-fuel charge of the microthruster. The obtained results can be used for rapid and effective estimation of the spread of goal functions to provide stable physicochemical characteristics and impulse responses of solid-fuel mixtures in making and using microthrusters.

Shock Response and Phase Transitions of MgO at Planetary Impact Conditions.

PubMed

Root, Seth; Shulenburger, Luke; Lemke, Raymond W; Dolan, Daniel H; Mattsson, Thomas R; Desjarlais, Michael P

2015-11-06

The moon-forming impact and the subsequent evolution of the proto-Earth is strongly dependent on the properties of materials at the extreme conditions generated by this violent collision. We examine the high pressure behavior of MgO, one of the dominant constituents in Earth's mantle, using high-precision, plate impact shock compression experiments performed on Sandia National Laboratories' Z Machine and extensive quantum calculations using density functional theory (DFT) and quantum Monte Carlo (QMC) methods. The combined data span from ambient conditions to 1.2 TPa and 42 000 K, showing solid-solid and solid-liquid phase boundaries. Furthermore our results indicate that under impact the solid and liquid phases coexist for more than 100 GPa, pushing complete melting to pressures in excess of 600 GPa. The high pressure required for complete shock melting has implications for a broad range of planetary collision events.

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

NASA Astrophysics Data System (ADS)

Tran, Fabien; Hutter, Jürg

2013-05-01

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

Pushing the Theoretical Limit of Li-CFx Batteries: A Tale of Bi-functional Electrolyte

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

Rangasamy, Ezhiylmurugan; Li, Juchuan; Sahu, Gayatri

2014-01-01

In a typical battery, electrodes deliver capacities less or equal the theoretical maxima of the electrode materials.1 The inert electrolyte functions solely as the ionic conductor without contribution to the cell capacity because of its distinct mono-function in the concept of conventional batteries. Here we demonstrate that the most energy-dense Li-CFx battery2 delivers a capacity exceeding the theoretical maximum of CFx with a solid electrolyte of Li3PS4 (LPS) that has dual functions: as the inert electrolyte at the anode and the active component at the cathode. Such a bi-functional electrolyte reconciles both inert and active characteristics through a synergistic dischargemore » mechanism of CFx and LPS. Li3PS4 is known as an inactive solid electrolyte with a broad electrochemical window over 5 V.3 The synergy at the cathode is through LiF, the discharge product of CFx, which activates the electrochemical discharge of LPS at a close electrochemical potential of CFx. Therefore, the solid-state Li-CFx batteries output 126.6% energy beyond their theoretic limits without compromising the stability of the cell voltage. The extra energy comes from the electrochemical discharge of LPS, the inert electrolyte. This bi-functional electrolyte revolutionizes the concept of conventional batteries and opens a new avenue for the design of batteries with an unprecedentedly high energy density.« less

Molecular simulation of fluid mixtures in bulk and at solid-liquid interfaces

NASA Astrophysics Data System (ADS)

Kern, Jesse L.

The properties of a diverse range of mixture systems at interfaces are investigated using a variety of computational techniques. Molecular simulation is used to examine the thermodynamic, structural, and transport properties of heterogeneous systems of theoretical and practical importance. The study of binary hard-sphere mixtures at a hard wall demonstrates the high accuracy of recently developed classical-density functionals. The study of aluminum--gallium solid--liquid heterogeneous interfaces predicts a significant amount of prefreezing of the liquid by adopting the structure of the solid surface. The study of ethylene-expanded methanol within model silica mesopores shows the effect of confinement and surface functionalzation on the mixture composition and transport inside of the pores. From our molecular-dynamics study of binary hard-sphere fluid mixtures at a hard wall, we obtained high-precision calculations of the wall-fluid interfacial free energies, gamma. We have considered mixtures of varying diameter ratio, alpha = 0.7,0.8,0.9; mole fraction, x 1 = 0.25,0.50,0.75; and packing fraction, eta < 0.50. Using Gibbs-Cahn Integration, gamma is calculated from the system pressure, chemical potentials, and density profiles. Recent classical density-functional theory predictions agree very well with our results. Structural, thermodynamic, and transport properties of the aluminum--gallium solid--liquid interface at 368 K are obtained for the (100), (110), and (111) orientations using molecular dynamics. Density, potential energy, stress, and diffusion profiles perpendicular to the interface are calculated. The layers of Ga that form on the Al surface are strongly adsorbed and take the in-plane structure of the underlying crystal layers for all orientations, which results in significant compressive stress on the Ga atoms. Bulk methanol--ethylene mixtures under vapor-liquid equilibrium conditions have been characterized using Monte Carlo and molecular dynamics. The simulated vapor-liquid coexistence curves for the pure-component and binary mixtures agree well with experiment, as do the mixture volumetric expansion results. Using chemical potentials obtained from the bulk simulations, the filling of a number of model silica mesopores with ethylene and methanol is simulated. We report the compositions of the confined fluid mixtures over a range of pressures and for three degrees of nominal pore hydrophobicity.

Emission properties of body-centered cubic elemental metal photocathodes

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

Li, Tuo; Rickman, Benjamin L., E-mail: brickm2@uic.edu; Schroeder, W. Andreas

2015-04-07

A first principles analysis of photoemission is developed to explain the lower than expected rms transverse electron momentum measured using the solenoid scan technique for the body-centered cubic Group Vb (V, Nb, and Ta) and Group VIb (Cr, Mo, and W) metallic photocathodes. The density functional theory based analysis elucidates the fundamental role that the electronic band structure (and its dispersion) plays in determining the emission properties of solid-state photocathodes and includes evaluation of work function anisotropy using a thin-slab method.

Lunar ash flow with heat transfer.

NASA Technical Reports Server (NTRS)

Pai, S. I.; Hsieh, T.; O'Keefe, J. A.

1972-01-01

The most important heat-transfer process in the ash flow under consideration is heat convection. Besides the four important nondimensional parameters of isothermal ash flow (Pai et al., 1972), we have three additional important nondimensional parameters: the ratio of the specific heat of the gas, the ratio of the specific heat of the solid particles to that of gas, and the Prandtl number. We reexamine the one dimensional steady ash flow discussed by Pai et al. (1972) by including the effects of heat transfer. Numerical results for the pressure, temperature, density of the gas, velocities of gas and solid particles, and volume fraction of solid particles as function of altitude for various values of the Jeffreys number, initial velocity ratio, and two different gas species (steam and hydrogen) are presented.

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

Zhu, Jinlong; Wang, Yonggang; Li, Shuai

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-state battery. In this work, the sodium ionic transport pathways of the parent compound Na3OBr, as well as the modified layered antiperovskite Na4OI2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions hop within and among oxygen octahedra, and Br- ions are not involved. In the tetragonal Na4OI2 antiperovskite, Na ions, which connectmore » octahedra in the ab plane, have the lowest activation energy barrier. The transport of sodium ions along the c axis is assisted by I- ions.« less

A thermally self-sustained micro-power plant with integrated micro-solid oxide fuel cells, micro-reformer and functional micro-fluidic carrier

NASA Astrophysics Data System (ADS)

Scherrer, Barbara; Evans, Anna; Santis-Alvarez, Alejandro J.; Jiang, Bo; Martynczuk, Julia; Galinski, Henning; Nabavi, Majid; Prestat, Michel; Tölke, René; Bieberle-Hütter, Anja; Poulikakos, Dimos; Muralt, Paul; Niedermann, Philippe; Dommann, Alex; Maeder, Thomas; Heeb, Peter; Straessle, Valentin; Muller, Claude; Gauckler, Ludwig J.

2014-07-01

Low temperature micro-solid oxide fuel cell (micro-SOFC) systems are an attractive alternative power source for small-size portable electronic devices due to their high energy efficiency and density. Here, we report on a thermally self-sustainable reformer-micro-SOFC assembly. The device consists of a micro-reformer bonded to a silicon chip containing 30 micro-SOFC membranes and a functional glass carrier with gas channels and screen-printed heaters for start-up. Thermal independence of the device from the externally powered heater is achieved by exothermic reforming reactions above 470 °C. The reforming reaction and the fuel gas flow rate of the n-butane/air gas mixture controls the operation temperature and gas composition on the micro-SOFC membrane. In the temperature range between 505 °C and 570 °C, the gas composition after the micro-reformer consists of 12 vol.% to 28 vol.% H2. An open-circuit voltage of 1.0 V and maximum power density of 47 mW cm-2 at 565 °C is achieved with the on-chip produced hydrogen at the micro-SOFC membranes.

Droplets and the three-phase contact line at the nano-scale. Statics and dynamics

NASA Astrophysics Data System (ADS)

Yatsyshin, Petr; Sibley, David; Savva, Nikos; Kalliadasis, Serafim

2014-11-01

Understanding the behaviour of the solid-liquid-vapour contact line at the scale of several tens of molecular diameters is important in wetting hydrodynamics with applications in micro- and nano-fluidics, including the design of lab-on-a-chip devices and surfaces with specific wetting properties. Due to the fluid inhomogeneity at the nano-scale, the application of continuum-mechanical approaches is limited, and a natural way to remedy this is to seek descriptions accounting for the non-local molecular-level interactions. Density Functional Theory (DFT) for fluids offers a statistical-mechanical framework based on expressing the free energy of the fluid-solid pair as a functional of the spatially varying fluid density. DFT allows us to investigate small drops deposited on planar substrates whilst keeping track of the microscopic structural details of the fluid. Starting from a model of intermolecular forces, we systematically obtain interfaces, surface tensions, and the microscopic contact angle. Using a dynamic extension of equilibrium DFT, we investigate the diffusion-driven evolution of the three-phase contact line to gain insight into the dynamic behaviour of the microscopic contact angle, which is still under debate.

Freezing of simple systems using density functional theory

NASA Astrophysics Data System (ADS)

de Kuijper, A.; Vos, W. L.; Barrat, J.-L.; Hansen, J.-P.; Schouten, J. A.

1990-10-01

Density functional theory (DFT) has been applied to the study of the fluid-solid transition in systems with realistic potentials (soft cores and attractive forces): the purely repulsive WCA Lennard-Jones reference potential (LJT), the full Lennard-Jones potential (LJ) and the exponential-6 potential appropriate for helium and hydrogen. Three different DFT formalisms were used: the formulation of Haymet and Oxtoby (HO) and the new theories of Denton and Ashcroft (MWDA) and of Baus (MELA). The results for the melting pressure are compared with recent simulation and experimental data. The results of the HO version are always too high, the deviation increasing when going from the repulsive Lennard-Jones to the exponential-6 potential of H2. The MWDA gives too low results for the repulsive Lennard-Jones potential. At low temperatures, it fails for the full LJ potential while at high temperatures it is in good agreement. Including the attraction as a mean-field correction gives good results also for low temperatures. The MWDA results are too high for the exponential-6 potentials. The MELA fails completely for the LJT potential and the hydrogen exponential-6 potential, since it does not give a stable solid phase.

CO(2) capture properties of alkaline earth metal oxides and hydroxides: A combined density functional theory and lattice phonon dynamics study.

PubMed

Duan, Yuhua; Sorescu, Dan C

2010-08-21

By combining density functional theory and lattice phonon dynamics, the thermodynamic properties of CO(2) absorption/desorption reactions with alkaline earth metal oxides MO and hydroxides M(OH)(2) (where M=Be,Mg,Ca,Sr,Ba) are analyzed. The heats of reaction and the chemical potential changes of these solids upon CO(2) capture reactions have been calculated and used to evaluate the energy costs. Relative to CaO, a widely used system in practical applications, MgO and Mg(OH)(2) systems were found to be better candidates for CO(2) sorbent applications due to their lower operating temperatures (600-700 K). In the presence of H(2)O, MgCO(3) can be regenerated into Mg(OH)(2) at low temperatures or into MgO at high temperatures. This transition temperature depends not only on the CO(2) pressure but also on the H(2)O pressure. Based on our calculated results and by comparing with available experimental data, we propose a general computational search methodology which can be used as a general scheme for screening a large number of solids for use as CO(2) sorbents.

System and technique for characterizing fluids using ultrasonic diffraction grating spectroscopy

DOEpatents

Greenwood, Margaret S.

2005-04-12

A system for determining a property of a fluid based on ultrasonic diffraction grating spectroscopy includes a diffraction grating on a solid in contact with the fluid. An interrogation device delivers ultrasound through the solid and a captures a reflection spectrum from the diffraction grating. The reflection spectrum including a diffraction order equal to zero exhibits a peak whose location is used to determine speed of sound in the fluid. A separate measurement of the acoustic impedance is combined with the determined speed of sound to yield a measure of fluid density. A system for determining acoustic impedance includes an ultrasonic transducer on a first surface of a solid member, and an opposed second surface of the member is in contact with a fluid to be monitored. A longitudinal ultrasonic pulse is delivered through the solid member, and a multiplicity of pulse echoes caused by reflections of the ultrasonic pulse between the solid-fluid interface and the transducer-solid interface are detected. The decay rate of the detected echo amplitude as a function of echo number is used to determine acoustic impedance.

Nonlinear functional for solvation in Density Functional Theory

NASA Astrophysics Data System (ADS)

Gunceler, Deniz; Sundararaman, Ravishankar; Schwarz, Kathleen; Letchworth-Weaver, Kendra; Arias, T. A.

2013-03-01

Density functional calculations of molecules and surfaces in a liquid can accelerate the development of many technologies ranging from solar energy harvesting to lithium batteries. Such studies require the development of robust functionals describing the liquid. Polarizable continuum models (PCM's) have been applied to some solvated systems; but they do not sufficiently capture solvation effects to describe highly polar systems like surfaces of ionic solids. In this work, we present a nonlinear fluid functional within the framework of Joint Density Functional Theory. The fluid is treated not as a linear dielectric, but as a distribution of dipoles that responds to the solute, which we describe starting from the exact free energy functional for point dipoles. We also show PCM's can be recovered as the linear limit of our functional. Our description is of similar computational cost to PCM's, and captures complex solvation effects like dielectric saturation without requiring new fit parameters. For polar and nonpolar molecules, it achieves millihartree level agreement with experimental solvation energies. Furthermore, our functional now makes it possible to investigate chemistry on the surface of lithium battery materials, which PCM's predict to be unstable. Supported as part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001086

Transferability of electronic structure of four energetic materials by using single crystal and high resolution X-ray diffraction experiments

NASA Astrophysics Data System (ADS)

Chen, Yu-Sheng

The electronic structures of four energetic materials, trinitrodiazapentalene (C6H3N5O6, TNDAP), beta-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (C4H8N8O8, beta-HMX), 1,3,3-trinitroazetidine (C3H4N4O6, TNAZ), and hexahydro-1,3,5-trinitro-1,3,5-s-triazine (C3H6N6O6, RDX), have been analyzed using Hansen-Coppens multipole refinements, using high resolution X-ray diffraction data collected at low temperature, as well as from theoretical calculated structure factors from the solid state phase using density functional theory (DFT), plus B3LYP level theory, and the 6-31G* basis set. However, when comparing both the deformation density and the electrostatic potentials from the theoretical results in TNDAP and TNAZ, they disagree with the experimental results. Therefore, those results have been deposited in appendices A4 and A6, for future reference. In HMX and RDX the theoretical results are in good agreement with experimental results. The physical properties derived from the electronic structure in these four energetic materials, such as multipole populations, the values of the electron density and its Laplacian of the electron density at the bond critical points, have also been calculated using "Atoms in Molecules" (AIM) theory both from the solid state phase calculation, and the experiment, as well as directly calculated from the free molecule in the gas phase. The electron density and the magnitude of its Laplacian from the gas phase are always larger than for the solid state phase calculation and the experiment. This may be due to the packing effect. The transferability of the experimental electronic structure of the NO 2 groups from HMX to TNDAP, TNAZ and RDX are also presented here. Even though the major populated multipoles are robust (small e.s.d.'s), these are few in number, compared with other lower populated multipoles for which the populations span a larger range. Since the deformation electron density distributions are reconstructed using linear combinations of the multipoles, it is necessary to give more degrees of freedom in the refinements. Therefore, those electron density distributions which have a wider range of the multipole populations should not be fixed in the refinements. Utilizing the same coordinate system setup in the multipole refinements of the functional groups, this system can be used as a starting point for solving the charge distribution of a larger system.

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

PubMed

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Role of bond adaptability in the passivation of colloidal quantum dot solids.

PubMed

Thon, Susanna M; Ip, Alexander H; Voznyy, Oleksandr; Levina, Larissa; Kemp, Kyle W; Carey, Graham H; Masala, Silvia; Sargent, Edward H

2013-09-24

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

Search for the First-Order Liquid-to-Liquid Phase Transition in Low-Temperature Confined Water by Neutron Scattering

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

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I

2013-01-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaricmore » temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the alpha-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.« less

Search for the first-order liquid-to-liquid phase transition in low-temperature confined water by neutron scattering

NASA Astrophysics Data System (ADS)

Chen, Sow-Hsin; Wang, Zhe; Kolesnikov, Alexander I.; Zhang, Yang; Liu, Kao-Hsiang

2013-02-01

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaric temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the α-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.

Titanium α-ω phase transformation pathway and a predicted metastable structure

DOE PAGES

Zarkevich, Nickolai A.; Johnson, Duane D.

2016-01-15

A titanium is a highly utilized metal for structural lightweighting and its phases, transformation pathways (transition states), and structures have scientific and industrial importance. Using a proper solid-state nudged elastic band method employing two climbing images combined with density functional theory DFT + U methods for accurate energetics, we detail the pressure-induced α (ductile) to ω (brittle) transformation at the coexistence pressure. We also find two transition states along the minimal-enthalpy path and discover a metastable body-centered orthorhombic structure, with stable phonons, a lower density than the end-point phases, and decreasing stability with increasing pressure.

Challenges and Opportunities for Biophotonic Devices in the Liquid State and the Solid State

DTIC Science & Technology

2006-07-01

of the NPB:Eu device and a baseline device (without the NPB layer and emitting from the Alq3 layer) as a function of current density. The luminance...of the NPB:Eu device is clearly superior, with a maximum of 590 cd/m2 at 375 mA/cm2, whereas the Alq3 OLED peaks at only 45 cd/m2 at 30 mA/cm2...Luminance versus current density for Eu-doped BioLED and for baseline Alq3 device. 1-4244-0078-3/06/$20.00 (c) 2006 IEEE B. Electrofluidic

Molecular Dynamics Modeling of Thermal Properties of Aluminum Near Melting Line

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

Karavaev, A. V.; Dremov, V. V.; Sapozhnikov, F. A.

2006-08-03

In this work we present results of calculations of thermal properties of solid and liquid phases of aluminum at different densities and temperatures using classical molecular dynamics with EAM potential function. Dependencies of heat capacity CV on temperature and density have been analyzed. It was shown that when temperature increases, heat capacity CV behavior deviates from that by Dulong-Petit law. It may be explained by influence of anharmonicity of crystal lattice vibrations. Comparison of heat capacity CV of liquid phase with Grover's model has been performed. Dependency of aluminum melting temperature on pressure has been acquired.

Experimental study of the valence band of Bi 2 Se 3

DOE PAGES

Gao, Yi-Bin; He, Bin; Parker, David; ...

2014-09-26

The valence band of Bi 2Se 3 is investigated with Shubnikov - de Haas measurements, galvanomagnetic and thermoelectric transport. At low hole concentration, the hole Fermi surface is closed and box-like, but at higher concentrations it develops tube-like extensions that are open. The experimentally determined density-of-states effective mass is lighter than density-functional theory calculations predict; while we cannot give a definitive explanation for this, we suspect that the theory may lack sufficient precision to compute room-temperature transport properties, such as the Seebeck coefficient, in solids in which there are Van der Waals interlayer bonds.

Terahertz pulsed imaging as an advanced characterisation tool for film coatings--a review.

PubMed

Haaser, Miriam; Gordon, Keith C; Strachan, Clare J; Rades, Thomas

2013-12-05

Solid dosage forms are the pharmaceutical drug delivery systems of choice for oral drug delivery. These solid dosage forms are often coated to modify the physico-chemical properties of the active pharmaceutical ingredients (APIs), in particular to alter release kinetics. Since the product performance of coated dosage forms is a function of their critical coating attributes, including coating thickness, uniformity, and density, more advanced quality control techniques than weight gain are required. A recently introduced non-destructive method to quantitatively characterise coating quality is terahertz pulsed imaging (TPI). The ability of terahertz radiation to penetrate many pharmaceutical materials enables structural features of coated solid dosage forms to be probed at depth, which is not readily achievable with other established imaging techniques, e.g. near-infrared (NIR) and Raman spectroscopy. In this review TPI is introduced and various applications of the technique in pharmaceutical coating analysis are discussed. These include evaluation of coating thickness, uniformity, surface morphology, density, defects and buried structures as well as correlation between TPI measurements and drug release performance, coating process monitoring and scale up. Furthermore, challenges and limitations of the technique are discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Infrared spectra and density functional calculations for SMO2 molecules (M = Cr, Mo, W).

PubMed

Wang, Xuefeng; Andrews, Lester

2009-08-06

Infrared absorptions of the matrix isolated SMO2 (M = Cr, Mo, W) molecules were observed following laser-ablated metal atom reactions with SO2 during condensation in solid argon and neon. The symmetric and antisymmetric M-O stretching mode assignments were confirmed by appropriate S18O2 and S(16,18)O2 isotopic shifts. The much weaker Cr-S stretching mode was identified through its 34S shift. Density functional (B3LYP and BPW91) calculations were performed to obtain molecular structures and to reproduce the infrared spectra. Computed pyramidal structures for the SMO2 molecules are very similar to those for the analogous trioxides and this functional group in [MO2S(bdt)]2- complexes. Additional weaker absorptions are assigned to the (SO2)(SMO2) adducts, which are stabilized by a four-membered ring.

Mixed-linker UiO-66: structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density functional theory calculations.

PubMed

Taddei, Marco; Tiana, Davide; Casati, Nicola; van Bokhoven, Jeroen A; Smit, Berend; Ranocchiari, Marco

2017-01-04

The use of mixed-linker metal-organic frameworks (MIXMOFs) is one of the most effective strategies to modulate the physical-chemical properties of MOFs without affecting the overall crystal structure. In many instances, MIXMOFs have been recognized as solid solutions, with random distribution of ligands, in agreement with the empirical rule known as Vegard's law. In this work, we have undertaken a study combining high-resolution powder X-ray diffraction (HR-PXRD) and density functional theory (DFT) calculations with the aim of understanding the reasons why UiO-66-based amino- and bromo-functionalized MIXMOFs (MIXUiO-66) undergo cell expansion obeying Vegard's law and how this behaviour is related to their physical-chemical properties. DFT calculations predict that the unit cell in amino-functionalized UiO-66 experiences only minor expansion as a result of steric effects, whereas major modification to the electronic features of the framework leads to weaker metal-linker interaction and consequently to the loss of stability at higher degrees of functionalization. For bromo-functionalized UiO-66, steric repulsion due to the size of bromine yields a large cell expansion, but the electronic features remain very similar to pristine UiO-66, preserving the stability of the framework upon functionalization. MIXUiO-66 obtained by either direct synthesis or by post-synthetic exchange shows Vegard-like behaviour, suggesting that both preparation methods yield solid solutions, but the thermal stability and the textural properties of the post-synthetic exchanged materials do not display a clear dependence on the chemical composition, as observed for the MOFs obtained by direct synthesis.

High-order harmonic generation in solid slabs beyond the single-active-electron approximation

NASA Astrophysics Data System (ADS)

Hansen, Kenneth K.; Deffge, Tobias; Bauer, Dieter

2017-11-01

High-harmonic generation by a laser-driven solid slab is simulated using time-dependent density functional theory. Multiple harmonic plateaus up to very high harmonic orders are observed already at surprisingly low field strengths. The full all-electron harmonic spectra are, in general, very different from those of any individual Kohn-Sham orbital. Freezing the Kohn-Sham potential instead is found to be a good approximation for the laser intensities and harmonic orders considered. The origins of the plateau cutoffs are explained in terms of band gaps that can be reached by Kohn-Sham electrons and holes moving through the band structure.

Stability of micro-Cassie states on rough substrates

NASA Astrophysics Data System (ADS)

Guo, Zhenjiang; Liu, Yawei; Lohse, Detlef; Zhang, Xuehua; Zhang, Xianren

2015-06-01

We numerically study different forms of nanoscale gaseous domains on a model for rough surfaces. Our calculations based on the constrained lattice density functional theory show that the inter-connectivity of pores surrounded by neighboring nanoposts, which model the surface roughness, leads to the formation of stable microscopic Cassie states. We investigate the dependence of the stability of the micro-Cassie states on substrate roughness, fluid-solid interaction, and chemical potential and then address the differences between the origin of the micro-Cassie states and that of surface nanobubbles within similar models. Finally, we show that the micro-Cassie states share some features with experimentally observed micropancakes at solid-water interfaces.

Letter: Modeling reactive shock waves in heterogeneous solids at the continuum level with stochastic differential equations

NASA Astrophysics Data System (ADS)

Kittell, D. E.; Yarrington, C. D.; Lechman, J. B.; Baer, M. R.

2018-05-01

A new paradigm is introduced for modeling reactive shock waves in heterogeneous solids at the continuum level. Inspired by the probability density function methods from turbulent reactive flows, it is hypothesized that the unreacted material microstructures lead to a distribution of heat release rates from chemical reaction. Fluctuations in heat release, rather than velocity, are coupled to the reactive Euler equations which are then solved via the Riemann problem. A numerically efficient, one-dimensional hydrocode is used to demonstrate this new approach, and simulation results of a representative impact calculation (inert flyer into explosive target) are discussed.

Microscopic aspects of wetting using classical density functional theory

NASA Astrophysics Data System (ADS)

Yatsyshin, P.; Durán-Olivencia, M.-A.; Kalliadasis, S.

2018-07-01

Wetting is a rather efficient mechanism for nucleation of a phase (typically liquid) on the interface between two other phases (typically solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid–fluid and fluid–substrate intermolecular interactions brings about an entire ‘zoo’ of possible fluid configurations, such as liquid films with a thickness of a few nanometers, liquid nanodrops and liquid bridges. These fluid configurations are often associated with phase transitions occurring at the solid–gas interface and at lengths of just several molecular diameters away from the substrate. In this special issue article, we demonstrate how a fully microscopic classical density-functional framework can be applied to the efficient, rational and systematic exploration of the rich phase space of wetting phenomena. We consider a number of model prototype systems such as wetting on a planar wall, a chemically patterned wall and a wedge. Through density-functional computations we demonstrate that for these simply structured substrates the behaviour of the solid–gas interface is already highly complex and non-trivial.

Dynamics of two-phase interfaces and surface tensions: A density-functional theory perspective

NASA Astrophysics Data System (ADS)

Yatsyshin, Petr; Sibley, David N.; Duran-Olivencia, Miguel A.; Kalliadasis, Serafim

2016-11-01

Classical density functional theory (DFT) is a statistical mechanical framework for the description of fluids at the nanoscale, where the inhomogeneity of the fluid structure needs to be carefully accounted for. By expressing the grand free-energy of the fluid as a functional of the one-body density, DFT offers a theoretically consistent and computationally accessible way to obtain two-phase interfaces and respective interfacial tensions in a ternary solid-liquid-gas system. The dynamic version of DFT (DDFT) can be rigorously derived from the Smoluchowsky picture of the dynamics of colloidal particles in a solvent. It is generally agreed that DDFT can capture the diffusion-driven evolution of many soft-matter systems. In this context, we use DDFT to investigate the dynamic behaviour of two-phase interfaces in both equilibrium and dynamic wetting and discuss the possibility of defining a time-dependent surface tension, which still remains in debate. We acknowledge financial support from the European Research Council via Advanced Grant No. 247031 and from the Engineering and Physical Sciences Research Council of the UK via Grants No. EP/L027186 and EP/L020564.

Dynamics of bulk electron heating and ionization in solid density plasmas driven by ultra-short relativistic laser pulses

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

Huang, L. G., E-mail: lingen.huang@hzdr.de; Kluge, T.; Cowan, T. E.

The dynamics of bulk heating and ionization is investigated both in simulations and theory, which determines the crucial plasma parameters such as plasma temperature and density in ultra-short relativistic laser-solid target interactions. During laser-plasma interactions, the solid density plasma absorbs a fraction of laser energy and converts it into kinetic energy of electrons. A portion of the electrons with relativistic kinetic energy goes through the solid density plasma and transfers energy into the bulk electrons, which results in bulk electron heating. The bulk electron heating is finally translated into the processes of bulk collisional ionization inside the solid target. Amore » simple model based on the Ohmic heating mechanism indicates that the local and temporal profile of bulk return current is essential to determine the temporal evolution of bulk electron temperature. A series of particle-in-cell simulations showing the local heating model is robust in the cases of target with a preplasma and without a preplasma. Predicting the bulk electron heating is then benefit for understanding the collisional ionization dynamics inside the solid targets. The connection of the heating and ionization inside the solid target is further studied using Thomas-Fermi model.« less

Solid phase stability of molybdenum under compression: Sound velocity measurements and first-principles calculations

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

Zhang, Xiulu; Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology, 621010 Mianyang, Sichuan; Liu, Zhongli

2015-02-07

The high-pressure solid phase stability of molybdenum (Mo) has been the center of a long-standing controversy on its high-pressure melting. In this work, experimental and theoretical researches have been conducted to check its solid phase stability under compression. First, we performed sound velocity measurements from 38 to 160 GPa using the two-stage light gas gun and explosive loading in backward- and forward-impact geometries, along with the high-precision velocity interferometry. From the sound velocities, we found no solid-solid phase transition in Mo before shock melting, which does not support the previous solid-solid phase transition conclusion inferred from the sharp drops of themore » longitudinal sound velocity [Hixson et al., Phys. Rev. Lett. 62, 637 (1989)]. Then, we searched its structures globally using the multi-algorithm collaborative crystal structure prediction technique combined with the density functional theory. By comparing the enthalpies of body centered cubic structure with those of the metastable structures, we found that bcc is the most stable structure in the range of 0–300 GPa. The present theoretical results together with previous ones greatly support our experimental conclusions.« less

Calculation of nanodrop profile from fluid density distribution.

PubMed

Berim, Gersh O; Ruckenstein, Eli

2016-05-01

Two approaches are examined, which can be used to determine the drop profile from the fluid density distributions (FDDs) obtained on the basis of microscopic theories. For simplicity, only two-dimensional (cylindrical, or axisymmetrical) distributions are examined and it is assumed that the fluid is either in contact with a smooth solid or separated from the smooth solid by a lubricating liquid film. The first approach is based on the sharp-kink interface approximation in which the density of the liquid inside and the density of the vapor outside the drop are constant with the exception of the surface layer of the drop where the density is different from the above ones. In this case, the drop profile was calculated by minimizing the total potential energy of the system. The second approach is based on a nonuniform FDD obtained either by the density functional theory or molecular dynamics simulations. To determine the drop profile from such an FDD, which does not contain sharp interfaces, three procedures can be used. In the first two procedures, P1 and P2, the one-dimensional FDDs along straight lines which are parallel to the surface of the solid are extracted from the two-dimensional FDD. Each of those one-dimensional FDDs has a vapor-liquid interface at which the fluid density changes from vapor-like to liquid-like values. Procedure P1 uses the locations of the equimolar dividing surfaces for the one-dimensional FDDs as points of the drop profile. Procedure P2 is based on the assumption that the fluid density is constant on the surface of the drop, that density being selected either arbitrarily or as a fluid density at the location of the equimolar dividing surface for one of the one-dimensional FDDs employed in procedure P1. In the third procedure, P3, which is suggested for the first time in this paper, the one-dimensional FDDs are taken along the straight lines passing through a selected point inside the drop (radial line). Then, the drop profile is calculated like in procedure P1. It is shown, that procedure P3 provides a drop profile which is more reasonable than the other ones. Relationship of the discussed procedures to those used in image analysis is briefly discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

Jacob's Ladder as Sketched by Escher: Assessing the Performance of Broadly Used Density Functionals on Transition Metal Surface Properties.

PubMed

Vega, Lorena; Ruvireta, Judit; Viñes, Francesc; Illas, Francesc

2018-01-09

The present work surveys the performance of various widely used density functional theory exchange-correlation (xc) functionals in describing observable surface properties of a total of 27 transition metals with face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. A total of 81 low Miller index surfaces were considered employing slab models. Exemplary xc functionals within the three first rungs of Jacob's ladder were considered, including the Vosko-Wilk-Nusair xc functional within the local density approximation, the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA), and the Tao-Perdew-Staroverov-Scuseria functional as a meta-GGA functional. Hybrids were excluded in the survey because they are known to fail in properly describing metallic systems. In addition, two variants of PBE were considered, PBE adapted for solids (PBEsol) and revised PBE (RPBE), aimed at improving adsorption energies. Interlayer atomic distances, surface energies, and surface work functions were chosen as the scrutinized properties. A comparison with available experimental data, including single-crystal and polycrystalline values, shows that no xc functional is best at describing all of the surface properties. However, in statistical mean terms the PBEsol xc functional is advised, while PBE is recommended when considering both bulk and surface properties. On the basis of the present results, a discussion of adapting GGA functionals to the treatment of metallic surfaces in an alternative way to meta-GGA or hybrids is provided.

Procedure for Uranium-Molybdenum Density Measurements and Porosity Determination

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

Prabhakaran, Ramprashad; Devaraj, Arun; Joshi, Vineet V.

2016-08-13

The purpose of this document is to provide guidelines for preparing uranium-molybdenum (U-Mo) specimens, performing density measurements, and computing sample porosity. Typical specimens (solids) will be sheared to small rectangular foils, disks, or pieces of metal. A mass balance, solid density determination kit, and a liquid of known density will be used to determine the density of U-Mo specimens using the Archimedes principle. A standard test weight of known density would be used to verify proper operation of the system. By measuring the density of a U-Mo sample, it is possible to determine its porosity.

The morphology of blends of linear and branched polyethylenes

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

Wignall, G.D.; Londono, J.D.; Alamo, R.G.

1995-12-31

The state of mixing in blends of high density (HD), low density (LD) and linear low density (LLD) polyethylenes (PE) in the melt and solid states has been examined by small-angle x-ray and neutron scattering (SAXS and SANS). In the melt, SANS results indicate that HDPE/LDPE mixtures (with 1-2 branches/100 C) form a single phase. HDPE/LLDPE blends are also homogeneous when the branch content is low, but phase separate as the branching increases. In the solid state, after slow-cooling from the melt, the HDPE/LDPE system segregates into domains {approximately}10{sup 2} in size. For high concentrations of linear polymer ({phi} {ge}more » 0.5), there are separate stacks of HDPE and LDPE lamellae, and the measured SANS cross section agrees closely with the theoretical calculation based on the assumption of complete phase separation of the components. For predominantly branched blends ({phi} < 0.5), the phase segregation is less complete, and the components are separated within the same lamellar stack. Moreover, the phases no longer consist of the pure components, and the HDPE lamellae contain up to 15% LDPE. The segregation of components in the solid state is a consequence of crystallization mechanisms and the blend morphology is a strong function of the cooling rate. Rapid quenching to -78{degrees}C produces only one lamellar stack and these blends show extensive cocrystallization. Samples quenched less rapidly (e.g., into water at 23{degrees}C) show a similar structure to slowly cooled samples. The solid state morphology also depends on the type of branching and differences between HDPE/LDPE and HDPE/LLDPE blends will be reviewed.« less

Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts

NASA Astrophysics Data System (ADS)

Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.

2012-11-01

The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.

Ab initio and density functional computations of the vibrational spectrum, molecular geometry and some molecular properties of the antidepressant drug sertraline (Zoloft) hydrochloride

NASA Astrophysics Data System (ADS)

Sagdinc, Seda; Kandemirli, Fatma; Bayari, Sevgi Haman

2007-02-01

Sertraline hydrochloride is a highly potent and selective inhibitor of serotonin (5HT). It is a basic compound of pharmaceutical application for antidepressant treatment (brand name: Zoloft). Ab initio and density functional computations of the vibrational (IR) spectrum, the molecular geometry, the atomic charges and polarizabilities were carried out. The infrared spectrum of sertraline is recorded in the solid state. The observed IR wave numbers were analysed in light of the computed vibrational spectrum. On the basis of the comparison between calculated and experimental results and the comparison with related molecules, assignments of fundamental vibrational modes are examined. The X-ray geometry and experimental frequencies are compared with the results of our theoretical calculations.

Molecular structure and vibrational spectra of Irinotecan: a density functional theoretical study.

PubMed

Chinna Babu, P; Sundaraganesan, N; Sudha, S; Aroulmoji, V; Murano, E

2012-12-01

The solid phase FTIR and FT-Raman spectra of Irinotecan have been recorded in the regions 400-4000 and 50-4000 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(d) as basis set. The vibrational frequencies were calculated for Irinotecan by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared spectrum was also simulated from the calculated intensities. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2012 Elsevier B.V. All rights reserved.

Comparison between Gaussian-type orbitals and plane wave ab initio density functional theory modeling of layer silicates: Talc [Mg{sub 3}Si{sub 4}O{sub 10}(OH){sub 2}] as model system

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

Ulian, Gianfranco; Valdrè, Giovanni, E-mail: giovanni.valdre@unibo.it; Tosoni, Sergio

2013-11-28

The quantum chemical characterization of solid state systems is conducted with many different approaches, among which the adoption of periodic boundary conditions to deal with three-dimensional infinite condensed systems. This method, coupled to the Density Functional Theory (DFT), has been proved successful in simulating a huge variety of solids. Only in relatively recent years this ab initio quantum-mechanic approach has been used for the investigation of layer silicate structures and minerals. In the present work, a systematic comparison of different DFT functionals (GGA-PBEsol and hybrid B3LYP) and basis sets (plane waves and all-electron Gaussian-type orbitals) on the geometry, energy, andmore » phonon properties of a model layer silicate, talc [Mg{sub 3}Si{sub 4}O{sub 10}(OH){sub 2}], is presented. Long range dispersion is taken into account by DFT+D method. Results are in agreement with experimental data reported in literature, with minimal deviation given by the GTO/B3LYP-D* method regarding both axial lattice parameters and interaction energy and by PW/PBE-D for the unit-cell volume and angular values. All the considered methods adequately describe the experimental talc infrared spectrum.« less

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

Do, Hainam, E-mail: h.do@nottingham.ac.uk, E-mail: richard.wheatley@nottingham.ac.uk; Wheatley, Richard J., E-mail: h.do@nottingham.ac.uk, E-mail: richard.wheatley@nottingham.ac.uk

A robust and model free Monte Carlo simulation method is proposed to address the challenge in computing the classical density of states and partition function of solids. Starting from the minimum configurational energy, the algorithm partitions the entire energy range in the increasing energy direction (“upward”) into subdivisions whose integrated density of states is known. When combined with the density of states computed from the “downward” energy partitioning approach [H. Do, J. D. Hirst, and R. J. Wheatley, J. Chem. Phys. 135, 174105 (2011)], the equilibrium thermodynamic properties can be evaluated at any temperature and in any phase. The methodmore » is illustrated in the context of the Lennard-Jones system and can readily be extended to other molecular systems and clusters for which the structures are known.« less

Reducing wall plasma expansion with gold foam irradiated by laser

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

Zhang, Lu; Ding, Yongkun, E-mail: ding-yk@vip.sina.com; Jiang, Shaoen, E-mail: jiangshn@vip.sina.com

The experimental study on the expanding plasma movement of low-density gold foam (∼1% solid density) irradiated by a high power laser is reported in this paper. Experiments were conducted using the SG-III prototype laser. Compared to solid gold with 19.3 g/cc density, the velocities of X-ray emission fronts moving off the wall are much smaller for gold foam with 0.3 g/cc density. Theoretical analysis and MULTI 1D simulation results also show less plasma blow-off, and that the density contour movement velocities of gold foam are smaller than those of solid gold, agreeing with experimental results. These results indicate that foam walls havemore » advantages in symmetry control and lowering plasma fill when used in ignition hohlraum.« less

Hexachloroethane Obscurant Replacement

DTIC Science & Technology

2012-01-01

were not totally dispersed in aerosol form; significant solid slag formation was observed. Thus, smoke density efficiency was only one quarter of that...determine smoke density and analyze for toxicity of combustion gases and particulates. Results: Compositions containing divalent zinc and...solid slag formation was observed. Thus, smoke density efficiency was only one quarter of that of the hexachloroethane containing baseline. The

Planetesimal formation in self-gravitating discs - dust trapping by vortices

NASA Astrophysics Data System (ADS)

Gibbons, P. G.; Mamatsashvili, G. R.; Rice, W. K. M.

2015-11-01

The mechanism through which metre-sized boulders grow to km-sized planetesimals in protoplanetary discs is a subject of active research, since it is critical for planet formation. To avoid spiralling into the protostar due to aerodynamic drag, objects must rapidly grow from cm-sized pebbles, which are tightly coupled to the gas, to large boulders of 1-100 m in diameter. It is already well known that overdensities in the gaseous component of the disc provide potential sites for the collection of solids, and that significant density structures in the gaseous component of the disc (e.g. spiral density waves) can trap solids efficiently enough for the solid component of the disc to undergo further gravitational collapse due to their own self-gravity. In this work, we employ the PENCIL CODE to conduct local shearing sheet simulations of massive self-gravitating protoplanetary discs, to study the effect of anticyclonic transient vortices, or eddies, on the evolution of solids in these discs. We find that these types of structures are extremely efficient at concentrating small and intermediate-sized dust particles with friction times comparable to, or less than, the local orbital period of the disc. This can lead to significant over-densities in the solid component of the disc, with density enhancements comparable to, and even higher, than those within spiral density waves; increasing the rate of gravitational collapse of solids into bound structures.

Properties of real metallic surfaces: Effects of density functional semilocality and van der Waals nonlocality

PubMed Central

Patra, Abhirup; Bates, Jefferson E.; Sun, Jianwei; Perdew, John P.

2017-01-01

We have computed the surface energies, work functions, and interlayer surface relaxations of clean (111), (100), and (110) surfaces of Al, Cu, Ru, Rh, Pd, Ag, Pt, and Au. We interpret the surface energy from liquid metal measurements as the mean of the solid-state surface energies over these three lowest-index crystal faces. We compare experimental (and random phase approximation) reference values to those of a family of nonempirical semilocal density functionals, from the basic local density approximation (LDA) to our most advanced general purpose meta-generalized gradient approximation, strongly constrained and appropriately normed (SCAN). The closest agreement is achieved by the simplest density functional LDA, and by the most sophisticated one, SCAN+rVV10 (Vydrov–Van Voorhis 2010). The long-range van der Waals interaction, incorporated through rVV10, increases the surface energies by about 10%, and increases the work functions by about 3%. LDA works for metal surfaces through two known error cancellations. The Perdew–Burke–Ernzerhof generalized gradient approximation tends to underestimate both surface energies (by about 24%) and work functions (by about 4%), yielding the least-accurate results. The amount by which a functional underestimates these surface properties correlates with the extent to which it neglects van der Waals attraction at intermediate and long range. Qualitative arguments are given for the signs of the van der Waals contributions to the surface energy and work function. A standard expression for the work function in Kohn–Sham (KS) theory is shown to be valid in generalized KS theory. Interlayer relaxations from different functionals are in reasonable agreement with one another, and usually with experiment. PMID:29042509

Generalization of dielectric-dependent hybrid functionals to finite systems

DOE PAGES

Brawand, Nicholas P.; Voros, Marton; Govoni, Marco; ...

2016-10-04

The accurate prediction of electronic and optical properties of molecules and solids is a persistent challenge for methods based on density functional theory. We propose a generalization of dielectric-dependent hybrid functionals to finite systems where the definition of the mixing fraction of exact and semilocal exchange is physically motivated, nonempirical, and system dependent. The proposed functional yields ionization potentials, and fundamental and optical gaps of many, diverse molecular systems in excellent agreement with experiments, including organic and inorganic molecules and semiconducting nanocrystals. As a result, we further demonstrate that this hybrid functional gives the correct alignment between energy levels ofmore » the exemplary TTF-TCNQ donor-acceptor system.« less

The Fundamental Chemistry and Physics of Munitions under Extreme Conditions

DTIC Science & Technology

2011-02-01

I. I. Oleynik, S. V. Zybin, and C. T. White, “Density Functional Theory Calculations of Solid Nitromethane under Hydrostatic and Uniaxial...White (NRL), Ivan Oleynik (USF): anisotropic nonlinear elasticity and equations of states of crystalline EM (PETN, RDX, HMX, TATB, nitromethane ...and nitromethane ;  Aidan Thompson (SNL): shock-to-detonation transition in PETN and CL-20;  Ronnie Kosloff (Hebrew University of Jerusalem

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

51V solid-state NMR and density functional theory studies of vanadium environments in V(V)O2 dipicolinic acid complexes

NASA Astrophysics Data System (ADS)

Bolte, Stephanie E.; Ooms, Kristopher J.; Polenova, Tatyana; Baruah, Bharat; Crans, Debbie C.; Smee, Jason J.

2008-02-01

V51 solid-state NMR and density functional theory (DFT) investigations are reported for a series of pentacoordinate dioxovanadium(V)-dipicolinate [V(V )O2-dipicolinate] and heptacoordinate aquahydroxylamidooxovanadium(V)-dipicolinate [V(V)O-dipicolinate] complexes. These compounds are of interest because of their potency as phosphatase inhibitors as well as their insulin enhancing properties and potential for the treatment of diabetes. Experimental solid-state NMR results show that the electric field gradient tensors in the V(V )O2-dipicolinate derivatives are affected significantly by substitution on the dipicolinate ring and range from 5.8to8.3MHz. The chemical shift anisotropies show less dramatic variations with respect to the ligand changes and range between -550 and -600ppm. To gain insights on the origins of the NMR parameters, DFT calculations were conducted for an extensive series of the V(V )O2- and V(V)O-dipicolinate complexes. To assess the level of theory required for the accurate calculation of the V51 NMR parameters, different functionals, basis sets, and structural models were explored in the DFT study. It is shown that the original x-ray crystallographic geometries, including all counterions and solvation water molecules within 5Å of the vanadium, lead to the most accurate results. The choice of the functional and the basis set at a high level of theory has a relatively minor impact on the outcome of the chemical shift anisotropy calculations; however, the use of large basis sets is necessary for accurate calculations of the quadrupole coupling constants for several compounds of the V(V )O2 series. These studies demonstrate that even though the vanadium compounds under investigations exhibit distorted trigonal bipyramidal coordination geometry, they have a "perfect" trigonal bipyramidal electronic environment. This observation could potentially explain why vanadate and vanadium(V) adducts are often recognized as potent transition state analogs.

Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory

DOE PAGES

Gunawardana, K. G.S.H.; Song, Xueyu

2014-12-22

Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB 2 and AB 13 crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu 5Zr(C15 b), Cu 51Zr 14(β), Cu 10Zr 7(φ), CuZr(B2) and CuZr 2 (C11 b), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of themore » hard sphere crystal complexes in the two dimensional Gaussian space, namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu 10Zr 7(φ). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.« less

Classical density functional theory and the phase-field crystal method using a rational function to describe the two-body direct correlation function.

PubMed

Pisutha-Arnond, N; Chan, V W L; Iyer, M; Gavini, V; Thornton, K

2013-01-01

We introduce a new approach to represent a two-body direct correlation function (DCF) in order to alleviate the computational demand of classical density functional theory (CDFT) and enhance the predictive capability of the phase-field crystal (PFC) method. The approach utilizes a rational function fit (RFF) to approximate the two-body DCF in Fourier space. We use the RFF to show that short-wavelength contributions of the two-body DCF play an important role in determining the thermodynamic properties of materials. We further show that using the RFF to empirically parametrize the two-body DCF allows us to obtain the thermodynamic properties of solids and liquids that agree with the results of CDFT simulations with the full two-body DCF without incurring significant computational costs. In addition, the RFF can also be used to improve the representation of the two-body DCF in the PFC method. Last, the RFF allows for a real-space reformulation of the CDFT and PFC method, which enables descriptions of nonperiodic systems and the use of nonuniform and adaptive grids.

First-principles modeling of quantum nuclear effects and atomic interactions in solid 4He at high pressure

NASA Astrophysics Data System (ADS)

Cazorla, Claudio; Boronat, Jordi

2015-01-01

We present a first-principles computational study of solid 4He at T =0 K and pressures up to ˜160 GPa. Our computational strategy consists in using van der Waals density functional theory (DFT-vdW) to describe the electronic degrees of freedom in this material, and the diffusion Monte Carlo (DMC) method to solve the Schrödinger equation describing the behavior of the quantum nuclei. For this, we construct an analytical interaction function based on the pairwise Aziz potential that closely matches the volume variation of the cohesive energy calculated with DFT-vdW in dense helium. Interestingly, we find that the kinetic energy of solid 4He does not increase appreciably with compression for P ≥85 GPa. Also, we show that the Lindemann ratio in dense solid 4He amounts to 0.10 almost independently of pressure. The reliability of customary quasiharmonic DFT (QH DFT) approaches in describing quantum nuclear effects in solids is also studied. We find that QH DFT simulations, although provide a reasonable equation of state in agreement with experiments, are not able to reproduce correctly these critical effects in compressed 4He. In particular, we disclose huge discrepancies of at least ˜50 % in the calculated 4He kinetic energies using both the QH DFT and present DFT-DMC methods.

Unified description of the slip phenomena in sheared polymer films: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Priezjev, Nikolai

2010-03-01

The dynamic behavior of the slip length in shear flow of polymer melts past atomically smooth surfaces is investigated using MD simulations. The polymer melt was modeled as a collection of FENE-LJ bead-spring chains. We consider shear flow conditions at low pressures and weak wall-fluid interaction energy so that fluid velocity profiles are linear throughout the channel at all shear rates examined. In agreement with earlier studies we confirm that for shear- thinning fluids the slip length passes through a local minimum at low shear rates and then increases rapidly at higher shear rates. We found that the rate dependence of the slip length depends on the lattice orientation at high shear rates. The MD results show that the ratio of slip length to viscosity follows a master curve when plotted as a function of a single variable that depends on the structure factor, contact density and temperature of the first fluid layer near the solid wall. The universal dependence of the slip length holds for a number of parameters of the interface: fluid density and structure (chain length), wall-fluid interaction energy, wall density, lattice orientation, thermal or solid walls.

Optimization of Cold Spray Deposition of High-Density Polyethylene Powders

NASA Astrophysics Data System (ADS)

Bush, Trenton B.; Khalkhali, Zahra; Champagne, Victor; Schmidt, David P.; Rothstein, Jonathan P.

2017-10-01

When a solid, ductile particle impacts a substrate at sufficient velocity, the resulting heat, pressure and plastic deformation can produce bonding between the particle and the substrate. The use of a cool supersonic gas flow to accelerate these solid particles is known as cold spray deposition. The cold spray process has been commercialized for some metallic materials, but further research is required to unlock the exciting potential material properties possible with polymeric particles. In this work, a combined computational and experimental study was employed to study the cold spray deposition of high-density polyethylene powders over a wide range of particle temperatures and impact velocities. Cold spray deposition of polyethylene powders was demonstrated across a range broad range of substrate materials including several different polymer substrates with different moduli, glass and aluminum. A material-dependent window of successful deposition was determined for each substrate as a function of particle temperature and impact velocity. Additionally, a study of deposition efficiency revealed the optimal process parameters for high-density polyethylene powder deposition which yielded a deposition efficiency close to 10% and provided insights into the physical mechanics responsible for bonding while highlighting paths toward future process improvements.

T-dependence of the vibrational dynamics of IBP/diME-β-CD in solid state: A FT-IR spectral and quantum chemical study

NASA Astrophysics Data System (ADS)

Crupi, V.; Guella, G.; Majolino, D.; Mancini, I.; Rossi, B.; Stancanelli, R.; Venuti, V.; Verrocchio, P.; Viliani, G.

2010-05-01

Solid inclusion complex of the non-steroidal anti-inflammatory drug Ibuprofen (IBP, (2-[4-(2-methylpropyl)phenyl]-propanoic acid) with (2,6-dimethyl)-β-cyclodextrin (diME-β-CD) has been investigated by Fourier transform infrared spectroscopy in attenuated total reflectance geometry (FTIR-ATR spectroscopy) and numerical simulation. The complexation-induced changes in the FTIR-ATR spectrum of IBP have been interpreted by comparison with the theoretical vibrational wavenumbers and IR intensities of dimeric structures of IBP, derived from symmetric hydrogen bonding of the two carboxylic groups, computed by using Density Functional Theory (DFT) calculations. From temperature-dependent studies, the enthalpy change ΔH associated with the binding of IBP with diME-β-CD for 1:1 stoichiometry, in solid phase, has been estimated.

Comparison of Intermolecular Forces in Anhydrous Sorbitol and Solvent Cocrystals.

PubMed

Dierks, Teresa M; Korter, Timothy M

2017-08-03

The hygroscopicity of solid sorbitol is important for its utilization as a sweetener in the pharmaceutical and food industries. The molecular foundations of sorbitol hydration characteristics are explored here using two solvated cocrystals, sorbitol-water and sorbitol-pyridine. In this work, solid-state density functional theory and terahertz time-domain spectroscopy were used to evaluate the relative stabilities of these cocrystals as compared to anhydrous sorbitol in terms of conformational and cohesive energies. The modification of the hydrogen-bonding network in crystalline sorbitol by solvent molecules gives new insight into the origins of the notable stability of sorbitol-water as compared to similar solids such as mannitol-water. In particular, the energy analysis reveals that the relative instability of the mannitol hydrate is based primarily in the lack of water-water interactions which provide considerable stabilization in the sorbitol-water crystal.

Magnetic islands modelled by a phase-field-crystal approach

NASA Astrophysics Data System (ADS)

Faghihi, Niloufar; Mkhonta, Simiso; Elder, Ken R.; Grant, Martin

2018-03-01

Using a minimal model based on the phase-field-crystal formalism, we study the coupling between the density and magnetization in ferromagnetic solids. Analytical calculations for the square phase in two dimensions are presented and the small deformation properties of the system are examined. Furthermore, numerical simulations are conducted to study the influence of an external magnetic field on various phase transitions, the anisotropic properties of the free energy functional, and the scaling behaviour of the growth of the magnetic domains in a crystalline solid. It is shown that the energy of the system can depend on the direction of the magnetic moments, with respect to the crystalline direction. Furthermore, the growth of the magnetic domains in a crystalline solid is studied and is shown that the growth of domains is in agreement with expected behaviour.

Theoretical calculation of the melting curve of Cu-Zr binary alloys

DOE PAGES

Gunawardana, K. G.S.H.; Wilson, S. R.; Mendelev, M. I.; ...

2014-11-14

Helmholtz free energies of the dominant binary crystalline solids found in the Cu-Zr system at high temperatures close to the melting curve are calculated. This theoretical approach combines fundamental measure density functional theory (applied to the hard-sphere reference system) and a perturbative approach to include the attractive interactions. The studied crystalline solids are Cu(fcc), Cu 51Zr 14(β), CuZr(B 2), CuZr 2(C11b), Zr(hcp), and Zr(bcc). The calculated Helmholtz free energies of crystalline solids are in good agreement with results from molecular-dynamics (MD) simulations. Using the same perturbation approach, the liquid phase free energies are calculated as a function of composition andmore » temperature, from which the melting curve of the entire composition range of this system can be obtained. Phase diagrams are determined in this way for two leading embedded atom method potentials, and the results are compared with experimental data. Furthermore, theoretical melting temperatures are compared both with experimental values and with values obtained directly from MD simulations at several compositions.« less

Accurate Exchange-Correlation Energies for the Warm Dense Electron Gas.

PubMed

Malone, Fionn D; Blunt, N S; Brown, Ethan W; Lee, D K K; Spencer, J S; Foulkes, W M C; Shepherd, James J

2016-09-09

The density matrix quantum Monte Carlo (DMQMC) method is used to sample exact-on-average N-body density matrices for uniform electron gas systems of up to 10^{124} matrix elements via a stochastic solution of the Bloch equation. The results of these calculations resolve a current debate over the accuracy of the data used to parametrize finite-temperature density functionals. Exchange-correlation energies calculated using the real-space restricted path-integral formalism and the k-space configuration path-integral formalism disagree by up to ∼10% at certain reduced temperatures T/T_{F}≤0.5 and densities r_{s}≤1. Our calculations confirm the accuracy of the configuration path-integral Monte Carlo results available at high density and bridge the gap to lower densities, providing trustworthy data in the regime typical of planetary interiors and solids subject to laser irradiation. We demonstrate that the DMQMC method can calculate free energies directly and present exact free energies for T/T_{F}≥1 and r_{s}≤2.

Tuning the density profile of surface-grafted hyaluronan and the effect of counter-ions.

PubMed

Berts, Ida; Fragneto, Giovanna; Hilborn, Jöns; Rennie, Adrian R

2013-07-01

The present paper investigates the structure and composition of grafted sodium hyaluronan at a solid-liquid interface using neutron reflection. The solvated polymer at the surface could be described with a density profile that decays exponentially towards the bulk solution. The density profile of the polymer varied depending on the deposition protocol. A single-stage deposition resulted in denser polymer layers, while layers created with a two-stage deposition process were more diffuse and had an overall lower density. Despite the diffuse density profile, two-stage deposition leads to a higher surface excess. Addition of calcium ions causes a strong collapse of the sodium hyaluronan chains, increasing the polymer density near the surface. This effect is more pronounced on the sample prepared by two-stage deposition due to the initial less dense profile. This study provides an understanding at a molecular level of how surface functionalization alters the structure and how surface layers respond to changes in calcium ions in the solvent.

Purification of metal-organic framework materials

DOEpatents

Farha, Omar K.; Hupp, Joseph T.

2012-12-04

A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

Purification of metal-organic framework materials

DOEpatents

Farha, Omar K.; Hupp, Joseph T.

2015-06-30

A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

Towards an exact correlated orbital theory for electrons

NASA Astrophysics Data System (ADS)

Bartlett, Rodney J.

2009-12-01

The formal and computational attraction of effective one-particle theories like Hartree-Fock and density functional theory raise the question of how far such approaches can be taken to offer exact results for selected properties of electrons in atoms, molecules, and solids. Some properties can be exactly described within an effective one-particle theory, like principal ionization potentials and electron affinities. This fact can be used to develop equations for a correlated orbital theory (COT) that guarantees a correct one-particle energy spectrum. They are built upon a coupled-cluster based frequency independent self-energy operator presented here, which distinguishes the approach from Dyson theory. The COT also offers an alternative to Kohn-Sham density functional theory (DFT), whose objective is to represent the electronic density exactly as a single determinant, while paying less attention to the energy spectrum. For any estimate of two-electron terms COT offers a litmus test of its accuracy for principal Ip's and Ea's. This feature for approximating the COT equations is illustrated numerically.

Ill-posedness of Dynamic Equations of Compressible Granular Flow

NASA Astrophysics Data System (ADS)

Shearer, Michael; Gray, Nico

2017-11-01

We introduce models for 2-dimensional time-dependent compressible flow of granular materials and suspensions, based on the rheology of Pouliquen and Forterre. The models include density dependence through a constitutive equation in which the density or volume fraction of solid particles with material density ρ* is taken as a function of an inertial number I: ρ = ρ * Φ(I), in which Φ(I) is a decreasing function of I. This modelling has different implications from models relying on critical state soil mechanics, in which ρ is treated as a variable in the equations, contributing to a flow rule. The analysis of the system of equations builds on recent work of Barker et al in the incompressible case. The main result is the identification of a criterion for well-posedness of the equations. We additionally analyze a modification that applies to suspensions, for which the rheology takes a different form and the inertial number reflects the role of the fluid viscosity.

Molecular dynamic simulation of Copper and Platinum nanoparticles Poiseuille flow in a nanochannels

NASA Astrophysics Data System (ADS)

Toghraie, Davood; Mokhtari, Majid; Afrand, Masoud

2016-10-01

In this paper, simulation of Poiseuille flow within nanochannel containing Copper and Platinum particles has been performed using molecular dynamic (MD). In this simulation LAMMPS code is used to simulate three-dimensional Poiseuille flow. The atomic interaction is governed by the modified Lennard-Jones potential. To study the wall effects on the surface tension and density profile, we placed two solid walls, one at the bottom boundary and the other at the top boundary. For solid-liquid interactions, the modified Lennard-Jones potential function was used. Velocity profiles and distribution of temperature and density have been obtained, and agglutination of nanoparticles has been discussed. It has also shown that with more particles, less time is required for the particles to fuse or agglutinate. Also, we can conclude that the agglutination time in nanochannel with Copper particles is faster that in Platinum nanoparticles. Finally, it is demonstrated that using nanoparticles raises thermal conduction in the channel.

Solid-liquid like phase transition in a confined granular suspension

NASA Astrophysics Data System (ADS)

Sakai, Nariaki; Lechenault, Frederic; Adda Bedia, Mokhtar

We present an experimental study of a liquid-solid like phase transition in a two-dimensional granular media. Particles are placed in a vertical Hele-Show cell filled with a denser solution of cesium-chloride. Thus, when the cell is rotated around its axis, hydrostatic pressure exerts a centripetal force on the particles which confines them towards the center. This force is in competition with gravity, thus by modifying the rotation rate, it is possible to transform continuously and reversibly the sample from a disordered loose state to an ordered packed state. The system presents many similarities with thermal systems at equilibrium like density and interface fluctuations, and the transition between the two phases goes through a coexistence state, where there is nucleation and growth of locally ordered domains which are captured by the correlation function of the hexatic order parameter. We discuss the possibility to extend the grand-canonical formalism to out-of equilibrium systems, in order to uncover a state equation between the density and the pressure in the medium.

Microstructurally Based Prediction of High Strain Failure Modes in Crystalline Solids

DTIC Science & Technology

2016-07-05

SECURITY CLASSIFICATION OF: New three-dimensional dislocation-density based crystalline plasticity formulations was used with grain-boundary (GB...Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 High strain-rate; failure, crsytalline plasticity , dislocation-density...Solids Report Title New three-dimensional dislocation-density based crystalline plasticity formulations was used with grain-boundary (GB) kinematic

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

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

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

Forces Generated by High Velocity Impact of Ice on a Rigid Structure

NASA Technical Reports Server (NTRS)

Pereira, J. Michael; Padula, Santo A., II; Revilock, Duane M.; Melis, Matthew E.

2006-01-01

Tests were conducted to measure the impact forces generated by cylindrical ice projectiles striking a relatively rigid target. Two types of ice projectiles were used, solid clear ice and lower density fabricated ice. Three forms of solid clear ice were tested: single crystal, poly-crystal, and "rejected" poly-crystal (poly-crystal ice in which defects were detected during inspection.) The solid ice had a density of approximately 56 lb/cu ft (0.9 gm/cu cm). A second set of test specimens, termed "low density ice" was manufactured by molding shaved ice into a cylindrical die to produce ice with a density of approximately 40 lb/cu ft (0.65 gm/cu cm). Both the static mechanical characteristics and the crystalline structure of the ice were found to have little effect on the observed transient response. The impact forces generated by low density ice projectiles, which had very low mechanical strength, were comparable to those of full density solid ice. This supports the hypothesis that at a velocity significantly greater than that required to produce fracture in the ice, the mechanical properties become relatively insignificant, and the impact forces are governed by the shape and mass of the projectile.

Prediction of changes in important physical parameters during composting of separated animal slurry solid fractions.

PubMed

Chowdhury, Md Albarune; de Neergaard, Andreas; Jensen, Lars Stoumann

2014-01-01

Solid-liquid separation of animal slurry, with solid fractions used for composting, has gained interest recently. However, efficient composting of separated animal slurry solid fractions (SSFs) requires a better understanding of the process dynamics in terms of important physical parameters and their interacting physical relationships in the composting matrix. Here we monitored moisture content, bulk density, particle density and air-filled porosity (AFP) during composting of SSF collected from four commercially available solid-liquid separators. Composting was performed in laboratory-scale reactors for 30 days (d) under forced aeration and measurements were conducted on the solid samples at the beginning of composting and at 10-d intervals during composting. The results suggest that differences in initial physical properties of SSF influence the development of compost maximum temperatures (40-70 degreeC). Depending on SSF, total wet mass and volume losses (expressed as % of initial value) were up to 37% and 34%, respectively. After 30 d of composting, relative losses of total solids varied from 17.9% to 21.7% and of volatile solids (VS) from 21.3% to 27.5%, depending on SSF. VS losses in all composts showed different dynamics as described by the first-order kinetic equation. The estimated component particle density of 1441 kg m-3 for VS and 2625 kg m-3 for fixed solids can be used to improve estimates of AFP for SSF within the range tested. The linear relationship between wet bulk density and AFP reported by previous researchers held true for SSF.

The Penetration Behavior of an Annular Gas-Solid Jet Impinging on a Liquid Bath: The Effects of the Density and Size of Solid Particles

NASA Astrophysics Data System (ADS)

Chang, J. S.; Sohn, H. Y.

2012-08-01

Top-blow injection of a gas-solid jet through a circular lance is used in the Mitsubishi Continuous Smelting Process. One problem associated with this injection is the severe erosion of the hearth refractory below the lances. A new configuration of the lance to form an annular gas-solid jet rather than the circular jet was designed in this laboratory. With this new configuration, the solid particles fed through the center tube leave the lance at a much lower velocity than the gas, and the penetration behavior of the jet is significantly different from that with a circular lance where the solid particles leave the lance at the same high velocity as the gas. In previous cold-model investigations in this laboratory, the effects of the gas velocity, particle feed rate, lance height of the annular lance, and the cross-sectional area of the gas jet were studied and compared with the circular lance. This study examined the effect of the density and size of the solid particles on the penetration behavior of the annular gas-solid jet, which yielded some unexpected results. The variation in the penetration depth with the density of the solid particles at the same mass feed rate was opposite for the circular lance and the annular lance. In the case of the circular lance, the penetration depth became shallower as the density of the solid particles increased; on the contrary, for the annular lance, the penetration depth became deeper with the increasing density of particles. However, at the same volumetric feed rate of the particles, the density effect was small for the circular lance, but for the annular lance, the jets with higher density particles penetrated more deeply. The variation in the penetration depth with the particle diameter was also different for the circular and the annular lances. With the circular lance, the penetration depth became deeper as the particle size decreased for all the feed rates, but with the annular lance, the effect of the particle size was small. The overall results including the previous work indicated that the penetration behavior of an annular jet is much less sensitive to the variations in operating variables than that of a circular jet. Correlation equations for the penetration depth that show good agreements with the measured values have been developed.

Forming a three-dimensional porous organic network via solid-state explosion of organic single crystals.

PubMed

Bae, Seo-Yoon; Kim, Dongwook; Shin, Dongbin; Mahmood, Javeed; Jeon, In-Yup; Jung, Sun-Min; Shin, Sun-Hee; Kim, Seok-Jin; Park, Noejung; Lah, Myoung Soo; Baek, Jong-Beom

2017-11-17

Solid-state reaction of organic molecules holds a considerable advantage over liquid-phase processes in the manufacturing industry. However, the research progress in exploring this benefit is largely staggering, which leaves few liquid-phase systems to work with. Here, we show a synthetic protocol for the formation of a three-dimensional porous organic network via solid-state explosion of organic single crystals. The explosive reaction is realized by the Bergman reaction (cycloaromatization) of three enediyne groups on 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene. The origin of the explosion is systematically studied using single-crystal X-ray diffraction and differential scanning calorimetry, along with high-speed camera and density functional theory calculations. The results suggest that the solid-state explosion is triggered by an abrupt change in lattice energy induced by release of primer molecules in the 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene crystal lattice.

Terahertz spectroscopy and computational investigation of the flufenamic acid/nicotinamide cocrystal.

PubMed

Delaney, Sean P; Korter, Timothy M

2015-04-02

Terahertz spectroscopy probes the low-frequency vibrations that are sensitive to both the intermolecular and intramolecular interactions of molecules in the solid state. Thus, terahertz spectroscopy can be a useful tool in the investigation of crystalline pharmaceutical compounds, where slight changes in the packing arrangement can modify the overall effectiveness of a drug formulation. This is especially true for cases of polymorphic systems, hydrates/solvates, and cocrystals. In this work, the cocrystal of flufenamic acid with nicotinamide was investigated using terahertz spectroscopy and solid-state density functional theory. The solid-state simulations enable understanding of the low-frequency vibrations seen in the terahertz spectra, while also providing insight into the energetics involved in the formation of the cocrystal. The comparison of the cocrystal to the pure forms of the molecular components reveals that the cocrystal has better overall binding energy, driven by increased intermolecular hydrogen bond strength and greater London dispersion forces and that the trifluoromethyl torsional potential is significantly different between the studied solids.

Tilts, dopants, vacancies and non-stoichiometry: Understanding and designing the properties of complex solid oxide perovskites from first principles

NASA Astrophysics Data System (ADS)

Bennett, Joseph W.

Perovskite oxides of formula ABO3 have a wide range of structural, electrical and mechanical properties, making them vital materials for many applications, such as catalysis, ultrasound machines and communication devices. Perovskite solid solutions with high piezoelectric response, such as ferroelectrics, are of particular interest as they can be employed as sensors in SONAR devices. Ferroelectric materials are unique in that their chemical and electrical properties can be non-invasively and reversibly changed, by switching the bulk polarization. This makes ferroelectrics useful for applications in non-volatile random access memory (NVRAM) devices. Perovskite solid solutions with a lower piezoelectric response than ferroelectrics are important for communication technology, as they function well as electroceramic capacitors. Also of interest is how these materials act as a component in a solid oxide fuel cell, as they can function as an efficient source of energy. Altering the chemical composition of these solid oxide materials offers an opportunity to change the desired properties of the final ceramic, adding a degree of flexibility that is advantageous for a variety of applications. These solid oxides are complex, sometimes disordered systems that are a challenge to study experimentally. However, as it is their complexity which produces favorable properties, highly accurate modeling which captures the essential features of the disordered structure is necessary to explain the behavior of current materials and predict favorable compositions for new materials. Methodological improvements and faster computer speeds have made first-principles and atomistic calculations a viable tool for understanding these complex systems. Offering a combination of accuracy and computational speed, the density functional theory (DFT) approach can reveal details about the microscopic structure and interactions of complex systems. Using DFT and a combination of principles from both inorganic chemistry and materials science, I have been able to gain insights into solid oxide perovskite-based systems.

Exposing high-energy surfaces by rapid-anneal solid phase epitaxy

DOE PAGES

Wang, Y.; Song, Y.; Peng, R.; ...

2017-08-08

The functional design of nanoscale transition metal oxide heterostructures depends critically on the growth of atomically flat epitaxial thin films. Much of the time, improved functionality is expected for heterostructures and surfaces with orientations that do not have the lowest surface free energy. For example, crystal faces with a high surface free energy, such as rutile (001) planes, frequently exhibit higher catalytic activities but are correspondingly harder to synthesize due to energy-lowering faceting transitions. We propose a broadly applicable rapid-anneal solid phase epitaxial synthesis approach for the creation of atomically flat, high surface free energy oxide heterostructures. We also demonstratemore » its efficacy via the synthesis of atomically flat, epitaxial RuO 2(001) films with a superior oxygen evolution activity, quantified by their lower onset potential and higher current density, relative to that of more common RuO 2(110) films.« less

Design, fabrication and characterization of a double layer solid oxide fuel cell (DLFC)

NASA Astrophysics Data System (ADS)

Wang, Guangjun; Wu, Xiangying; Cai, Yixiao; Ji, Yuan; Yaqub, Azra; Zhu, Bin

2016-11-01

A double layer solid oxide fuel cell (DLSOFC) without using the electrolyte (layer) has been designed by integrating advantages of positive electrode material of lithium ion battery(LiNi0.8Co0.15Al0.05O2) and oxygen-permeable membranes material (trace amount cobalt incorporated terbium doped ceria, TDC + Co) based on the semiconductor physics principle. Instead of using an electrolyte layer, the depletion layer between the anode and cathode served as an electronic insulator to block the electrons but to maintain the electrolyte function for ionic transport. Thus the device with two layers can realize the function of SOFC and at the same time avoids the electronic short circuiting problem. Such novel DLFC showed good performance at low temperatures, for instance, a maximum power density of 230 mWcm-2 was achieved at 500 °C. The working principle of the new device is presented.

Tailoring gadolinium-doped ceria-based solid oxide fuel cells to achieve 2 W cm(-2) at 550 °C.

PubMed

Lee, Jin Goo; Park, Jeong Ho; Shul, Yong Gun

2014-06-04

Low-temperature operation is necessary for next-generation solid oxide fuel cells due to the wide variety of their applications. However, significant increases in the fuel cell losses appear in the low-temperature solid oxide fuel cells, which reduce the cell performance. To overcome this problem, here we report Gd0.1Ce0.9O1.95-based low-temperature solid oxide fuel cells with nanocomposite anode functional layers, thin electrolytes and core/shell fibre-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ-Gd0.1Ce0.9O1.95 cathodes. In particular, the report describes the use of the advanced electrospinning and Pechini process in the preparation of the core/shell-fibre-structured cathodes. The fuel cells show a very high performance of 2 W cm(-2) at 550 °C in hydrogen, and are stable for 300 h even under the high current density of 1 A cm(-2). Hence, the results suggest that stable and high-performance solid oxide fuel cells at low temperatures can be achieved by modifying the microstructures of solid oxide fuel cell components.

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids

PubMed Central

2013-01-01

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1H and 13C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1H and 13C chemical shifts for directly bonded 13C–1H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure. PMID:24386493

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids.

PubMed

Dudenko, Dmytro V; Williams, P Andrew; Hughes, Colan E; Antzutkin, Oleg N; Velaga, Sitaram P; Brown, Steven P; Harris, Kenneth D M

2013-06-13

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1 H and 13 C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1 H and 13 C chemical shifts for directly bonded 13 C- 1 H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure.

Progress and prospect on failure mechanisms of solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Ma, Jun; Chen, Bingbing; Wang, Longlong; Cui, Guanglei

2018-07-01

By replacing traditional liquid organic electrolyte with solid-state electrolyte, the solid-state lithium batteries powerfully come back to the energy storage field due to their eminent safety and energy density. In recent years, a variety of solid-state lithium batteries based on excellent solid-state electrolytes are developed. However, the performance degradation of solid-state lithium batteries during cycling and storing is still a serious challenge for practical application. Therefore, this review summarizes the research progress of solid-state lithium batteries from the perspectives of failure phenomena and failure mechanisms. Additionally, the development of methodologies on studying the failure mechanisms of solid-state lithium batteries is also reviewed. Moreover, some perspectives on the remaining questions for understanding the failure behaviors and achieving long cycle life, high safety and high energy density solid-state lithium batteries are presented. This review will help researchers to recognize the status of solid-state lithium batteries objectively and attract much more research interest in conquering the failure issues of solid-state lithium batteries.

Influence of effective stress and dry density on the permeability of municipal solid waste.

PubMed

Zhang, Zhenying; Wang, Yingfeng; Xu, Hui; Fang, Yuehua; Wu, Dazhi

2018-05-01

A landfill is one of the main sites for disposal of municipal solid waste and the current landfill disposal system faces several problems. For instance, excessive leachate water is an important factor leading to landfill instability. Understanding the permeability characteristics of municipal solid waste is a relevant topic in the field of environmental geotechnical engineering. In this paper, the current research progress on permeability characteristics of municipal solid waste is discussed. A review of recent studies indicates that the research in this field is divided into two categories based on the experimental method employed: field tests and laboratory tests. This paper summarizes test methods, landfill locations, waste ages, dry densities and permeability coefficients across different studies that focus on permeability characteristics. Additionally, an experimental study on compressibility and permeability characteristics of fresh municipal solid waste under different effective stresses and compression times was carried out. Moreover, the relationships between the permeability coefficient and effective stress as well as dry density were obtained and a permeability prediction model was established. Finally, the experimental results from the existing literature and this paper were compared and the effects of effective stress and dry density on the permeability characteristics of municipal solid waste were summarized. This study provides the basis for analysis of leachate production in a landfill.

Solid-state structures and properties of scandium hydride; hydrogen storage and switchable mirrors application

NASA Astrophysics Data System (ADS)

Khodja, Khadidja; Bouhadda, Youcef; Seddik, Larbi; Benyelloul, Kamel

2016-05-01

First-principles calculation has been performed on the rare earth hydride ScH2 for hydrogen storage and switchable mirror applications, using the pseudo-potentials and plane waves based on the density-functional theory (DFT). The electronic and structural properties are studied within both local-density and generalized gradient approximations for exchange energy. The formation energy and the optical properties have been investigated and discussed. Our calculated results are generally in good agreement with theoretical and experimental data. Contribution to the topical issue "Materials for Energy Harvesting, Conversion and Storage (ICOME 2015) - Elected submissions", edited by Jean-Michel Nunzi, Rachid Bennacer and Mohammed El Ganaoui

A New Approach to Determine the Density of Liquids and Solids without Measuring Mass and Volume: Introducing the "Solidensimeter"

ERIC Educational Resources Information Center

Kiriktas, Halit; Sahin, Mehmet; Eslek, Sinan; Kiriktas, Irem

2018-01-01

This study aims to design a mechanism with which the density of any solid or liquid can be determined without measuring its mass and volume in order to help students comprehend the concept of density more easily. The "solidensimeter" comprises of two scaled and nested glass containers (graduated cylinder or beaker) and sufficient water.…

Measuring Young's Modulus the Easy Way, and Tracing the Effects of Measurement Uncertainties

ERIC Educational Resources Information Center

Nunn, John

2015-01-01

The speed of sound in a solid is determined by the density and elasticity of the material. Young's modulus can therefore be calculated once the density and the speed of sound in the solid are measured. The density can be measured relatively easily, and the speed of sound through a rod can be measured very inexpensively by setting up a longitudinal…

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

NASA Astrophysics Data System (ADS)

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

2011-10-01

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

Uncovering a reconstructive solid-solid phase transition in a metal-organic framework.

PubMed

Longley, L; Li, N; Wei, F; Bennett, T D

2017-11-01

A nanoporous three-dimensional metal-organic framework (MOF), ZnPurBr undergoes a transition to a previously unreported high-temperature phase, ZnPurBr-ht. The transition, which proceeds without mass loss, is uncovered through the use of differential scanning calorimetry (DSC). The new crystal structure was solved using single-crystal X-ray diffraction, and the mechanical properties of both phases investigated by nanoindentation and density functional theory. The anisotropy of the calculated Young's moduli showed good agreement with the crystallographic alignment of the stiff purinate organic linker. The results provide a prototypical example of the importance of the use of DSC in the MOF field, where its use is not currently standard in characterization.

Symmetry properties of the electron density and following from it limits on the KS-DFT applications

NASA Astrophysics Data System (ADS)

Kaplan, Ilya G.

2018-03-01

At present, the Density Functional Theory (DFT) approach elaborated by Kohn with co-authors more than 50 years ago became the most widely used method for study molecules and solids. Using modern computation facilities, it can be applied to systems with million atoms. In the atmosphere of such great popularity, it is particularly important to know the limits of the applicability of DFT methods. In this report, I will discuss two cases when the conventional DFT approaches, using only electron density ρ and its gradients, cannot be applied (I will not consider the Ψ-versions of DFT). The first case is quite evident. In the degenerated states, the electron density may not be defined, since electronic and nuclear motions cannot be separated, the vibronic interaction mixed them. The second case is related to the spin of the state. As it was rigorously proved by group theoretical methods at the theorem level, the electron density does not depend on the total spin S of the arbitrary N-electron state. It means that the Kohn-Sham equations have the same form for states with different S. The critical survey of elaborated DFT procedures, taking into account spin, shows that they modified only exchange functionals, the correlation functionals do not correspond to the spin of the state. The point is that the conception of spin cannot be defined in the framework of the electron density formalism, which corresponds to the one-particle reduced density matrix. This is the main reason of the problems arising in the study by DFT of magnetic properties of the transition metals. The possible way of resolving these problems can be found in the two-particle reduced density matrix formulation of DFT.

Fabrication of Cu-Ni mixed phase layer using DC electroplating and suppression of Kirkendall voids in Sn-Ag-Cu solder joints

NASA Astrophysics Data System (ADS)

Chee, Sang-Soo; Lee, Jong-Hyun

2014-05-01

A solderable layer concurrently containing Cu-rich and Ni-rich phases (mixed-phase layer, MPL) was fabricated by direct current electroplating under varying process conditions. Current density was considered as the main parameter to adjust the microstructure and composition of MPL during the electroplating process, and deposit thickness were evaluated as functions of plating time. As a result, it was observed that the coral-like structure that consisted of Cu-rich and Ni-rich phases grew in the thickness direction. The most desirable microstructure was obtained at a relatively low current density of 0.4 mA/cm2. In other words, the surface was the smoothest and defect-free at this current density. The electroplating rate was slightly enhanced with an increase in current density. Investigations of its solid-state reaction properties, including the formation of Kirkendall voids, were also carried out after reflow soldering with Sn-3.0 Ag-0.5 Cu solder balls. In the solid-state aging experiment at 125°C, Kirkendall voids at the normal Sn-3.0 Ag-0.5 Cu solder/Cu interface were easily formed after just 240 h. Meanwhile, the presence of an intermetallic compound (IMC) layer created in the solder/MPL interface indicated a slightly lower growth rate, and no Kirkendall voids were observed in the IMC layer even after 720 h.

Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

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

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane

In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

Density functional theory study of defect energies and space charge distribution at a solid-oxide electrolyte surface

NASA Astrophysics Data System (ADS)

Han, Chu; Bongiorno, Angelo

2014-03-01

Yttrium-doped barium zirconate (BZY) is a proton conducting electrolyte forming a class of novel materials for new generation of solid oxide fuel cells, for hydrogen separation and purification, and for electrolysis of water. Here we use density functional theory calculations to compute the energy of protons and oxygen vacancies at the surface and in the bulk of lightly Y-doped BZY materials. We found that protons are energetically more stable at the surface termination than in the bulk of BZY by about 1 eV. In contrast, doubly-positively charged oxygen vacancies are found to form iso-energetic defects at both the terminal surface layer and in the bulk of BZY, while in the sub-surface region the defect energy raises by about 1 eV with respect to the value in the bulk. The energetic behavior of protons and oxygen vacancies in the near surface region of BZY is attributed to the competition of strain and electrostatic effects. Lattice model representations of BZY surfaces are then used in combination with Monte Carlo simulations to solve the Poisson-Boltzmann equation and investigate the implication of the results above on the structure of the space charge region at the surface of BZY materials.

Electrochemical performance of Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 cermet anodes with functionally graded structures for intermediate-temperature solid oxide fuel cell fueled with syngas

NASA Astrophysics Data System (ADS)

Miyake, Michihiro; Iwami, Makoto; Takeuchi, Mizue; Nishimoto, Shunsuke; Kameshima, Yoshikazu

2018-06-01

The electrochemical performance of layered Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 (GDC) cermet anodes is investigated for intermediate-temperature solid oxide fuel cells (IT-SOFCs) at 600 °C using humidified (3% H2O) model syngas with a molar ratio of H2/CO = 3/2 as the fuel. From the results obtained, the electrochemical performance of the functionally graded multi-layered anodes is found to be superior to the mono-layered anodes. The test cell with a bi-layered anode consisting of 100 mass% Ni0.8Cu0.2/0 mass% GDC (10M/0E) and 70 mass% Ni0.8Cu0.2/30 mass% GDC (7M/3E) exhibits high power density. The test cell with a tri-layered anode consisting of 10M/0E, 7M/3E, and 50 mass% Ni0.8Cu0.2/50 mass% GDC (5M/5E) exhibits an even higher power density, suggesting that 10M/0E and 5M/5E layers contribute to the current collecting part and active part, respectively.

Density-Functional-Theory Modeling of Cation Diffusion in Bulk La 1 - x Sr x MnO 3 ± δ ( x = 0.0 – 0.25 ) for Solid-Oxide Fuel-Cell Cathodes

DOE PAGES

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; ...

2017-10-04

In this work, the A - and B -site cation migration pathways involving defect complexes in bulk La 1-xSr xMnO 3±δ (LSM) at x = 0.0-0.25 are investigated based on density-functional-theory modeling for solid-oxide fuel-cell (SOFC) cathode applications. We propose a dominant A -site cation migration mechanism which involves an A -site cation (e.g., Lamore » $$x\\atop{A}$$) V A"' of a V A"' -V B"' cluster, where La$$x\\atop{A}$$, V A"' and V B"' are La 3+, A-site vacancy, and B-site vacancy in bulk LSM, respectively, and V A"' -V B"' is the first nearest-neighbor V A"' and V B"' pair. This hop exhibits an approximately 1.6-eV migration barrier as compared to approximately 2.9 eV of the La$$x\\atop{A}$$ hop into a V A"'. This decrease in the cation migration barrier is attributed to the presence of the V B"' relieving the electrostatic repulsion and steric constraints to the migrating A-site cations in the transition-state image configurations.« less

Quantitative Computer Tomography for Determining Composition of Microgravity and Ground Based Solid Solutions

NASA Technical Reports Server (NTRS)

Gillies, D. C.; Engel, H. P.

1999-01-01

Advances in x-ray Computer Tomography (CT) have been led by the medical profession, and by evaluation of industrial products, particularly castings. Porosity can readily be determined as a function of the density of a material, and CT is thus an industrially important NDE tool. Providing high purity, 100% dense standards of pure elements and compounds can be fabricated, the composition of solid solution alloys can be determined by measuring the CT number, which is a function of the absorption of the sample. Average densities across slices 1 mm thick can generally be determined to better than 1 percent. With present technology this spatial sensitivity is less than ideal, but important benefits can nevertheless be obtained by using CT, particularly single crystals, prior to making any destructive assault upon the sample. The sample can in fact be examined prior to removal from the mold within which it has been grown and, in the cases of microgravity flight samples, before removal from the cartridge assembly. This greatly assists the researcher in the characterization of the products, particularly as a guide to cutting and sampling. Examples of work with germanium-silicon alloys and mercury cadmium telluride taken with a radioactive cobalt source will be demonstrated.

Pressure-enabled phonon engineering in metals

PubMed Central

Lanzillo, Nicholas A.; Thomas, Jay B.; Watson, Bruce; Washington, Morris; Nayak, Saroj K.

2014-01-01

We present a combined first-principles and experimental study of the electrical resistivity in aluminum and copper samples under pressures up to 2 GPa. The calculations are based on first-principles density functional perturbation theory, whereas the experimental setup uses a solid media piston–cylinder apparatus at room temperature. We find that upon pressurizing each metal, the phonon spectra are blue-shifted and the net electron–phonon interaction is suppressed relative to the unstrained crystal. This reduction in electron–phonon scattering results in a decrease in the electrical resistivity under pressure, which is more pronounced for aluminum than for copper. We show that density functional perturbation theory can be used to accurately predict the pressure response of the electrical resistivity in these metals. This work demonstrates how the phonon spectra in metals can be engineered through pressure to achieve more attractive electrical properties. PMID:24889627

Communication: Unraveling the 4He droplet-mediated soft-landing from ab initio-assisted and time-resolved density functional simulations: Au@4He300/TiO2(110)

NASA Astrophysics Data System (ADS)

de Lara-Castells, María Pilar; Aguirre, Néstor F.; Stoll, Hermann; Mitrushchenkov, Alexander O.; Mateo, David; Pi, Martí

2015-04-01

An ab-initio-based methodological scheme for He-surface interactions and zero-temperature time-dependent density functional theory for superfluid 4He droplets motion are combined to follow the short-time collision dynamics of the Au@4He300 system with the TiO2(110) surface. This composite approach demonstrates the 4He droplet-assisted sticking of the metal species to the surface at low landing energy (below 0.15 eV/atom), thus providing the first theoretical evidence of the experimentally observed 4He droplet-mediated soft-landing deposition of metal nanoparticles on solid surfaces [Mozhayskiy et al., J. Chem. Phys. 127, 094701 (2007) and Loginov et al., J. Phys. Chem. A 115, 7199 (2011)].

Instrumental effects on the temperature and density derived from the light ion mass spectrometer

NASA Technical Reports Server (NTRS)

Craven, P. D.; Reasoner, D. L.

1983-01-01

An expression for the flux into a retarding potential analyzer (RPA) is derived which takes into account the instrumental effect of a dependence on energy of the solid angle of the acceptance cone. A second instrumental effect of a limited bandpass is briefly discussed. Using the (LIMS) instrument on SCATHA, it is shown that temperatures and densities derived without considering the effect of the solid angle dependence on energy will be too low, dramatically so for E(t) E(1), where E(1) is the e folding distance of the solid angle dependence and E(t) is the thermal energy of the plasma. For E(t) E(1), there is effectively no impact on the derived temperatures and densities if the solid angle effect is ignored.

Large scale GW calculations

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

Govoni, Marco; Galli, Giulia

We present GW calculations of molecules, ordered and disordered solids and interfaces, which employ an efficient contour deformation technique for frequency integration and do not require the explicit evaluation of virtual electronic states nor the inversion of dielectric matrices. We also present a parallel implementation of the algorithm, which takes advantage of separable expressions of both the single particle Green’s function and the screened Coulomb interaction. The method can be used starting from density functional theory calculations performed with semilocal or hybrid functionals. The newly developed technique was applied to GW calculations of systems of unprecedented size, including water/semiconductor interfacesmore » with thousands of electrons.« less

Large Scale GW Calculations

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

Govoni, Marco; Galli, Giulia

We present GW calculations of molecules, ordered and disordered solids and interfaces, which employ an efficient contour deformation technique for frequency integration and do not require the explicit evaluation of virtual electronic states nor the inversion of dielectric matrices. We also present a parallel implementation of the algorithm which takes advantage of separable expressions of both the single particle Green's function and the screened Coulomb interaction. The method can be used starting from density functional theory calculations performed with semilocal or hybrid functionals. We applied the newly developed technique to GW calculations of systems of unprecedented size, including water/semiconductor interfacesmore » with thousands of electrons.« less

Large scale GW calculations

DOE PAGES

Govoni, Marco; Galli, Giulia

2015-01-12

We present GW calculations of molecules, ordered and disordered solids and interfaces, which employ an efficient contour deformation technique for frequency integration and do not require the explicit evaluation of virtual electronic states nor the inversion of dielectric matrices. We also present a parallel implementation of the algorithm, which takes advantage of separable expressions of both the single particle Green’s function and the screened Coulomb interaction. The method can be used starting from density functional theory calculations performed with semilocal or hybrid functionals. The newly developed technique was applied to GW calculations of systems of unprecedented size, including water/semiconductor interfacesmore » with thousands of electrons.« less

Infrared observations and laboratory simulations of interstellar CH_4_ and SO_2_.

NASA Astrophysics Data System (ADS)

Boogert, A. C. A.; Schutte, W. A.; Helmich, F. P.; Tielens, A. G. G. M.; Wooden, D. H.

1997-02-01

Interstellar CH_4_ may consume a fair amount of the carbon budget in dense molecular clouds, but probably less than CO, CH_3_OH, and CO_2_. However, it can only be observed at wavelength regions in the infrared that are heavily affected by the earth atmosphere. With new space and airborne missions (e.g. ISO, SOFIA) in mind we have studied the near infrared absorption spectra of solid and gaseous CH_4_. We obtained laboratory spectra of the ν_4_ deformation mode (1302cm^-1^, 7.68μm) of solid CH_4_ in astrophysically relevant mixtures. We found that the peak position and width of this absorption band vary strongly as a function of molecular environment, compared to temperature and particle shape effects. Hence, observations of this feature will provide a powerful probe of the molecular composition of interstellar ices. Also the gas phase CH_4_ ro-vibrational spectrum of the same band has been calculated. Using observed physical conditions around the protostar W 33A, we show that unresolved gaseous CH_4_ lines are detectable (at the 2-5% level) at a resolution R>1000, when the column density N>=10^16^ cm^-2^. An astrophysically relevant molecule with a very strong transition in the same wavelength regime, is SO_2_. We studied the ν _3_ asymmetric stretching mode (1319 cm^-1^, 7.58 μm) of solid SO_2_ in several mixtures, revealing that the peak position, width and detailed profile of this band are very sensitive to the molecular environment. Besides probing the composition of ice mantles, observations of solid SO_2_ will provide important information on the sulfur budget locked up in grain mantles, which is currently poorly known. We compare the laboratory and calculated spectra of CH_4_ and SO_2_ with previously published ground based spectra and new airborne observations of young stellar objects in the 7-8μm region. W 33A, NGC 7538 : IRS1 and IRS9 show a feature near 7.68μm that is consistent with absorption by solid CH_4_ or the Q-branch of gaseous CH_4_. The column density of solid CH_4_ would be 0.3-4% of solid H_2_O, indicating that solid CH_4_ consumes 0.5+/-0.3% of the cosmic carbon abundance. A gaseous origin would imply a column density of at least this amount, being highly dependent on the assumed temperature of the absorbing gas. A second absorption feature is detected toward W 33A and NGC 7538 : IRS1 at 7.58 μm. The peak position and width of this feature are consistent with the ν_3_ mode of solid SO_2_ in a matrix of solid CH_3_OH or pure SO_2_. The derived column density is 0.1-1% of solid H_2_O, indicating that solid SO_2_ locks up 0.6-6% of the cosmic sulfur abundance. This study shows that 7-8μm spectroscopy of dense molecular clouds, using new airborne and space-based platforms, will provide valuable information on the composition of icy grain mantles and molecular cloud chemistry.

Extended analytical solutions for effective elastic moduli of cracked porous media

NASA Astrophysics Data System (ADS)

Nguyen, Sy-Tuan; To, Quy Dong; Vu, Minh Ngoc

2017-05-01

Extended solutions are derived, on the basis of the micromechanical methods, for the effective elastic moduli of porous media containing stiff pores and both open and closed cracks. Analytical formulas of the overall bulk and shear moduli are obtained as functions of the elastic moduli of the solid skeleton, porosity and the densities of open and closed cracks families. We show that the obtained results are extensions of the classical widely used Walsh's (JGR, 1965) and Budiansky-O‧Connell's (JGR, 1974) solutions. Parametric sensitivity analysis clarifies the impact of the model parameters on the effective elastic properties. An inverse analysis, using sonic and density data, is considered to quantify the density of both open and closed cracks. It is observed that the density of closed cracks depends strongly on stress condition while the dependence of open cracks on the confining stress is negligible.

Theory of amorphous ices.

PubMed

Limmer, David T; Chandler, David

2014-07-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens.

Isochoric Heating of Solid-Density Matter with an Ultrafast Proton Beam

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

Key, M H; Mackinnon, A J; Patel, P K

A new technique is described for the isochoric heating (i.e., heating at constant volume) of matter to high energy-density plasma states (>10{sup 5} J/g) on a picosecond timescale (10{sup -12} sec). An intense, collimated, ultrashort-pulse beam of protons--generated by a high-intensity laser pulse--is used to isochorically heat a solid density material to a temperature of several eV. The duration of heating is shorter than the timescale for significant hydrodynamic expansion to occur, hence the material is heated to a solid density warm dense plasma state. Using spherically-shaped laser targets a focused proton beam is produced and used to heat amore » smaller volume to over 20 eV. The technique described of ultrafast proton heating provides a unique method for creating isochorically heated high-energy density plasma states.« less

Achieving High-Energy-High-Power Density in a Flexible Quasi-Solid-State Sodium Ion Capacitor.

PubMed

Li, Hongsen; Peng, Lele; Zhu, Yue; Zhang, Xiaogang; Yu, Guihua

2016-09-14

Simultaneous integration of high-energy output with high-power delivery is a major challenge for electrochemical energy storage systems, limiting dual fine attributes on a device. We introduce a quasi-solid-state sodium ion capacitor (NIC) based on a battery type urchin-like Na2Ti3O7 anode and a capacitor type peanut shell derived carbon cathode, using a sodium ion conducting gel polymer as electrolyte, achieving high-energy-high-power characteristics in solid state. Energy densities can reach 111.2 Wh kg(-1) at power density of 800 W kg(-1), and 33.2 Wh kg(-1) at power density of 11200 W kg(-1), which are among the best reported state-of-the-art NICs. The designed device also exhibits long-term cycling stability over 3000 cycles with capacity retention ∼86%. Furthermore, we demonstrate the assembly of a highly flexible quasi-solid-state NIC and it shows no obvious capacity loss under different bending conditions.

The Cassie-Wenzel transition of fluids on nanostructured substrates: Macroscopic force balance versus microscopic density-functional theory.

PubMed

Tretyakov, Nikita; Papadopoulos, Periklis; Vollmer, Doris; Butt, Hans-Jürgen; Dünweg, Burkhard; Daoulas, Kostas Ch

2016-10-07

Classical density functional theory is applied to investigate the validity of a phenomenological force-balance description of the stability of the Cassie state of liquids on substrates with nanoscale corrugation. A bulk free-energy functional of third order in local density is combined with a square-gradient term, describing the liquid-vapor interface. The bulk free energy is parameterized to reproduce the liquid density and the compressibility of water. The square-gradient term is adjusted to model the width of the water-vapor interface. The substrate is modeled by an external potential, based upon the Lennard-Jones interactions. The three-dimensional calculation focuses on substrates patterned with nanostripes and square-shaped nanopillars. Using both the force-balance relation and density-functional theory, we locate the Cassie-to-Wenzel transition as a function of the corrugation parameters. We demonstrate that the force-balance relation gives a qualitatively reasonable description of the transition even on the nanoscale. The force balance utilizes an effective contact angle between the fluid and the vertical wall of the corrugation to parameterize the impalement pressure. This effective angle is found to have values smaller than the Young contact angle. This observation corresponds to an impalement pressure that is smaller than the value predicted by macroscopic theory. Therefore, this effective angle embodies effects specific to nanoscopically corrugated surfaces, including the finite range of the liquid-solid potential (which has both repulsive and attractive parts), line tension, and the finite interface thickness. Consistently with this picture, both patterns (stripes and pillars) yield the same effective contact angles for large periods of corrugation.

The structure and properties of a simple model mixture of amphiphilic molecules and ions at a solid surface

NASA Astrophysics Data System (ADS)

Pizio, O.; Sokołowski, S.; Sokołowska, Z.

2014-05-01

We investigate microscopic structure, adsorption, and electric properties of a mixture that consists of amphiphilic molecules and charged hard spheres in contact with uncharged or charged solid surfaces. The amphiphilic molecules are modeled as spheres composed of attractive and repulsive parts. The electrolyte component of the mixture is considered in the framework of the restricted primitive model (RPM). The system is studied using a density functional theory that combines fundamental measure theory for hard sphere mixtures, weighted density approach for inhomogeneous charged hard spheres, and a mean-field approximation to describe anisotropic interactions. Our principal focus is in exploring the effects brought by the presence of ions on the distribution of amphiphilic particles at the wall, as well as the effects of amphiphilic molecules on the electric double layer formed at solid surface. In particular, we have found that under certain thermodynamic conditions a long-range translational and orientational order can develop. The presence of amphiphiles produces changes of the shape of the differential capacitance from symmetric or non-symmetric bell-like to camel-like. Moreover, for some systems the value of the potential of the zero charge is non-zero, in contrast to the RPM at a charged surface.

Sodium ion transport mechanisms in antiperovskite electrolytes Na 3OBr and Na 4OI 2: An in Situ neutron diffraction study

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

Zhu, Jinlong; Wang, Yonggang; Li, Shuai

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-stat battery. In this work, the sodium ionic transport pathways of the parent compound Na 3OBr, as well as the modified layered antiperovskite Na 4OI 2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na 3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions ho within and among oxygen octahedra, and Br - ions are not involved in the tetragonal Namore » 4OI 2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. In conclusion, the transport of sodium ions along the c axis is assisted by I - ions.« less

Visualising crystal packing interactions in solid-state NMR: Concepts and applications

NASA Astrophysics Data System (ADS)

Zilka, Miri; Sturniolo, Simone; Brown, Steven P.; Yates, Jonathan R.

2017-10-01

In this article, we introduce and apply a methodology, based on density functional theory and the gauge-including projector augmented wave approach, to explore the effects of packing interactions on solid-state nuclear magnetic resonance (NMR) parameters. A visual map derived from a so-termed "magnetic shielding contribution field" can be made of the contributions to the magnetic shielding of a specific site—partitioning the chemical shift to specific interactions. The relation to the established approaches of examining the molecule to crystal change in the chemical shift and the nuclear independent chemical shift is established. The results are applied to a large sample of 71 molecular crystals and three further specific examples from supermolecular chemistry and pharmaceuticals. This approach extends the NMR crystallography toolkit and provides insight into the development of both cluster based approaches to the predictions of chemical shifts and for empirical predictions of chemical shifts in solids.

Unsteady combustion of solid propellants

NASA Astrophysics Data System (ADS)

Chung, T. J.; Kim, P. K.

The oscillatory motions of all field variables (pressure, temperature, velocity, density, and fuel fractions) in the flame zone of solid propellant rocket motors are calculated using the finite element method. The Arrhenius law with a single step forward chemical reaction is used. Effects of radiative heat transfer, impressed arbitrary acoustic wave incidence, and idealized mean flow velocities are also investigated. Boundary conditions are derived at the solid-gas interfaces and at the flame edges which are implemented via Lagrange multipliers. Perturbation expansions of all governing conservation equations up to and including the second order are carried out so that nonlinear oscillations may be accommodated. All excited frequencies are calculated by means of eigenvalue analyses, and the combustion response functions corresponding to these frequencies are determined. It is shown that the use of isoparametric finite elements, Gaussian quadrature integration, and the Lagrange multiplier boundary matrix scheme offers a convenient approach to two-dimensional calculations.

High-pressure/high-temperature polymorphs of energetic materials by first-principles simulations

NASA Astrophysics Data System (ADS)

Le, Nam; Schweigert, Igor

2017-06-01

Energetic molecular crystals exhibit complex phase diagrams that include solid-solid phase transitions, melting, and decomposition. Sorescu and Rice have recently demonstrated that first-principles molecular dynamics (MD) simulations based on dispersion-corrected density functional theory (DFT) can capture the α to γ phase transition in hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) on time scales of several picoseconds. Motivated by their work, we are using DFT-based MD to model the relative stability of solid phases in several molecular crystals. In this presentation, we report simulations of pentaerythritol tetranitrate (PETN) and 2,4,6-trinitrotoluene (TNT) under high pressures and temperatures and compare them with experimentally observed polymorphs. This work was supported by the U.S. Naval Research Laboratory via the National Research Council and by the Office of Naval Research through the U.S. Naval Research Laboratory.

Shock response and phase transitions of MgO at planetary impact conditions

DOE PAGES

Root, Seth; Shulenburger, Luke; Lemke, Raymond W.; ...

2015-11-04

The moon-forming impact and the subsequent evolution of the proto-Earth is strongly dependent on the properties of materials at the extreme conditions generated by this violent collision. We examine the high pressure behavior of MgO, one of the dominant constituents in Earth’s mantle, using high-precision, plate impact shock compression experiments performed on Sandia National Laboratories’ Z Machine and extensive quantum calculations using density functional theory (DFT) and quantum Monte Carlo (QMC) methods. The combined data span from ambient conditions to 1.2 TPa and 42,000 K, showing solid-solid and solid-liquid phase boundaries. Furthermore our results indicate that under impact the solidmore » and liquid phases coexist for more than 100 GPa, pushing complete melting to pressures in excess of 600 GPa. Furthermore, the high pressure required for complete shock melting has implications for a broad range of planetary collision events.« less

Photonic band gap in isotropic hyperuniform disordered solids with low dielectric contrast.

PubMed

Man, Weining; Florescu, Marian; Matsuyama, Kazue; Yadak, Polin; Nahal, Geev; Hashemizad, Seyed; Williamson, Eric; Steinhardt, Paul; Torquato, Salvatore; Chaikin, Paul

2013-08-26

We report the first experimental demonstration of a TE-polarization photonic band gap (PBG) in a 2D isotropic hyperuniform disordered solid (HUDS) made of dielectric media with a dielectric index contrast of 1.6:1, very low for PBG formation. The solid is composed of a connected network of dielectric walls enclosing air-filled cells. Direct comparison with photonic crystals and quasicrystals permitted us to investigate band-gap properties as a function of increasing rotational isotropy. We present results from numerical simulations proving that the PBG observed experimentally for HUDS at low index contrast has zero density of states. The PBG is associated with the energy difference between complementary resonant modes above and below the gap, with the field predominantly concentrated in the air or in the dielectric. The intrinsic isotropy of HUDS may offer unprecedented flexibilities and freedom in applications (i. e. defect architecture design) not limited by crystalline symmetries.

UV absorption spectrum of allene radical cations in solid argon

NASA Astrophysics Data System (ADS)

Chin, Chih-Hao; Lin, Meng-Yeh; Huang, Tzu-Ping; Wu, Yu-Jong

2018-05-01

Electron bombardment during deposition of an Ar matrix containing a small proportion of allene generated allene cations. Further irradiation of the matrix sample at 385 nm destroyed the allene cations and formed propyne cations in solid Ar. Both cations were identified according to previously reported IR absorption bands. Using a similar technique, we recorded the ultraviolet absorption spectrum of allene cations in solid Ar. The vibrationally resolved progression recorded in the range of 266-237 nm with intervals of about 800 cm-1 was assigned to the A2E ← X2E transition of allene cations, and the broad continuum absorption recorded in the region of 229-214 nm was assigned to their B2A1 ← X2E transition. These assignments were made based on the observed photolytic behavior of the progressions and the vertical excitation energies and oscillator strengths calculated using time-dependent density functional theory.

Sodium ion transport mechanisms in antiperovskite electrolytes Na 3OBr and Na 4OI 2: An in Situ neutron diffraction study

DOE PAGES

Zhu, Jinlong; Wang, Yonggang; Li, Shuai; ...

2016-06-02

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-stat battery. In this work, the sodium ionic transport pathways of the parent compound Na 3OBr, as well as the modified layered antiperovskite Na 4OI 2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na 3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions ho within and among oxygen octahedra, and Br - ions are not involved in the tetragonal Namore » 4OI 2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. In conclusion, the transport of sodium ions along the c axis is assisted by I - ions.« less

A metallicity recipe for rocky planets

NASA Astrophysics Data System (ADS)

Dawson, Rebekah I.; Chiang, Eugene; Lee, Eve J.

2015-10-01

Planets with sizes between those of Earth and Neptune divide into two populations: purely rocky bodies whose atmospheres contribute negligibly to their sizes, and larger gas-enveloped planets possessing voluminous and optically thick atmospheres. We show that whether a planet forms rocky or gas-enveloped depends on the solid surface density of its parent disc. Assembly times for rocky cores are sensitive to disc solid surface density. Lower surface densities spawn smaller planetary embryos; to assemble a core of given mass, smaller embryos require more mergers between bodies farther apart and therefore exponentially longer formation times. Gas accretion simulations yield a rule of thumb that a rocky core must be at least 2M⊕ before it can acquire a volumetrically significant atmosphere from its parent nebula. In discs of low solid surface density, cores of such mass appear only after the gas disc has dissipated, and so remain purely rocky. Higher surface density discs breed massive cores more quickly, within the gas disc lifetime, and so produce gas-enveloped planets. We test model predictions against observations, using planet radius as an observational proxy for gas-to-rock content and host star metallicity as a proxy for disc solid surface density. Theory can explain the observation that metal-rich stars host predominantly gas-enveloped planets.

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

Castaño-González, E.-E.; Seña, N.; Mendoza-Estrada, V.

In this paper, we carried out first-principles calculations in order to investigate the structural and electronic properties of the binary compound gallium antimonide (GaSb). This theoretical study was carried out using the Density Functional Theory within the plane-wave pseudopotential method. The effects of exchange and correlation (XC) were treated using the functional Local Density Approximation (LDA), generalized gradient approximation (GGA): Perdew–Burke–Ernzerhof (PBE), Perdew-Burke-Ernzerhof revised for solids (PBEsol), Perdew-Wang91 (PW91), revised Perdew–Burke–Ernzerhof (rPBE), Armiento–Mattson 2005 (AM05) and meta-generalized gradient approximation (meta-GGA): Tao–Perdew–Staroverov–Scuseria (TPSS) and revised Tao–Perdew–Staroverov–Scuseria (RTPSS) and modified Becke-Johnson (MBJ). We calculated the densities of state (DOS) and band structuremore » with different XC potentials identified and compared them with the theoretical and experimental results reported in the literature. It was discovered that functional: LDA, PBEsol, AM05 and RTPSS provide the best results to calculate the lattice parameters (a) and bulk modulus (B{sub 0}); while for the cohesive energy (E{sub coh}), functional: AM05, RTPSS and PW91 are closer to the values obtained experimentally. The MBJ, Rtpss and AM05 values found for the band gap energy is slightly underestimated with those values reported experimentally.« less

The ionic versus metallic nature of 2D electrides: a density-functional description.

PubMed

Dale, Stephen G; Johnson, Erin R

2017-10-18

The two-dimensional (2D) electrides are a highly unusual class of materials, possessing interstitial electron layers sandwiched between cationic atomic layers of the solid. In this work, density-functional theory, with the exchange-hole dipole moment dispersion correction, is used to investigate exfoliation and interlayer sliding of the only two experimentally known 2D electrides: [Ca 2 N] + e - and [Y 2 C] 2+ (2e - ). Examination of the valence states during exfoliation identifies intercalated electrons in the bulk and weakly-bound surface-states in the fully-expanded case. The calculated exfoliation energies for the 2D electrides are found to be much higher than for typical 2D materials, which is attributed to the ionic nature of the electrides and the strong Coulomb forces governing the interlayer interactions. Conversely, the calculated sliding barriers are found to be quite low, comparable to those for typical 2D materials, and are effectively unchanged by exclusion of dispersion. We conjecture that the metallic nature of the interstitial electrons allows the atomic layers to move relative to each other without significantly altering the interlayer binding. Finally, comparison with previous works reveals the importance of a system-dependent dispersion correction in the density-functional treatment.

Sputtering from a Porous Material by Penetrating Ions

NASA Technical Reports Server (NTRS)

Rodriguez-Nieva, J. F.; Bringa, E. M.; Cassidy, T. A.; Johnson, R. E.; Caro, A.; Fama, M.; Loeffler, M.; Baragiola, R. A.; Farkas, D.

2012-01-01

Porous materials are ubiquitous in the universe and weathering of porous surfaces plays an important role in the evolution of planetary and interstellar materials. Sputtering of porous solids in particular can influence atmosphere formation, surface reflectivity, and the production of the ambient gas around materials in space, Several previous studies and models have shown a large reduction in the sputtering of a porous solid compared to the sputtering of the non-porous solid. Using molecular dynamics simulations we study the sputtering of a nanoporous solid with 55% of the solid density. We calculate the electronic sputtering induced by a fast, penetrating ion, using a thermal spike representation of the deposited energy. We find that sputtering for this porous solid is, surprisingly, the same as that for a full-density solid, even though the sticking coefficient is high.

Structural, Electronic, and Optical Properties of BiOX1-xYx (X, Y = F, Cl, Br, and I) Solid Solutions from DFT Calculations.

PubMed

Zhao, Zong-Yan; Liu, Qing-Lu; Dai, Wen-Wu

2016-08-23

Six BiOX1-xYx (X, Y = F, Cl, Br, and I) solid solutions have been systematically investigated by density functional theory calculations. BiOCl1-xBrx, BiOBr1-xIx, and BiOCl1-xIx solid solutions have very small bowing parameters; as such, some of their properties increase almost linearly with increasing x. For BiOF1-xYx solid solutions, the bowing parameters are very large and it is extremely difficult to fit the related calculated data by a single equation. Consequently, BiOX1-xYx (X, Y = Cl, Br, and I) solid solutions are highly miscible, while BiOF1-xYx (Y = Cl, Br, and I) solid solutions are partially miscible. In other words, BiOF1-xYx solid solutions have miscibility gaps or high miscibility temperature, resulting in phase separation and F/Y inhomogeneity. Comparison and analysis of the calculated results and the related physical-chemical properties with different halogen compositions indicates that the parameters of BiOX1-xYx solid solutions are determined by the differences of the physical-chemical properties of the two halogen compositions. In this way, the large deviation of some BiOX1-xYx solid solutions from Vegard's law observed in experiments can be explained. Moreover, the composition ratio of BiOX1-xYx solid solutions can be measured or monitored using optical measurements.

A DFT study on structural, vibrational properties, and quasiparticle band structure of solid nitromethane.

PubMed

Appalakondaiah, S; Vaitheeswaran, G; Lebègue, S

2013-05-14

We report a detailed theoretical study of the structural and vibrational properties of solid nitromethane using first principles density functional calculations. The ground state properties were calculated using a plane wave pseudopotential code with either the local density approximation, the generalized gradient approximation, or with a correction to include van der Waals interactions. Our calculated equilibrium lattice parameters and volume using a dispersion correction are found to be in reasonable agreement with the experimental results. Also, our calculations reproduce the experimental trends in the structural properties at high pressure. We found a discontinuity in the bond length, bond angles, and also a weakening of hydrogen bond strength in the pressure range from 10 to 12 GPa, picturing the structural transition from phase I to phase II. Moreover, we predict the elastic constants of solid nitromethane and find that the corresponding bulk modulus is in good agreement with experiments. The calculated elastic constants show an order of C11> C22 > C33, indicating that the material is more compressible along the c-axis. We also calculated the zone center vibrational frequencies and discuss the internal and external modes of this material under pressure. From this, we found the softening of lattice modes around 8-11 GPa. We have also attempted the quasiparticle band structure of solid nitromethane with the G0W0 approximation and found that nitromethane is an indirect band gap insulator with a value of the band gap of about 7.8 eV with G0W0 approximation. Finally, the optical properties of this material, namely the absorptive and dispersive part of the dielectric function, and the refractive index and absorption spectra are calculated and the contribution of different transition peaks of the absorption spectra are analyzed. The static dielectric constant and refractive indices along the three inequivalent crystallographic directions indicate that this material has a considerable optical anisotropy.

The phase diagram and transport properties of MgO from theory and experiment

NASA Astrophysics Data System (ADS)

Shulenburger, Luke

2013-06-01

Planetary structure and the formation of terrestrial planets have received tremendous interest due to the discovery of so called super-earth exoplanets. MgO is a major constituent of Earth's mantle, the rocky cores of gas giants and is a likely component of the interiors of many of these exoplanets. The high pressure - high temperature behavior of MgO directly affects equation of state models for planetary structure and formation. In this work, we examine MgO under extreme conditions using experimental and theoretical methods to determine its phase diagram and transport properties. Using plate impact experiments on Sandia's Z facility the solid-solid phase transition from B1 to B2 is clearly determined. The melting transition, on the other hand, is subtle, involving little to no signal in us-up space. Theoretical work utilizing density functional theory (DFT) provides a complementary picture of the phase diagram. The solid-solid phase transition is identified through a series of quasi-harmonic phonon calculations and thermodynamic integration, while the melt boundary is found using phase coexistence calculations. One issue of particular import is the calculation of reflectivity along the Hugoniot and the influence of the ionic structure on the transport properties. Particular care is necessary because of the underestimation of the band gap and attendant overestimation of transport properties due to the use of semi-local density functional theory. We will explore the impact of this theoretical challenge and its potential solutions in this talk. The integrated use of DFT simulations and high-accuracy shock experiments together provide a comprehensive understanding of MgO under extreme conditions. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Electrodeposition of Polypyrrole and Reduced Graphene Oxide onto Carbon Bundle Fibre as Electrode for Supercapacitor.

PubMed

Abdul Bashid, Hamra Assyaima; Lim, Hong Ngee; Kamaruzaman, Sazlinda; Abdul Rashid, Suraya; Yunus, Robiah; Huang, Nay Ming; Yin, Chun Yang; Rahman, Mohammad Mahbubur; Altarawneh, Mohammednoor; Jiang, Zhong Tao; Alagarsamy, Pandikumar

2017-12-01

A nanocomposite comprising of polypyrrole and reduced graphene oxide was electrodeposited onto a carbon bundle fibre (CBF) through a two-step approach (CBF/PPy-rGO-2). The CBF/PPy-rGO-2 had a highly porous structure compared to a nanocomposite of polypyrrole and reduced graphene oxide that was electrodeposited onto a CBF in a one-step approach (CBF/PPy-rGO), as observed through a field emission scanning electron microscope. An X-ray photoelectron spectroscopic analysis revealed the presence of hydrogen bond between the oxide functional groups of rGO and the amine groups of PPy in PPy-rGO-2 nanocomposite. The fabricated CBF/PPy-rGO-2 nanocomposite material was used as an electrode material in a symmetrical solid-state supercapacitor, and the device yielded a specific capacitance, energy density and power density of 96.16 F g - 1 , 13.35 Wh kg - 1 and of 322.85 W kg - 1 , respectively. Moreover, the CBF/PPy-rGO-2 showed the capacitance retention of 71% after 500 consecutive charge/discharge cycles at a current density of 1 A g - 1 . The existence of a high degree of porosity in CBF/PPy-rGO-2 significantly improved the conductivity and facilitated the ionic penetration. The CBF/PPy-rGO-2-based symmetrical solid-state supercapacitor device demonstrated outstanding pliability because the cyclic voltammetric curves remained the same upon bending at various angles. Carbon bundle fibre modified with porous polypyrrole/reduced graphene oxide nanocomposite for flexible miniature solid-state supercapacitor.

Theory of amorphous ices

PubMed Central

Limmer, David T.; Chandler, David

2014-01-01

We derive a phase diagram for amorphous solids and liquid supercooled water and explain why the amorphous solids of water exist in several different forms. Application of large-deviation theory allows us to prepare such phases in computer simulations. Along with nonequilibrium transitions between the ergodic liquid and two distinct amorphous solids, we establish coexistence between these two amorphous solids. The phase diagram we predict includes a nonequilibrium triple point where two amorphous phases and the liquid coexist. Whereas the amorphous solids are long-lived and slowly aging glasses, their melting can lead quickly to the formation of crystalline ice. Further, melting of the higher density amorphous solid at low pressures takes place in steps, transitioning to the lower-density glass before accessing a nonequilibrium liquid from which ice coarsens. PMID:24858957

Densitometry By Acoustic Levitation

NASA Technical Reports Server (NTRS)

Trinh, Eugene H.

1989-01-01

"Static" and "dynamic" methods developed for measuring mass density of acoustically levitated solid particle or liquid drop. "Static" method, unknown density of sample found by comparison with another sample of known density. "Dynamic" method practiced with or without gravitational field. Advantages over conventional density-measuring techniques: sample does not have to make contact with container or other solid surface, size and shape of samples do not affect measurement significantly, sound field does not have to be know in detail, and sample can be smaller than microliter. Detailed knowledge of acoustic field not necessary.

CARS applications to combustion diagnostics

NASA Astrophysics Data System (ADS)

Eckbreth, Alan C.

1986-01-01

Attention is given to broadband or multiplex CARS of combustion processes, using pulsed lasers whose intensity is sufficiently great for instantaneous measurement of medium properties. This permits probability density functions to be assembled from a series of single-pulse measurements, on the basis of which the true parameter average and the magnitude of the turbulent fluctuations can be ascertained. CARS measurements have been conducted along these lines in diesel engines, gas turbine combustors, scramjets, and solid rocket propellants.

Electrochemical oxygen concentrator as an oxygen compressor

NASA Technical Reports Server (NTRS)

1975-01-01

A solid polymer electrolyte (SPE) oxygen compressor is described which generates pressures of 3000 psi. The SPE is a cation exchange membrane with chemical compatibility, and has the capability of withstanding 5000 psi. Other features of the compressor described include: gasketless sealing, porus plate cell supports, and conductive cooling. Results are presented of a computer program which defines the power of the system as a function of density, temperature, pressure, membrane thickness, and water content.

Hierarchical optimization for neutron scattering problems

DOE PAGES

Bao, Feng; Archibald, Rick; Bansal, Dipanshu; ...

2016-03-14

In this study, we present a scalable optimization method for neutron scattering problems that determines confidence regions of simulation parameters in lattice dynamics models used to fit neutron scattering data for crystalline solids. The method uses physics-based hierarchical dimension reduction in both the computational simulation domain and the parameter space. We demonstrate for silicon that after a few iterations the method converges to parameters values (interatomic force-constants) computed with density functional theory simulations.

Hierarchical optimization for neutron scattering problems

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

Bao, Feng; Archibald, Rick; Bansal, Dipanshu

In this study, we present a scalable optimization method for neutron scattering problems that determines confidence regions of simulation parameters in lattice dynamics models used to fit neutron scattering data for crystalline solids. The method uses physics-based hierarchical dimension reduction in both the computational simulation domain and the parameter space. We demonstrate for silicon that after a few iterations the method converges to parameters values (interatomic force-constants) computed with density functional theory simulations.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Ohmic resistance of metal contacts with GaInAsP/InP double heterostructures as a function of the composition of the capping layer

NASA Astrophysics Data System (ADS)

Vogel, K.; Maly, D.; Puchert, R.; Schade, U.

1988-11-01

Characteristics of low-resistance Au-Cr-Au contacts with a quaternary solid solution, isoperiodic with GaInAsP, were determined as a function of the composition. These contacts were used in injection lasers emitting in the range of 1.3 μm. The smallest specific resistance (2 × 10- 5 Ω · cm2) was obtained for a contact with a GaInAs layer characterized by a hole density of ~ 1019 cm- 3.

Interface structure between tetraglyme and graphite

NASA Astrophysics Data System (ADS)

Minato, Taketoshi; Araki, Yuki; Umeda, Kenichi; Yamanaka, Toshiro; Okazaki, Ken-ichi; Onishi, Hiroshi; Abe, Takeshi; Ogumi, Zempachi

2017-09-01

Clarification of the details of the interface structure between liquids and solids is crucial for understanding the fundamental processes of physical functions. Herein, we investigate the structure of the interface between tetraglyme and graphite and propose a model for the interface structure based on the observation of frequency-modulation atomic force microscopy in liquids. The ordering and distorted adsorption of tetraglyme on graphite were observed. It is found that tetraglyme stably adsorbs on graphite. Density functional theory calculations supported the adsorption structure. In the liquid phase, there is a layered structure of the molecular distribution with an average distance of 0.60 nm between layers.

Rankine-Hugoniot relationships for molecular crystal explosives calculated using density functional theory based molecular dynamics

NASA Astrophysics Data System (ADS)

Mattsson, Ann E.; Wixom, Ryan R.; Mattsson, Thomas R.

2011-06-01

Density Functional Theory (DFT) has become a crucial tool for understanding the behavior of matter. The ability to perform high-fidelity calculations is most important for cases where experiments are impossible, dangerous, and/or prohibitively expensive to perform. For molecular crystals, successful use of DFT has been hampered by an inability to correctly describe the van der Waals' dominated equilibrium state. We have explored a way of bypassing this problem by using the Armiento-Mattsson 2005 (AM05) exchange-correlation functional. This functional is highly accurate for a wide range of solids, in particular in compression. Another advantage is that AM05 does not include any van der Waals' attraction. We will demonstrate the method on the PETN Hugoniot, and discuss our confidence in the results and ongoing research aimed at improvement. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Complex Fluids at Interfaces and Interfaces of Complex Fluids

NASA Astrophysics Data System (ADS)

Nouri, Mariam

The present thesis deals with two independent projects and is consequently divided into two parts. The first part details a computational study of the fluid structure of ring-shaped molecules and their positional and orientational molecular organizations in different degrees of confinement, while the second part concerns an experimental study of phase behavior and interfacial phenomena in confined colloid-polymer systems. In the first part, ring-shaped molecules are studied using Monte Carlo simulation techniques in one, two and three dimensions. The model used to describe ring-shaped molecules is composed of hard-spheres linked together to form planar rigid rings. For rings of various sizes and for a wide range of densities, positional and orientational orderings are reported in forms of pair distribution functions of the ring centers and correlation functions of the ring normal orientations. Special emphasis is given to understand structural formation at interfaces, i.e., the structure and orderings of these molecules when they are confined to two dimensions. In a plane but the rings themselves are free to rotate around all axes, nematic ordering is observed at sufficiently high densities. In the second part, phase equilibria of confined aqueous colloid-polymer systems are studied experimentally using fluorescence microscopy. Aqueous mixtures of fluorescent polystyrene spheres and polyacrylamide are confined between a glass slide and a coverslip. The phase diagram is determined as a function of the colloidal and polymer concentrations. Liquid-liquid phase coexistence between a colloid-rich phase and a polymer-rich phase occurs at intermediate polymer concentrations, while liquid-solid phase coexistence between a polymer-rich liquid and a colloid-rich solid is observed at high polymer concentrations. Interfacial thickness and tension of the interface between these coexisting phases are measured using image analysis techniques. It is also observed that the colloid-rich solid and liquid domains coarsen mainly by Ostwald ripening.

Superhydrophobic gecko feet with high adhesive forces towards water and their bio-inspired materials.

PubMed

Liu, Kesong; Du, Jiexing; Wu, Juntao; Jiang, Lei

2012-02-07

Functional integration is an inherent characteristic for multiscale structures of biological materials. In this contribution, we first investigate the liquid-solid adhesive forces between water droplets and superhydrophobic gecko feet using a high-sensitivity micro-electromechanical balance system. It was found, in addition to the well-known solid-solid adhesion, the gecko foot, with a multiscale structure, possesses both superhydrophobic functionality and a high adhesive force towards water. The origin of the high adhesive forces of gecko feet to water could be attributed to the high density nanopillars that contact the water. Inspired by this, polyimide films with gecko-like multiscale structures were constructed by using anodic aluminum oxide templates, exhibiting superhydrophobicity and a strong adhesive force towards water. The static water contact angle is larger than 150° and the adhesive force to water is about 66 μN. The resultant gecko-inspired polyimide film can be used as a "mechanical hand" to snatch micro-liter liquids. We expect this work will provide the inspiration to reveal the mechanism of the high-adhesive superhydrophobic of geckos and extend the practical applications of polyimide materials. This journal is © The Royal Society of Chemistry 2012

Theoretical investigation of thermodynamic stability and mobility of the oxygen vacancy in ThO 2 –UO 2 solid solutions

DOE PAGES

Liu, B.; Aidhy, D. S.; Zhang, Y.; ...

2014-10-16

The thermodynamic stability and the migration energy barriers of oxygen vacancies in ThO 2 –UO 2 solid solutions are investigated by density functional theory calculations. In pure ThO 2, the formation energy of oxygen vacancy is 7.58 eV and 1.46 eV under O rich and O poor conditions, respectively, while its migration energy barrier is 1.97 eV. The addition of UO 2 into ThO 2 significantly decreases the energetics of formation and migration of the oxygen vacancy. Among the range of UO 2-ThO 2 solid solutions studied in this work, UO 2 exhibits the lowest formation energy (5.99 eV andmore » -0.13 eV under O rich and O poor conditions, respectively) and Th 0.25U0 .75O 2 exhibits the lowest migration energy barrier (~ 1 eV). Moreover, by considering chemical potential, the phase diagram of oxygen vacancy as a function of both temperature and oxygen partial pressure is shown, which could help to gain experimental control over oxygen vacancy concentration.« less

Designing solid-liquid interphases for sodium batteries.

PubMed

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin; Gunceler, Deniz; Zachman, Michael J; Tu, Zhengyuan; Shin, Jung Hwan; Nath, Pooja; Agrawal, Akanksha; Kourkoutis, Lena F; Arias, Tomas A; Archer, Lynden A

2017-10-12

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

Communication: Unraveling the {sup 4}He droplet-mediated soft-landing from ab initio-assisted and time-resolved density functional simulations: Au@{sup 4}He{sub 300}/TiO{sub 2}(110)

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

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Aguirre, Néstor F.; Stoll, Hermann

2015-04-07

An ab-initio-based methodological scheme for He-surface interactions and zero-temperature time-dependent density functional theory for superfluid {sup 4}He droplets motion are combined to follow the short-time collision dynamics of the Au@{sup 4}He{sub 300} system with the TiO{sub 2}(110) surface. This composite approach demonstrates the {sup 4}He droplet-assisted sticking of the metal species to the surface at low landing energy (below 0.15 eV/atom), thus providing the first theoretical evidence of the experimentally observed {sup 4}He droplet-mediated soft-landing deposition of metal nanoparticles on solid surfaces [Mozhayskiy et al., J. Chem. Phys. 127, 094701 (2007) and Loginov et al., J. Phys. Chem. A 115,more » 7199 (2011)].« less

Time-dependent broken-symmetry density functional theory simulation of the optical response of entangled paramagnetic defects: Color centers in lithium fluoride

NASA Astrophysics Data System (ADS)

Janesko, Benjamin G.

2018-02-01

Parameter-free atomistic simulations of entangled solid-state paramagnetic defects may aid in the rational design of devices for quantum information science. This work applies time-dependent density functional theory (TDDFT) embedded-cluster simulations to a prototype entangled-defect system, namely two adjacent singlet-coupled F color centers in lithium fluoride. TDDFT calculations accurately reproduce the experimental visible absorption of both isolated and coupled F centers. The most accurate results are obtained by combining spin symmetry breaking to simulate strong correlation, a large fraction of exact (Hartree-Fock-like) exchange to minimize the defect electrons' self-interaction error, and a standard semilocal approximation for dynamical correlations between the defect electrons and the surrounding ionic lattice. These results motivate application of two-reference correlated ab initio approximations to the M-center, and application of TDDFT in parameter-free simulations of more complex entangled paramagnetic defect architectures.

Infrared spectroscopy and density functional calculations on titanium-dinitrogen complexes

NASA Astrophysics Data System (ADS)

Yoo, Hae-Wook; Choi, Changhyeok; Cho, Soo Gyeong; Jung, Yousung; Choi, Myong Yong

2018-04-01

Titanium-nitrogen complexes were generated by laser ablated titanium (Ti) atoms and N2 gas molecules in this study. These complexes were isolated on the pre-deposited solid Ar matrix on the pre-cooled KBr window (T ∼ 5.4 K), allowing infrared spectra to be measured. Laser ablation experiments with 15N2 isotope provided distinct isotopic shifts in the infrared spectra that strongly implicated the formation of titanium-nitrogen complexes, Ti(NN)x. Density functional theory (DFT) calculations were employed to investigate the molecular structures, electronic ground state, relative energies, and IR frequencies of the anticipated Ti(NN)x complexes. Based on laser ablation experiments and DFT calculations, we were able to assign multiple Ti(NN)x (x = 1-6) species. Particularly, Ti(NN)5 and Ti(NN)6, which have high nitrogen content, may serve as good precursors in preparing polynitrogens.

High-Energy-Density Shear Flow and Instability Experiments

NASA Astrophysics Data System (ADS)

Doss, F. W.; Flippo, K. A.; Merritt, E. C.; di Stefano, C. A.; Devolder, B. G.; Kurien, S.; Kline, J. L.

2017-10-01

High-energy-density shear experiments have been performed by LANL at the OMEGA Laser Facility and National Ignition Facility (NIF). The experiments have been simulated using the LANL radiation-hydrocode RAGE and have been used to assess turbulence models ability to function in the high-energy-density, inertial- fusion-relevant regime. Beginning with the basic configuration of two counter-oriented shock-driven flows of >= 100 km/s, which initiate a strong shear instability across an initially solid-density, 20 μm thick Al plate, variations of the experiment to details of the initial conditions have been performed. These variations have included increasing the fluid densities (by modifying the plate material from Al to Ti and Cu), imposing sinusoidal seed perturbations on the plate, and directly modifying the plate's intrinsic surface roughness. Radiography of the unseeded layer has revealed the presence of emergent Kelvin-Helmholtz structures which may be analyzed to infer fluid-mechanical properties including turbulent energy density. This work is conducted by the US DOE by LANL under contract DE-0AC52-06NA25396. This abstract is LA-UR-16-24930.

Separation of solids by varying the bulk density of a fluid separating medium

DOEpatents

Peterson, Palmer L.; Duffy, James B.; Tokarz, Richard D.

1978-01-01

A method and apparatus for separating objects having a density greater than a selected density value from objects having a density less than said selected density value. The method typically comprises: (a) providing a separation vessel having an upper and lower portion, said vessel containing a liquid having a density exceeding said selected density value; (b) reducing the apparent density of the liquid to said selected density value by introducing solid, bubble-like bodies having a density less than that of the liquid into the lower portion of the vessel and permitting them to rise therethrough; (c) introducing the objects to be separated into the separation vessel and permitting the objects having a density greater than the apparent density of the liquid to sink to the lower portion of the vessel, while the objects having a density less than said selected density value float in the upper portion of the vessel; and (d) separately removing the higher density objects in the lower portion and the lower density objects in the upper portion from the separation vessel. The apparatus typically comprises: (a) a vessel containing a liquid having a density such that at least part of said objects having a density exceeding said selected density value will float therein; (b) means to place said objects into said vessel; (c) means to reduce the effective density of at least a portion of said liquid to said selected density value, whereby said objects having a density exceeding said selected density value sink into said liquid and said objects having a density less than said selected density value remain afloat, said means to adjust the effective density comprising solid, bubble-like bodies having a density less than said selected density value and means for introducing said bodies into said liquid; and (d) means for separately removing said objects having a density exceeding said selected density value and said objects having a density less than said selected density value from said vessel.

Immersed Boundary Methods for Optimization of Strongly Coupled Fluid-Structure Systems

NASA Astrophysics Data System (ADS)

Jenkins, Nicholas J.

Conventional methods for design of tightly coupled multidisciplinary systems, such as fluid-structure interaction (FSI) problems, traditionally rely on manual revisions informed by a loosely coupled linearized analysis. These approaches are both inaccurate for a multitude of applications, and they require an intimate understanding of the assumptions and limitations of the procedure in order to soundly optimize the design. Computational optimization, in particular topology optimization, has been shown to yield remarkable results for problems in solid mechanics using density interpolations schemes. In the context of FSI, however, well defined boundaries play a key role in both the design problem and the mechanical model. Density methods neither accurately represent the material boundary, nor provide a suitable platform to apply appropriate interface conditions. This thesis presents a new framework for shape and topology optimization of FSI problems that uses for the design problem the Level Set method (LSM) to describe the geometry evolution in the optimization process. The Extended Finite Element method (XFEM) is combined with a fictitiously deforming fluid domain (stationary arbitrary Lagrangian-Eulerian method) to predict the FSI response. The novelty of the proposed approach lies in the fact that the XFEM explicitly captures the material boundary defined by the level set iso-surface. Moreover, the XFEM provides a means to discretize the governing equations, and weak immersed boundary conditions are applied with Nitsche's Method to couple the fields. The flow is predicted by the incompressible Navier-Stokes equations, and a finite-deformation solid model is developed and tested for both hyperelastic and linear elastic problems. Transient and stationary numerical examples are presented to validate the FSI model and numerical solver approach. Pertaining to the optimization of FSI problems, the parameters of the discretized level set function are defined as explicit functions of the optimization variables, and the parameteric optimization problem is solved by nonlinear programming methods. The gradients of the objective and constrains are computed by the adjoint method for the global monolithic fluid-solid system. Two types of design problems are explored for optimization of the fluid-structure response: 1) the internal structural topology is varied, preserving the fluid-solid interface geometry, and 2) the fluid-solid interface is manipulated directly, which leads to simultaneously configuring both internal structural topology and outer mold shape. The numerical results show that the LSM-XFEM approach is well suited for designing practical applications, while at the same time reducing the requirement on highly refined mesh resolution compared to traditional density methods. However, these results also emphasize the need for a more robust embedded boundary condition framework. Further, the LSM can exhibit greater dependence on initial design seeding, and can impede design convergence. In particular for the strongly coupled FSI analysis developed here, the thinning and eventual removal of structural members can cause jumps in the evolution of the optimization functions.

First-principles calculations of lattice dynamics and thermal properties of polar solids

DOE PAGES

Wang, Yi; Shang, Shun -Li; Fang, Huazhi; ...

2016-05-13

Although the theory of lattice dynamics was established six decades ago, its accurate implementation for polar solids using the direct (or supercell, small displacement, frozen phonon) approach within the framework of density-function-theory-based first-principles calculations had been a challenge until recently. It arises from the fact that the vibration-induced polarization breaks the lattice periodicity, whereas periodic boundary conditions are required by typical first-principles calculations, leading to an artificial macroscopic electric field. In conclusion, the article reviews a mixed-space approach to treating the interactions between lattice vibration and polarization, its applications to accurately predicting the phonon and associated thermal properties, and itsmore » implementations in a number of existing phonon codes.« less

Investigating the Co-Adsorption Behavior of Nucleic-Acid Base (Thymine and Cytosine) and Melamine at Liquid/Solid Interface

NASA Astrophysics Data System (ADS)

Zhao, Huiling; Li, Yinli; Chen, Dong; Liu, Bo

2016-12-01

The co-adsorption behavior of nucleic-acid base (thymine; cytosine) and melamine was investigated by scanning tunneling microscopy (STM) technique at liquid/solid (1-octanol/graphite) interface. STM characterization results indicate that phase separation happened after dropping the mixed solution of thymine-melamine onto highly oriented pyrolytic graphite (HOPG) surface, while the hetero-component cluster-like structure was observed when cytosine-melamine binary assembly system is used. From the viewpoints of non-covalent interactions calculated by using density functional theory (DFT) method, the formation mechanisms of these assembled structures were explored in detail. This work will supply a methodology to design the supramolecular assembled structures and the hetero-component materials composed by biological and chemical compound.

Origins of hydration differences in homochiral and racemic crystals of aspartic acid.

PubMed

Juliano, Thomas R; Korter, Timothy M

2015-02-26

The propensity for crystalline hydrates of organic molecules to form is related to the strength of the interactions between molecules, including the chiral composition of the molecular solids. Specifically, homochiral versus racemic crystalline samples can exhibit distinct differences in their ability to form energetically stable hydrates. The focus of the current study is a comparison of the crystal structures and intermolecular forces found in solid-state L-aspartic acid, DL-aspartic acid, and L-aspartic acid monohydrate. The absence of experimental evidence for the DL-aspartic acid monohydrate is considered here in terms of the enhanced thermodynamic stability of the DL-aspartic acid anhydrate crystal as compared to the L-aspartic acid anhydrate as revealed through solid-state density functional theory calculations and terahertz spectroscopic measurements. The results indicate that anhydrous DL-aspartic acid is the more stable solid, not due to intermolecular forces alone but also due to the improved conformations of the molecules within the racemic solid. Hemihydrated and monohydrated forms of DL-aspartic acid have been computationally evaluated, and in each case, the hydrates produce destabilized aspartic acid conformations that prevent DL-aspartic acid hydrate formation from occurring.

Density functional theory for prediction of far-infrared vibrational frequencies: molecular crystals of astrophysical interest

NASA Astrophysics Data System (ADS)

Ennis, C.; Auchettl, R.; Appadoo, D. R. T.; Robertson, E. G.

2017-11-01

Solid-state density functional theory code has been implemented for the structure optimization of crystalline methanol, acetaldehyde and acetic acid and for the calculation of infrared frequencies. The results are compared to thin film spectra obtained from low-temperature experiments performed at the Australian Synchrotron. Harmonic frequency calculations of the internal modes calculated at the B3LYP-D3/m-6-311G(d) level shows higher deviation from infrared experiment than more advanced theory applied to the gas phase. Importantly for the solid-state, the simulation of low-frequency molecular lattice modes closely resembles the observed far-infrared features after application of a 0.92 scaling factor. This allowed experimental peaks to be assigned to specific translation and libration modes, including acetaldehyde and acetic acid lattice features for the first time. These frequency calculations have been performed without the need for supercomputing resources that are required for large molecular clusters using comparable levels of theory. This new theoretical approach will find use for the rapid characterization of intermolecular interactions and bonding in crystals, and the assignment of far-infrared spectra for crystalline samples such as pharmaceuticals and molecular ices. One interesting application may be for the detection of species of prebiotic interest on the surfaces of Kuiper-Belt and Trans-Neptunian Objects. At such locations, the three small organic molecules studied here could reside in their crystalline phase. The far-infrared spectra for their low-temperature solid phases are collected under planetary conditions, allowing us to compile and assign their most intense spectral features to assist future far-infrared surveys of icy Solar system surfaces.

Multiscale Experimental and Theoretical Investigations of Spin Crossover FeII Complexes: Examples of [Fe(phen)2(NCS)2] and [Fe(PM-BiA)2(NCS)2

PubMed Central

Matar, Samir F.; Guionneau, Philippe; Chastanet, Guillaume

2015-01-01

For spin crossover (SCO) complexes, computation results are reported and confirmed with experiments at multiscale levels of the isolated molecule and extended solid on the one hand and theory on the other hand. The SCO phenomenon which characterizes organometallics based on divalent iron in an octahedral FeN6-like environment with high spin (HS) and low spin (LS) states involves the LS/HS switching at the cost of small energies provided by temperature, pressure or light, the latter connected with Light-Induced Excited Spin-State Trapping (LIESST) process. Characteristic infra red (IR) and Raman vibration frequencies are computed within density functional theory (DFT) framework. In [Fe(phen)2(NCS)2] a connection of selected frequencies is established with an ultra-fast light-induced LS → HS photoswitching mechanism. In the extended solid, density of state DOS and electron localization function (ELF) are established for both LS and HS forms, leading to characterizion of the compound as an insulator in both spin states with larger gaps for LS configuration, while keeping molecular features in the solid. In [Fe(PM-BiA)2(NCS)2], by combining DFT and classical molecular dynamics, the properties and the domains of existence of the different phases are obtained by expressing the potential energy surfaces in a short range potential for Fe–N interactions. Applying such Fe–N potentials inserted in a classical force field and carrying out molecular dynamics (MD) in so-called “semi-classical MD” calculations, lead to the relative energies of HS/LS configurations of the crystal and to the assessment of the experimental (P, T) phase diagram. PMID:25686037

The morphology of blends of linear and branched polyethylenes by small-angle neutron and x-ray scattering

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

Londono, J.D.; Wignall, G.D.; Lin, J.S.

1995-12-31

The solid-state morphology and liquid-state homogeneity of blends of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) were investigated by small-angle neutron and x-ray scattering (SANS and SAXS). The solid state morphology was investigated as a function of composition and cooling rate from the melt. After slow cooling, the evidence indicated that the mixtures were either completely (HDPE-rich blends) or almost completely (LDPE-rich blends) phase separated into separate HDPE and LDPE lamellae over the whole compositional range. In contrast, for rapidly quenched blends the components are extensively co-crystallized for all concentrations, though the SANS data indicated that the branched component hadmore » a tendency to be preferentially located in the inter-lamellar regions. In the liquid state, the blends were homogeneous at all compositions, showing that the solid state morphology is not determined by the melt structure, but is a function of the crystallization kinetics. Further evidence for blend homogeneity in the liquid is presented. In particular the authors examine the hypothesis that a phase separated mixture might give a scattering pattern similar to a homogeneous blend if the domain sizes were larger than the maximum spatial resolution of the SANS experiment (D > 2{pi}/Q{sub min} {approximately} 2,000 {angstrom}). In this scenario, the differential scattering cross section d{Sigma}/d{Omega}(Q) {approximately} Q{sup {minus}2}, though phase separation decreases the cross section in this Q-range with respect to the homogeneous blend. For HDPE/LDPE blends in the melt, this decrease in intensity was not observed, thus ruling out the possibility of phase separation.« less

40 CFR 63.4730 - What records must I keep?

Code of Federal Regulations, 2010 CFR

2010-07-01

... to determine the mass fraction of organic HAP and density for each coating, thinner, and cleaning material and the volume fraction of coating solids for each coating. If you conducted testing to determine mass fraction of organic HAP, density, or volume fraction of coating solids, you must keep a copy of...

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

1989-01-01

Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

Information Theory and the Earth's Density Distribution

NASA Technical Reports Server (NTRS)

Rubincam, D. P.

1979-01-01

An argument for using the information theory approach as an inference technique in solid earth geophysics. A spherically symmetric density distribution is derived as an example of the method. A simple model of the earth plus knowledge of its mass and moment of inertia lead to a density distribution which was surprisingly close to the optimum distribution. Future directions for the information theory approach in solid earth geophysics as well as its strengths and weaknesses are discussed.

NMR Investigations of Noncovalent Carbon Tetrel Bonds. Computational Assessment and Initial Experimental Observation.

PubMed

Southern, Scott A; Bryce, David L

2015-12-10

Group IV tetrel elements may act as tetrel bond donors, whereby a region of positive electrostatic potential (σ-hole) interacts with a Lewis base. The results of calculations of NMR parameters are reported for a series of model compounds exhibiting tetrel bonding from a methyl carbon to the oxygen or nitrogen atoms in various functional groups. The (13)C chemical shift (δiso) and the (1c)J((13)C,Y) coupling (Y = (17)O, (15)N) across the tetrel bond are recorded as a function of geometry. The sensitivity of the NMR parameters to the noncovalent interaction is demonstrated via an increase in δiso and in |(1c)J((13)C,Y)| as the tetrel bond shortens. Gauge-including projector-augmented wave density functional theory (DFT) calculations of δiso are reported for crystals that exhibit tetrel bonding in the solid state. Experimental δiso values for solid sarcosine and its tetrel-bonded salts corroborate the computational findings. This work offers new insights into tetrel bonding and facilitates the incorporation of tetrel bonds as restraints in NMR crystallographic structure refinement.

Fabrication of Homogeneous High-Density Antibody Microarrays for Cytokine Detection

PubMed Central

Hospach, Ingeborg; Joseph, Yvonne; Mai, Michaela Kathrin; Krasteva, Nadejda; Nelles, Gabriele

2014-01-01

Cytokine proteins are known as biomarker molecules, characteristic of a disease or specific body condition. Monitoring of the cytokine pattern in body fluids can contribute to the diagnosis of diseases. Here we report on the development of an array comprised of different anti-cytokine antibodies on an activated solid support coupled with a fluorescence readout mechanism. Optimization of the array preparation was done in regard of spot homogeneity and spot size. The proinflammatory cytokines Tumor Necrosis Factor alpha (TNFα) and Interleukin 6 (IL-6) were chosen as the first targets of interest. First, the solid support for covalent antibody immobilization and an adequate fluorescent label were selected. Three differently functionalized glass substrates for spotting were compared: amine and epoxy, both having a two-dimensional structure, and the NHS functionalized hydrogel (NHS-3D). The NHS-hydrogel functionalization of the substrate was best suited to antibody immobilization. Then, the optimization of plotting parameters and geometry as well as buffer media were investigated, considering the ambient analyte theory of Roger Ekins. As a first step towards real sample studies, a proof of principle of cytokine detection has been established. PMID:27600349

Diffusion of Zr, Ru, Ce, Y, La, Sr and Ba fission products in UO 2

DOE PAGES

Perriot, R.; Liu, X. -Y.; Stanek, C. R.; ...

2015-01-08

The diffusivity of the solid fission products (FP) Zr (Zr 4+), Ru (Ru 4+, Ru 3+), Ce (Ce 4+), Y (Y 3+), La (La 3+), Sr (Sr 2+) and Ba (Ba 2+) by a vacancy mechanism has been calculated, using a combination of density functional theory (DFT) and empirical potential (EP) calculations. The activation energies for the solid fission products are compared to the activation energy for Xe fission gas atoms calculated previously. Apart from Ru, the solid fission products all exhibit higher activation energy than Xe. Furthermore, for all solid FPs except Y 3+, the migration of the FPmore » has lower barrier than the migration of a neighboring U atom, making the latter the rate limiting step for direct migration. An indirect mechanism, consisting of two successive migrations around the FP, is also investigated. The calculated diffusivities show that most solid fission products diffuse with rates similar to U self-diffusion. But, Ru, Ba and Sr exhibit faster diffusion than the other solid FPs, with Ru 3+ and Ru 4+ diffusing even faster than Xe for T < 1200 K. The diffusivities correlate with the observed fission product solubility in UO 2, and the tendency to form metallic and oxide second phase inclusions.« less

FSILP: fuzzy-stochastic-interval linear programming for supporting municipal solid waste management.

PubMed

Li, Pu; Chen, Bing

2011-04-01

Although many studies on municipal solid waste management (MSW management) were conducted under uncertain conditions of fuzzy, stochastic, and interval coexistence, the solution to the conventional linear programming problems of integrating fuzzy method with the other two was inefficient. In this study, a fuzzy-stochastic-interval linear programming (FSILP) method is developed by integrating Nguyen's method with conventional linear programming for supporting municipal solid waste management. The Nguyen's method was used to convert the fuzzy and fuzzy-stochastic linear programming problems into the conventional linear programs, by measuring the attainment values of fuzzy numbers and/or fuzzy random variables, as well as superiority and inferiority between triangular fuzzy numbers/triangular fuzzy-stochastic variables. The developed method can effectively tackle uncertainties described in terms of probability density functions, fuzzy membership functions, and discrete intervals. Moreover, the method can also improve upon the conventional interval fuzzy programming and two-stage stochastic programming approaches, with advantageous capabilities that are easily achieved with fewer constraints and significantly reduces consumption time. The developed model was applied to a case study of municipal solid waste management system in a city. The results indicated that reasonable solutions had been generated. The solution can help quantify the relationship between the change of system cost and the uncertainties, which could support further analysis of tradeoffs between the waste management cost and the system failure risk. Copyright © 2010 Elsevier Ltd. All rights reserved.

A transferable force field for CdS-CdSe-PbS-PbSe solid systems

NASA Astrophysics Data System (ADS)

Fan, Zhaochuan; Koster, Rik S.; Wang, Shuaiwei; Fang, Changming; Yalcin, Anil O.; Tichelaar, Frans D.; Zandbergen, Henny W.; van Huis, Marijn A.; Vlugt, Thijs J. H.

2014-12-01

A transferable force field for the PbSe-CdSe solid system using the partially charged rigid ion model has been successfully developed and was used to study the cation exchange in PbSe-CdSe heteronanocrystals [A. O. Yalcin et al., "Atomic resolution monitoring of cation exchange in CdSe-PbSe heteronanocrystals during epitaxial solid-solid-vapor growth," Nano Lett. 14, 3661-3667 (2014)]. In this work, we extend this force field by including another two important binary semiconductors, PbS and CdS, and provide detailed information on the validation of this force field. The parameterization combines Bader charge analysis, empirical fitting, and ab initio energy surface fitting. When compared with experimental data and density functional theory calculations, it is shown that a wide range of physical properties of bulk PbS, PbSe, CdS, CdSe, and their mixed phases can be accurately reproduced using this force field. The choice of functional forms and parameterization strategy is demonstrated to be rational and effective. This transferable force field can be used in various studies on II-VI and IV-VI semiconductor materials consisting of CdS, CdSe, PbS, and PbSe. Here, we demonstrate the applicability of the force field model by molecular dynamics simulations whereby transformations are initiated by cation exchange.

Stability and Solid Solutions of Hydrous Alumino-Silicates in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Panero, W. R.; Caracas, R.

2017-12-01

The degree to which the Earth's mantle stores and cycles water in excess of the storage capacity of nominally anhydrous minerals is dependent upon the stability of hydrous phases under mantle-relevant pressures, temperatures, and compositions. Two hydrous phases, phase D and phase H are stable to the pressures and temperatures of the Earth's lower mantle, suggesting that the Earth's lower mantle may participate in the cycling of water. Each phase has a wide solid solution series between MgSi2O6H2-Al2SiO6H2 and MgSiO4H2-2δAlOOH-SiO2, respectively, yet most work addresses end-member compositions for analysis of stability and elastic properties. We present the results of density functional theory calculations on the stability, structure, bonding, partitioning, and elasticity of hydrous phases D and H in the Al2O3-SiO2-MgO-H2O system, addressing the solid solution series through a statistical sampling of site occupancy and calculation of the partition function from the grand canonical ensemble. We find that the addition of Al to the endmember compositions stabilizes each phase to higher temperatures through additional configurational entropy. We further find that solid solutions tend not to undergo hydrogen-bond symmetrization as is found in the end member compositions as a result of non-symmetric bonding environments.

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells.

PubMed

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A; Liu, Meilin

2011-06-21

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C(3)H(8), CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H(2)O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

Band gap bowing in NixMg1−xO

PubMed Central

Niedermeier, Christian A.; Råsander, Mikael; Rhode, Sneha; Kachkanov, Vyacheslav; Zou, Bin; Alford, Neil; Moram, Michelle A.

2016-01-01

Epitaxial transparent oxide NixMg1−xO (0 ≤ x ≤ 1) thin films were grown on MgO(100) substrates by pulsed laser deposition. High-resolution synchrotron X-ray diffraction and high-resolution transmission electron microscopy analysis indicate that the thin films are compositionally and structurally homogeneous, forming a completely miscible solid solution. Nevertheless, the composition dependence of the NixMg1−xO optical band gap shows a strong non-parabolic bowing with a discontinuity at dilute NiO concentrations of x < 0.037. Density functional calculations of the NixMg1−xO band structure and the density of states demonstrate that deep Ni 3d levels are introduced into the MgO band gap, which significantly reduce the fundamental gap as confirmed by optical absorption spectra. These states broaden into a Ni 3d-derived conduction band for x > 0.074 and account for the anomalously large band gap narrowing in the NixMg1−xO solid solution system. PMID:27503808

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells

PubMed Central

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A.; Liu, Meilin

2011-01-01

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C3H8, CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity. PMID:21694705

Electricity production from municipal solid waste using microbial fuel cells.

PubMed

Chiu, H Y; Pai, T Y; Liu, M H; Chang, C A; Lo, F C; Chang, T C; Lo, H M; Chiang, C F; Chao, K P; Lo, W Y; Lo, S W; Chu, Y L

2016-07-01

The organic content of municipal solid waste has long been an attractive source of renewable energy, mainly as a solid fuel in waste-to-energy plants. This study focuses on the potential to use microbial fuel cells to convert municipal solid waste organics into energy using various operational conditions. The results showed that two-chamber microbial fuel cells with carbon felt and carbon felt allocation had a higher maximal power density (20.12 and 30.47 mW m(-2) for 1.5 and 4 L, respectively) than those of other electrode plate allocations. Most two-chamber microbial fuel cells (1.5 and 4 L) had a higher maximal power density than single-chamber ones with corresponding electrode plate allocations. Municipal solid waste with alkali hydrolysis pre-treatment and K3Fe(CN)6 as an electron acceptor improved the maximal power density to 1817.88 mW m(-2) (~0.49% coulomb efficiency, from 0.05-0.49%). The maximal power density from experiments using individual 1.5 and 4 L two-chamber microbial fuel cells, and serial and parallel connections of 1.5 and 4 L two-chamber microbial fuel cells, was found to be in the order of individual 4 L (30.47 mW m(-2)) > serial connection of 1.5 and 4 L (27.75) > individual 1.5 L (20.12) > parallel connection of 1.5 and 4 L (17.04) two-chamber microbial fuel cells . The power density using municipal solid waste microbial fuel cells was compared with information in the literature and discussed. © The Author(s) 2016.

Atomistic Modeling of the Fluid-Solid Interface in Simple Fluids

NASA Astrophysics Data System (ADS)

Hadjiconstantinou, Nicolas; Wang, Gerald

2017-11-01

Fluids can exhibit pronounced structuring effects near a solid boundary, typically manifested in a layered structure that has been extensively shown to directly affect transport across the interface. We present and discuss several results from molecular-mechanical modeling and molecular-dynamics (MD) simulations aimed at characterizing the structure of the first fluid layer directly adjacent to the solid. We identify a new dimensionless group - termed the Wall number - which characterizes the degree of fluid layering, by comparing the competing effects of wall-fluid interaction and thermal energy. We find that in the layering regime, several key features of the first layer layer - including its distance from the solid, its width, and its areal density - can be described using mean-field-energy arguments, as well as asymptotic analysis of the Nernst-Planck equation. For dense fluids, the areal density and the width of the first layer can be related to the bulk fluid density using a simple scaling relation. MD simulations show that these results are broadly applicable and robust to the presence of a second confining solid boundary, different choices of wall structure and thermalization, strengths of fluid-solid interaction, and wall geometries.

Thermal conductivity switch: Optimal semiconductor/metal melting transition

NASA Astrophysics Data System (ADS)

Kim, Kwangnam; Kaviany, Massoud

2016-10-01

Scrutinizing distinct solid/liquid (s /l ) and solid/solid (s /s ) phase transitions (passive transitions) for large change in bulk (and homogenous) thermal conductivity, we find the s /l semiconductor/metal (S/M) transition produces the largest dimensionless thermal conductivity switch (TCS) figure of merit ZTCS (change in thermal conductivity divided by smaller conductivity). At melting temperature, the solid phonon and liquid molecular thermal conductivities are comparable and generally small, so the TCS requires localized electron solid and delocalized electron liquid states. For cyclic phase reversibility, the congruent phase transition (no change in composition) is as important as the thermal transport. We identify X Sb and X As (X =Al , Cd, Ga, In, Zn) and describe atomic-structural metrics for large ZTCS, then show the superiority of S/M phonon- to electron-dominated transport melting transition. We use existing experimental results and theoretical and ab initio calculations of the related properties for both phases (including the Kubo-Greenwood and Bridgman formulations of liquid conductivities). The 5 p orbital of Sb contributes to the semiconductor behavior in the solid-phase band gap and upon disorder and bond-length changes in the liquid phase this changes to metallic, creating the large contrast in thermal conductivity. The charge density distribution, electronic localization function, and electron density of states are used to mark this S/M transition. For optimal TCS, we examine the elemental selection from the transition, basic, and semimetals and semiconductor groups. For CdSb, addition of residual Ag suppresses the bipolar conductivity and its ZTCS is over 7, and for Zn3Sb2 it is expected to be over 14, based on the structure and transport properties of the better-known β -Zn4Sb3 . This is the highest ZTCS identified. In addition to the metallic melting, the high ZTCS is due to the electron-poor nature of II-V semiconductors, leading to the significantly low phonon conductivity.

Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory

DTIC Science & Technology

2017-04-18

fundamental gap but there is little effect on the optical spectra. We therefore believe that the method is robust and can be used for studies of... quantitative DFT- based prediction of excited-state properties in molecu- lar solids.[28, 29] In this approach, one first computes the underlying gas...gradient ap- proximation (GGA). In some cases , the fraction of SR Fock exchange, α, can be determined from first-principles based on satisfaction of

Effect of argon implantation on solid-state dewetting: control of size and surface density of silicon nanocrystals.

PubMed

Almadori, Y; Borowik, Ł; Chevalier, N; Barbé, J-C

2017-01-27

Thermally induced solid-state dewetting of ultra-thin films on insulators is a process of prime interest, since it is capable of easily forming nanocrystals. If no particular treatment is performed to the film prior to the solid-state dewetting, it is already known that the size, the shape and the density of nanocrystals is governed by the initial film thickness. In this paper, we report a novel approach to control the size and the surface density of silicon nanocrystals based on an argon-implantation preliminary surface treatment. Using 7.5 nm thin layers of silicon, we show that increasing the implantation dose tends to form smaller silicon nanocrystals with diameter and height lower than 50 nm and 30 nm, respectively. Concomitantly, the surface density is increased by a factor greater than 20, going from 5 μm -2 to values over 100 μm -2 .

First principles study on structural, electronic and optical properties of Ga1-xBxP ternary alloys (x = 0, 0.25, 0.5, 0.75 and 1)

NASA Astrophysics Data System (ADS)

Hoat, D. M.; Rivas Silva, J. F.; Méndez Blas, A.

2018-07-01

The structural, electronic and optical properties of GaP, BP binary compounds and their ternary alloys Ga1-xBxP (x = 0.25, 0.5 and 0.75) have been studied by full-potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT) as implemented in WIEN2k package. Local density approximation (LDA) and generalized gradient approximation (GGA) as proposed by Perdew-Burke-Ernzerhof (PBE), Wu-Cohen (WC) and PBE for solid (PBESol) were used for treatment of exchange-correlation effect in calculations. Additionally, the Tran-Blaha modified Becke-Johnson (mBJ) potential was also employed for electronic and optical calculations due to that it gives very accurate band gap of solids. As B concentration increases, the lattice constant reduces and the energy band gap firstly decreases for small composition x and then it shows increasing trend until pure BP. Our results show that the indirect-direct band gap transition can be reached from x = 0.33. The linear optical properties, such as reflectivity, absorption coefficient, refractive index and optical conductivity of binary compounds and ternary alloys were derived from their calculated complex dielectric function in wide energy range up to 30 eV, and the alloying effect on these properties was also analyzed in detail.

The phase diagram of solid hydrogen at high pressure: A challenge for first principles calculations

NASA Astrophysics Data System (ADS)

Azadi, Sam; Foulkes, Matthew

2015-03-01

We present comprehensive results for the high-pressure phase diagram of solid hydrogen. We focus on the energetically most favorable molecular and atomic crystal structures. To obtain the ground-state static enthalpy and phase diagram, we use semi-local and hybrid density functional theory (DFT) as well as diffusion quantum Monte Carlo (DMC) methods. The closure of the band gap with increasing pressure is investigated utilizing quasi-particle many-body calculations within the GW approximation. The dynamical phase diagram is calculated by adding proton zero-point energies (ZPE) to static enthalpies. Density functional perturbation theory is employed to calculate the proton ZPE and the infra-red and Raman spectra. Our results clearly demonstrate the failure of DFT-based methods to provide an accurate static phase diagram, especially when comparing insulating and metallic phases. Our dynamical phase diagram obtained using fully many-body DMC calculations shows that the molecular-to-atomic phase transition happens at the experimentally accessible pressure of 374 GPa. We claim that going beyond mean-field schemes to obtain derivatives of the total energy and optimize crystal structures at the many-body level is crucial. This work was supported by the UK engineering and physics science research council under Grant EP/I030190/1, and made use of computing facilities provided by HECTOR, and by the Imperial College London high performance computing centre.

Fuel cell tubes and method of making same

DOEpatents

Borglum, Brian P.

1999-11-30

A method of manufacturing porous ceramic tubes for fuel cells with improved properties and higher manufacturing yield is disclosed. The method involves extruding a closed end fuel cell tube, such as an air electrode of a solid oxide fuel cell, in which the closed end also functions as the sintering support. The resultant fuel cell tube has a superior porosity distribution which allows improved diffusion of oxygen at the closed end of the tube during operation of the fuel cell. Because this region has the highest current density, performance enhancement and improved reliability of the fuel cell tube result. Furthermore, the higher manufacturing yield associated with the present method decreases the overall fuel cell cost. A method of manufacturing porous ceramic tubes for fuel cells with improved properties and higher manufacturing yield is disclosed. The method involves extruding a closed end fuel cell tube, such as an air electrode of a solid oxide fuel cell, in which the closed end also functions as the sintering support. The resultant fuel cell tube has a superior porosity distribution which allows improved diffusion of oxygen at the closed end of the tube during operation of the fuel cell. Because this region has the highest current density, performance enhancement and improved reliability of the fuel cell tube result. Furthermore, the higher manufacturing yield associated with the present method decreases the overall fuel cell cost.

An innovative method for the non-destructive identification of photodegradation products in solid state: 1H-14N NMR-NQR and DFT/QTAIM study of photodegradation of nifedipine (anti-hypertensive) to nitrosonifedipine (potential anti-oxidative).

PubMed

Latosińska, J N; Latosińska, M; Seliger, J; Zagar, V

2012-08-30

Stability of the antihypertensive drug nifedipine (NIF) has been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT). Photodegradation of NIF to its metabolite in vivo nitrosonifedipine, NO-NIF (antioxidative agent) upon long term daylight exposure was detected and the changes in the molecular structure of NIF were analysed. The photoconversion of NIF to NO-NIF in solid was found to be accompanied with the electron density redistribution at nitrogen sites (NH to N and NO(2) to NO) and proved to be successfully detected with identification of photoproducts by (1)H-(14)N NQDR and DFT methods. The increase in the e(2)qQ/h and η describing EFG tendency towards non-spherical symmetry was significantly greater upon the reduction of NO(2) site than upon hydrogen abstraction from NH site. The level of sensitivity of detection of the photodegradation product was about 1% of the original sample. The Quantum Theory of Atoms in Molecules (QTAIM) analysis has been found useful in predicting photoreactive sites in the molecules and finding the explanation of differences in reactivity between parent NIF and its photoproduct NO-NIF. Using NIF as a model, this study demonstrates the suitability of NQDR supported by DFT for non-destructive determination of the photodegradation products in solid state. Copyright © 2012 Elsevier B.V. All rights reserved.

Multi-element microelectropolishing method

DOEpatents

Lee, Peter J.

1994-01-01

A method is provided for microelectropolishing a transmission electron microscopy nonhomogeneous multi-element compound foil. The foil is electrolyzed at different polishing rates for different elements by rapidly cycling between different current densities. During a first portion of each cycle at a first voltage a first element electrolyzes at a higher current density than a second element such that the material of the first element leaves the anode foil at a faster rate than the second element and creates a solid surface film, and such that the solid surface film is removed at a faster rate than the first element leaves the anode foil. During a second portion of each cycle at a second voltage the second element electrolyzes at a higher current density than the first element, and the material of the second element leaves the anode foil at a faster rate than the first element and creates a solid surface film, and the solid surface film is removed at a slower rate than the second element leaves the foil. The solid surface film is built up during the second portion of the cycle, and removed during the first portion of the cycle.

An Experiment in Physical Chemistry: Polymorphism and Phase Stability in Acetaminophen (Paracetamol)

ERIC Educational Resources Information Center

Myrick, Michael L.; Baranowski, Megan; Profeta, Luisa T. M.

2010-01-01

Differential scanning calorimetry analyses of two easily prepared polymorphs of acetaminophen (also known as paracetamol) are recorded. The density of the forms can be found in the literature. Rules for heats of transition, heats of fusion, and density, as well as methods for determining the solid-solid transition temperature between the forms,…

Density functional theory studies on the electronic, structural, phonon dynamical and thermo-stability properties of bicarbonates MHCO3, M = Li, Na, K

NASA Astrophysics Data System (ADS)

Duan, Yuhua; Zhang, Bo; Sorescu, Dan C.; Johnson, J. Karl; Majzoub, Eric H.; Luebke, David R.

2012-08-01

The structural, electronic, phonon dispersion and thermodynamic properties of MHCO3 (M = Li, Na, K) solids were investigated using density functional theory. The calculated bulk properties for both their ambient and the high-pressure phases are in good agreement with available experimental measurements. Solid phase LiHCO3 has not yet been observed experimentally. We have predicted several possible crystal structures for LiHCO3 using crystallographic database searching and prototype electrostatic ground state modeling. Our total energy and phonon free energy (FPH) calculations predict that LiHCO3 will be stable under suitable conditions of temperature and partial pressures of CO2 and H2O. Our calculations indicate that the {{HCO}}_{3}^{-} groups in LiHCO3 and NaHCO3 form an infinite chain structure through O⋯H⋯O hydrogen bonds. In contrast, the {{HCO}}_{3}^{-} anions form dimers, ({{HCO}}_{3}^{-})_{2}, connected through double hydrogen bonds in all phases of KHCO3. Based on density functional perturbation theory, the Born effective charge tensor of each atom type was obtained for all phases of the bicarbonates. Their phonon dispersions with the longitudinal optical-transverse optical splitting were also investigated. Based on lattice phonon dynamics study, the infrared spectra and the thermodynamic properties of these bicarbonates were obtained. Over the temperature range 0-900 K, the FPH and the entropies (S) of MHCO3 (M =Li, Na, K) systems vary as FPH(LiHCO3) > FPH(NaHCO3) > FPH(KHCO3) and S(KHCO3) > S(NaHCO3) > S(LiHCO3), respectively, in agreement with the available experimental data. Analysis of the predicted thermodynamics of the CO2 capture reactions indicates that the carbonate/bicarbonate transition reactions for Na and K could be used for CO2 capture technology, in agreement with experiments.

Predicting the tensile strength of compacted multi-component mixtures of pharmaceutical powders.

PubMed

Wu, Chuan-Yu; Best, Serena M; Bentham, A Craig; Hancock, Bruno C; Bonfield, William

2006-08-01

Pharmaceutical tablets are generally produced by compacting a mixture of several ingredients, including active drugs and excipients. It is of practical importance if the properties of such tablets can be predicted on the basis of the ones for constituent components. The purpose of this work is to develop a theoretical model which can predict the tensile strength of compacted multi-component pharmaceutical mixtures. The model was derived on the basis of the Ryshkewitch-Duckworth equation that was originally proposed for porous materials. The required input parameters for the model are the relative density or solid fraction (ratio of the volume of solid materials to the total volume of the tablets) of the multi-component tablets and parameters associated with the constituent single-component powders, which are readily accessible. The tensile strength of tablets made of various powder blends at different relative density was also measured using diametrical compression. It has been shown that the tensile strength of the multi-component powder compacts is primarily a function of the solid fraction. Excellent agreement between prediction and experimental data for tablets of binary, ternary and four-component blends of some widely used pharmaceutical excipients was obtained. It has been demonstrated that the proposed model can well predict the tensile strength of multi-component pharmaceutical tablets. Thus, the model will be a useful design tool for formulation engineers in the pharmaceutical industry.

Physics behind the oscillation of pressure tensor autocorrelation function for nanocolloidal dispersions.

PubMed

Wang, Tao; Wang, Xinwei; Luo, Zhongyang; Cen, Kefa

2008-08-01

In this work, extensive equilibrium molecular dynamics simulations are conducted to explore the physics behind the oscillation of pressure tensor autocorrelation function (PTACF) for nanocolloidal dispersions, which leads to strong instability in viscosity calculation. By reducing the particle size and density, we find the intensity of the oscillation decreases while the frequency of the oscillation becomes higher. Careful analysis of the relationship between the oscillation and nanoparticle characteristics reveals that the stress wave scattering/reflection at the particle-liquid interface plays a critical role in PTACF oscillation while the Brownian motion/vibration of solid particles has little effect. Our modeling proves that it is practical to eliminate the PTACF oscillation through suppressing the acoustic mismatch at the solid-liquid interface by designing special nanoparticle materials. It is also found when the particle size is comparable with the wavelength of the stress wave, diffraction of stress wave happens at the interface. Such effect substantially reduces the PTACF oscillation and improves the stability of viscosity calculation.

Design of defect spins in piezoelectric aluminum nitride for solid-state hybrid quantum technologies

DOE PAGES

Seo, Hosung; Govoni, Marco; Galli, Giulia

2016-02-15

Spin defects in wide-band gap semiconductors are promising systems for the realization of quantum bits, or qubits, in solid-state environments. To date, defect qubits have only been realized in materials with strong covalent bonds. Here, we introduce a strain-driven scheme to rationally design defect spins in functional ionic crystals, which may operate as potential qubits. In particular, using a combination of state-of-the-art ab-initio calculations based on hybrid density functional and many-body perturbation theory, we predicted that the negatively charged nitrogen vacancy center in piezoelectric aluminum nitride exhibits spin-triplet ground states under realistic uni- and bi-axial strain conditions; such states maymore » be harnessed for the realization of qubits. As a result, the strain-driven strategy adopted here can be readily extended to a wide range of point defects in other wide-band gap semiconductors, paving the way to controlling the spin properties of defects in ionic systems for potential spintronic technologies.« less

Local Structural Investigations, Defect Formation, and Ionic Conductivity of the Lithium Ionic Conductor Li 4 P 2 S 6

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

Dietrich, Christian; Sadowski, Marcel; Sicolo, Sabrina

Glassy, glass–ceramic, and crystalline lithium thiophosphates have attracted interest in their use as solid electrolytes in all-solid-state batteries. Despite similar structural motifs, including PS 4 3–, P 2S 6 4–, and P 2S 7 4– polyhedra, these materials exhibit a wide range of possible compositions, crystal structures, and ionic conductivities. Here, we present a combined approach of Bragg diffraction, pair distribution function analysis, Raman spectroscopy, and 31P magic angle spinning nuclear magnetic resonance spectroscopy to study the underlying crystal structure of Li 4P 2S 6. In this work, we show that the material crystallizes in a planar structural arrangement asmore » a glass ceramic composite, explaining the observed relatively low ionic conductivity, depending on the fraction of glass content. Calculations based on density functional theory provide an understanding of occurring diffusion pathways and ionic conductivity of this Li + ionic conductor.« less

Microscopic calculations of liquid and solid neutron star matter

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

Chakravarty, Sudip; Miller, Michael D.; Chia-Wei, Woo

1974-02-01

As the first step to a microscopic determination of the solidification density of neutron star matter, variational calculations are performed for both liquid and solid phases using a very simple model potential. The potential, containing only the repulsive part of the Reid /sup 1/S/sub o/ interaction, together with Boltzmann statistics defines a homework problem'' which several groups involved in solidification calculations have agreed to solve. The results were to be compared for the purpose of checking calculational techniques. For the solid energy good agreement with Canuto and Chitre was found. Both the liquid and solid energies are much lower thanmore » those of Pandharipande. It is shown that for this oversimplified model, neutron star matter will remain solid down to ordinary nuclear matter density.« less

Endothelial cell density after photorefractive keratectomy for moderate myopia using a 213 nm solid-state laser system.

PubMed

Tsiklis, Nikolaos S; Kymionis, George D; Pallikaris, Aristofanis I; Diakonis, Vasilios F; Ginis, Harilaos S; Kounis, George A; Panagopoulou, Sophia I; Pallikaris, Ioannis G

2007-11-01

To evaluate whether photorefractive keratectomy (PRK) for moderate myopia using a solid-state laser with a wavelength of 213 nm alters the corneal endothelial cell density. University refractive surgery center. The corneal endothelium was analyzed preoperatively and 1, 6, and 12 months postoperatively using corneal confocal microscopy (modified HRT II with a Rostock Cornea Module, Heidelberg Engineering) in 60 eyes (30 patients). Patients were randomized to have myopic PRK using a 213 nm wavelength solid-state laser (study group) or a conventional 193 nm wavelength excimer laser (control group). Three endothelial images were acquired in each of 30 preoperative normal eyes to evaluate the repeatability of endothelial cell density measurements. Repeated-measures analysis of variance was used to compare the variations in endothelial cell density between the 2 lasers and the changes in endothelial cell density over time. There were no statistically significant differences in sex, age, corneal pachymetry, attempted correction, preoperative endothelial cell density, or postoperative refractive outcomes (uncorrected visual acuity, best spectacle-corrected visual acuity, and spherical equivalent refraction) between the 2 groups (P>.05). The coefficient of repeatability of endothelial cell density was 131 cells/mm(2). The measured endothelial cell count per 1.0 mm(2) did not significantly change up to 1 year postoperatively in either group (both P>.05). No statistically significant difference was found between the 2 groups in any postoperative interval (P>.05). Photorefractive keratectomy for moderate myopia using a 213 nm wavelength solid-state laser or a conventional 193 nm wavelength excimer laser did not significantly affect corneal endothelial density during the 1-year postoperative period.

Communication: A combined periodic density functional and incremental wave-function-based approach for the dispersion-accounting time-resolved dynamics of ⁴He nanodroplets on surfaces: ⁴He/graphene.

PubMed

de Lara-Castells, María Pilar; Stoll, Hermann; Civalleri, Bartolomeo; Causà, Mauro; Voloshina, Elena; Mitrushchenkov, Alexander O; Pi, Martí

2014-10-21

In this work we propose a general strategy to calculate accurate He-surface interaction potentials. It extends the dispersionless density functional approach recently developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] to adsorbate-surface interactions by including periodic boundary conditions. We also introduce a scheme to parametrize the dispersion interaction by calculating two- and three-body dispersion terms at coupled cluster singles and doubles and perturbative triples (CCSD(T)) level via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. The performance of the composite approach is tested on (4)He/graphene by determining the energies of the low-lying selective adsorption states, finding an excellent agreement with the best available theoretical data. Second, the capability of the approach to describe dispersionless correlation effects realistically is used to extract dispersion effects in time-dependent density functional simulations on the collision of (4)He droplets with a single graphene sheet. It is found that dispersion effects play a key role in the fast spreading of the (4)He nanodroplet, the evaporation-like process of helium atoms, and the formation of solid-like helium structures. These characteristics are expected to be quite general and highly relevant to explain experimental measurements with the newly developed helium droplet mediated deposition technique.

Discovering charge density functionals and structure-property relationships with PROPhet: A general framework for coupling machine learning and first-principles methods

DOE PAGES

Kolb, Brian; Lentz, Levi C.; Kolpak, Alexie M.

2017-04-26

Modern ab initio methods have rapidly increased our understanding of solid state materials properties, chemical reactions, and the quantum interactions between atoms. However, poor scaling often renders direct ab initio calculations intractable for large or complex systems. There are two obvious avenues through which to remedy this problem: (i) develop new, less expensive methods to calculate system properties, or (ii) make existing methods faster. This paper describes an open source framework designed to pursue both of these avenues. PROPhet (short for PROPerty Prophet) utilizes machine learning techniques to find complex, non-linear mappings between sets of material or system properties. Themore » result is a single code capable of learning analytical potentials, non-linear density functionals, and other structure-property or property-property relationships. These capabilities enable highly accurate mesoscopic simulations, facilitate computation of expensive properties, and enable the development of predictive models for systematic materials design and optimization. Here, this work explores the coupling of machine learning to ab initio methods through means both familiar (e.g., the creation of various potentials and energy functionals) and less familiar (e.g., the creation of density functionals for arbitrary properties), serving both to demonstrate PROPhet’s ability to create exciting post-processing analysis tools and to open the door to improving ab initio methods themselves with these powerful machine learning techniques.« less

Discovering charge density functionals and structure-property relationships with PROPhet: A general framework for coupling machine learning and first-principles methods

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

Kolb, Brian; Lentz, Levi C.; Kolpak, Alexie M.

Modern ab initio methods have rapidly increased our understanding of solid state materials properties, chemical reactions, and the quantum interactions between atoms. However, poor scaling often renders direct ab initio calculations intractable for large or complex systems. There are two obvious avenues through which to remedy this problem: (i) develop new, less expensive methods to calculate system properties, or (ii) make existing methods faster. This paper describes an open source framework designed to pursue both of these avenues. PROPhet (short for PROPerty Prophet) utilizes machine learning techniques to find complex, non-linear mappings between sets of material or system properties. Themore » result is a single code capable of learning analytical potentials, non-linear density functionals, and other structure-property or property-property relationships. These capabilities enable highly accurate mesoscopic simulations, facilitate computation of expensive properties, and enable the development of predictive models for systematic materials design and optimization. Here, this work explores the coupling of machine learning to ab initio methods through means both familiar (e.g., the creation of various potentials and energy functionals) and less familiar (e.g., the creation of density functionals for arbitrary properties), serving both to demonstrate PROPhet’s ability to create exciting post-processing analysis tools and to open the door to improving ab initio methods themselves with these powerful machine learning techniques.« less

On the Lennard-Jones and Devonshire theory for solid state thermodynamics

NASA Astrophysics Data System (ADS)

Lustig, Rolf

2017-06-01

The Lennard-Jones and Devonshire theory is developed into a self-consistent scheme for essentially complete thermodynamic information. The resulting methodology is compared with molecular simulation of the Lennard-Jones system in the face-centred-cubic solid state over an excessive range of state points. The thermal and caloric equations of state are in almost perfect agreement along the entire fluid-solid coexistence lines over more than six orders of magnitude in pressure. For homogeneous densities greater than twice the solid triple point density, the theory is essentially exact for derivatives of the Helmholtz energy. However, the fluid-solid phase equilibria are in disagreement with simulation. It is shown that the theory is in error by an additive constant to the Helmholtz energy A/(NkBT). Empirical inclusion of the error term makes all fluid-solid equilibria indistinguishable from exact results. Some arguments about the origin of the error are given.

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

Nonharmonicity in vibrated granular solids

NASA Astrophysics Data System (ADS)

Schreck, Carl

2012-02-01

We have shown that granular packings composed of frictionless particles with repulsive contact interactions are strongly nonharmonic. When infinitesimally perturbed along linear response eigenmodes of the static packing, energy leaks from the original mode of vibration to a continuum of frequencies due solely to contact breaking even when the system is under significant compression. Further, vibrated packings possess well-defined equilibrium positions that are different than those of the unperturbed packing. The vibrational density of states obtained using the displacement matrix and velocity autocorrelation function methods exhibit an increase in the number of low-frequency modes over that obtained from linear response of the static packing. The form of the density of states in vibrated granular packings is reminiscent of the low-frequency behavior of the vibrational density of states in fluid systems. We also investigate the effects of inter-particle friction, dissipation, particle shape, and degree of positional order on the density of states and thermal transport properties in driven granular packings.

Positional ordering of hard adsorbate particles in tubular nanopores

NASA Astrophysics Data System (ADS)

Gurin, Péter; Varga, Szabolcs; Martínez-Ratón, Yuri; Velasco, Enrique

2018-05-01

The phase behavior and structural properties of a monolayer of hard particles is examined in such a confinement where the adsorbed particles are constrained to the surface of a narrow hard cylindrical pore. The diameter of the pore is chosen such that only first- and second-neighbor interactions occur between the hard particles. The transfer operator method of [Percus and Zhang, Mol. Phys. 69, 347 (1990), 10.1080/00268979000100241] is reformulated to obtain information about the structure of the monolayer. We have found that a true phase transition is not possible in the examined range of pore diameters. The monolayer of hard spheres undergoes a structural change from fluidlike order to a zigzaglike solid one with increasing surface density. The case of hard cylinders is different in the sense that a layering takes place continuously between a low-density one-row and a high-density two-row monolayer. Our results reveal a clear discrepancy with classical density functional theories, which do not distinguish smecticlike ordering in bulk from that in narrow periodic pores.

The transition to the metallic state in low density hydrogen

DOE PAGES

McMinis, Jeremy; Morales, Miguel A.; Ceperley, David M.; ...

2015-11-18

Solid atomic hydrogen is one of the simplest systems to undergo a metal-insulator transition. Near the transition, the electronic degrees of freedom become strongly correlated and their description provides a difficult challenge for theoretical methods. As a result, the order and density of the phase transition are still subject to debate. In this work we use diffusion quantum Monte Carlo to benchmark the transition between the paramagnetic and anti-ferromagnetic phases of ground state body centered cubic atomic hydrogen. We locate the density of the transition by computing the equation of state for these two phases and identify the phase transitionmore » order by computing the band gap near the phase transition. These benchmark results show that the phase transition is continuous and occurs at a Wigner-Seitz radius of r s = 2.27(3)a 0. As a result, we compare our results to previously reported density functional theory, Hedin s GW approximation, and dynamical mean field theory results.« less

High-Density Near-Field Readout Using Solid Immersion Lens Made of KTaO3 Monocrystal

NASA Astrophysics Data System (ADS)

Shinoda, Masataka; Saito, Kimihiro; Kondo, Takao; Furuki, Motohiro; Takeda, Minoru; Nakaoki, Ariyoshi; Sasaura, Masahiro; Fujiura, Kazuo

2006-02-01

We developed solid immersion lenses made of a KTaO3 monocrystal. The refractive index of KTaO3 is 2.382 at a wavelength of 405 nm. Using KTaO3 as the raw material of a solid immersion lens, we could design an effective numerical aperture of 2.20. We observed an eye pattern of a 150 GB capacity with a 130 nm track pitch and a 47.6 nm bit length. The areal density is 104.3 Gbit/in.2.

Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of ferulic acid by density functional study

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sundaraganesan, N.; Manoharan, S.

2009-10-01

Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of ferulic acid (FA) (4-hydroxy-3-methoxycinnamic acid) were carried out by using density functional (DFT/B3LYP/BLYP) method with 6-31G(d,p) as basis set. The optimized geometrical parameters obtained by DFT calculations are in good agreement with single crystal XRD data. The vibrational spectral data obtained from solid phase FT-IR and FT-Raman spectra are assigned based on the results of the theoretical calculations. The observed spectra are found to be in good agreement with calculated values. The electric dipole moment ( μ) and the first hyperpolarizability ( β) values of the investigated molecule have been computed using ab initio quantum mechanical calculations. The calculation results also show that the FA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of FA was also reported. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The theoretical FT-IR and FT-Raman spectra for the title molecule have been constructed.

Pressure induced structural phase transition in solid oxidizer KClO3: A first-principles study

NASA Astrophysics Data System (ADS)

Yedukondalu, N.; Ghule, Vikas D.; Vaitheeswaran, G.

2013-05-01

High pressure behavior of potassium chlorate (KClO3) has been investigated from 0 to 10 GPa by means of first principles density functional theory calculations. The calculated ground state parameters, transition pressure, and phonon frequencies using semiempirical dispersion correction scheme are in excellent agreement with experiment. It is found that KClO3 undergoes a pressure induced first order phase transition with an associated volume collapse of 6.4% from monoclinic (P21/m) → rhombohedral (R3m) structure at 2.26 GPa, which is in good accord with experimental observation. However, the transition pressure was found to underestimate (0.11 GPa) and overestimate (3.57 GPa) using local density approximation and generalized gradient approximation functionals, respectively. Mechanical stability of both the phases is explained from the calculated single crystal elastic constants. In addition, the zone center phonon frequencies have been calculated using density functional perturbation theory at ambient as well as at high pressure and the lattice modes are found to soften under pressure between 0.6 and 1.2 GPa. The present study reveals that the observed structural phase transition leads to changes in the decomposition mechanism of KClO3 which corroborates with the experimental results.

Pressure induced structural phase transition in solid oxidizer KClO3: a first-principles study.

PubMed

Yedukondalu, N; Ghule, Vikas D; Vaitheeswaran, G

2013-05-07

High pressure behavior of potassium chlorate (KClO3) has been investigated from 0 to 10 GPa by means of first principles density functional theory calculations. The calculated ground state parameters, transition pressure, and phonon frequencies using semiempirical dispersion correction scheme are in excellent agreement with experiment. It is found that KClO3 undergoes a pressure induced first order phase transition with an associated volume collapse of 6.4% from monoclinic (P2(1)/m) → rhombohedral (R3m) structure at 2.26 GPa, which is in good accord with experimental observation. However, the transition pressure was found to underestimate (0.11 GPa) and overestimate (3.57 GPa) using local density approximation and generalized gradient approximation functionals, respectively. Mechanical stability of both the phases is explained from the calculated single crystal elastic constants. In addition, the zone center phonon frequencies have been calculated using density functional perturbation theory at ambient as well as at high pressure and the lattice modes are found to soften under pressure between 0.6 and 1.2 GPa. The present study reveals that the observed structural phase transition leads to changes in the decomposition mechanism of KClO3 which corroborates with the experimental results.

Uniform electron gases. III. Low-density gases on three-dimensional spheres.

PubMed

Agboola, Davids; Knol, Anneke L; Gill, Peter M W; Loos, Pierre-François

2015-08-28

By combining variational Monte Carlo (VMC) and complete-basis-set limit Hartree-Fock (HF) calculations, we have obtained near-exact correlation energies for low-density same-spin electrons on a three-dimensional sphere (3-sphere), i.e., the surface of a four-dimensional ball. In the VMC calculations, we compare the efficacies of two types of one-electron basis functions for these strongly correlated systems and analyze the energy convergence with respect to the quality of the Jastrow factor. The HF calculations employ spherical Gaussian functions (SGFs) which are the curved-space analogs of Cartesian Gaussian functions. At low densities, the electrons become relatively localized into Wigner crystals, and the natural SGF centers are found by solving the Thomson problem (i.e., the minimum-energy arrangement of n point charges) on the 3-sphere for various values of n. We have found 11 special values of n whose Thomson sites are equivalent. Three of these are the vertices of four-dimensional Platonic solids - the hyper-tetrahedron (n = 5), the hyper-octahedron (n = 8), and the 24-cell (n = 24) - and a fourth is a highly symmetric structure (n = 13) which has not previously been reported. By calculating the harmonic frequencies of the electrons around their equilibrium positions, we also find the first-order vibrational corrections to the Thomson energy.

Nanoscaled Na3PS4 Solid Electrolyte for All-Solid-State FeS2/Na Batteries with Ultrahigh Initial Coulombic Efficiency of 95% and Excellent Cyclic Performances.

PubMed

Wan, Hongli; Mwizerwa, Jean Pierre; Qi, Xingguo; Xu, Xiaoxiong; Li, Hong; Zhang, Qiang; Cai, Liangting; Hu, Yong-Sheng; Yao, Xiayin

2018-04-18

Nanosized Na 3 PS 4 solid electrolyte with an ionic conductivity of 8.44 × 10 -5 S cm -1 at room temperature is synthesized by a liquid-phase reaction. The resultant all-solid-state FeS 2 /Na 3 PS 4 /Na batteries show an extraordinary high initial Coulombic efficiency of 95% and demonstrate high energy density of 611 Wh kg -1 at current density of 20 mA g -1 at room temperature. The outstanding performances of the battery can be ascribed to good interface compatibility and intimate solid-solid contact at FeS 2 electrode/nanosized Na 3 PS 4 solid electrolytes interface. Meanwhile, excellent cycling stability is achieved for the battery after cycling at 60 mA g -1 for 100 cycles, showing a high capacity of 287 mAh g -1 with the capacity retention of 80%.

Pre-Bombing Population Density in Hiroshima and Nagasaki: Its Measurement and Impact on Radiation Risk Estimates in the Life Span Study of Atomic Bomb Survivors.

PubMed

French, Benjamin; Funamoto, Sachiyo; Sugiyama, Hiromi; Sakata, Ritsu; Cologne, John; Cullings, Harry M; Mabuchi, Kiyohiko; Preston, Dale L

2018-03-29

In the Life Span Study of atomic bomb survivors, differences in urbanicity between high-dose and low-dose survivors could confound the association between radiation dose and adverse outcomes. We obtained data on the pre-bombing population distribution in Hiroshima and Nagasaki, and quantified the impact of adjustment for population density on radiation risk estimates for mortality (1950-2003) and incident solid cancer (1958-2009). Population density ranged from 4,671-14,378 and 5,748-19,149 people/km2 in urban regions of Hiroshima and Nagasaki, respectively. Radiation risk estimates for solid cancer mortality were attenuated by 5.1%, but those for all-cause mortality and incident solid cancer were unchanged. There was no overall association between population density and adverse outcomes, but there was evidence that the association between density and mortality differed by age at exposure. Among survivors 10-14 years old in 1945, there was a positive association between population density and risk of all-cause mortality (relative risk, 1.053 per 5,000 people/km2 increase, 95% confidence interval: 1.027, 1.079) and solid cancer mortality (relative risk, 1.069 per 5,000 people/km2 increase, 95% confidence interval: 1.025, 1.115). Our results suggest that radiation risk estimates from the Life Span Study are not sensitive to unmeasured confounding by urban-rural differences.

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

DOE PAGES

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

2015-11-02

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

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

PubMed

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

2015-12-09

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

Structure-based coarse-graining for inhomogeneous liquid polymer systems.

PubMed

Fukuda, Motoo; Zhang, Hedong; Ishiguro, Takahiro; Fukuzawa, Kenji; Itoh, Shintaro

2013-08-07

The iterative Boltzmann inversion (IBI) method is used to derive interaction potentials for coarse-grained (CG) systems by matching structural properties of a reference atomistic system. However, because it depends on such thermodynamic conditions as density and pressure of the reference system, the derived CG nonbonded potential is probably not applicable to inhomogeneous systems containing different density regimes. In this paper, we propose a structure-based coarse-graining scheme to devise CG nonbonded potentials that are applicable to different density bulk systems and inhomogeneous systems with interfaces. Similar to the IBI, the radial distribution function (RDF) of a reference atomistic bulk system is used for iteratively refining the CG nonbonded potential. In contrast to the IBI, however, our scheme employs an appropriately estimated initial guess and a small amount of refinement to suppress transfer of the many-body interaction effects included in the reference RDF into the CG nonbonded potential. To demonstrate the application of our approach to inhomogeneous systems, we perform coarse-graining for a liquid perfluoropolyether (PFPE) film coated on a carbon surface. The constructed CG PFPE model favorably reproduces structural and density distribution functions, not only for bulk systems, but also at the liquid-vacuum and liquid-solid interfaces, demonstrating that our CG scheme offers an easy and practical way to accurately determine nonbonded potentials for inhomogeneous systems.

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Polymer on Top: Current Limits and Future Perspectives of Quantitatively Evaluating Surface Grafting.

PubMed

Michalek, Lukas; Barner, Leonie; Barner-Kowollik, Christopher

2018-03-07

Well-defined polymer strands covalently tethered onto solid substrates determine the properties of the resulting functional interface. Herein, the current approaches to determine quantitative grafting densities are assessed. Based on a brief introduction into the key theories describing polymer brush regimes, a user's guide is provided to estimating maximum chain coverage and-importantly-examine the most frequently employed approaches for determining grafting densities, i.e., dry thickness measurements, gravimetric assessment, and swelling experiments. An estimation of the reliability of these determination methods is provided via carefully evaluating their assumptions and assessing the stability of the underpinning equations. A practical access guide for comparatively and quantitatively evaluating the reliability of a given approach is thus provided, enabling the field to critically judge experimentally determined grafting densities and to avoid the reporting of grafting densities that fall outside the physically realistic parameter space. The assessment is concluded with a perspective on the development of advanced approaches for determination of grafting density, in particular, on single-chain methodologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Energy Density science at the Linac Coherent Light Source

NASA Astrophysics Data System (ADS)

Glenzer, S. H.; Fletcher, L. B.; Hastings, J. B.

2016-03-01

The Matter in Extreme Conditions end station at the Linac Coherent Light Source holds great promise for novel pump-probe experiments to make new discoveries in high- energy density science. In recent experiments we have demonstrated the first spectrally- resolved measurements of plasmons using a seeded 8-keV x-ray laser beam. Forward x-ray Thomson scattering spectra from isochorically heated solid aluminum show a well-resolved plasmon feature that is down-shifted in energy by 19 eV from the incident 8 keV elastic scattering feature. In this spectral range, the simultaneously measured backscatter spectrum shows no spectral features indicating observation of collective plasmon oscillations on a scattering length comparable to the screening length. This technique is a prerequisite for Thomson scattering measurements in compressed matter where the plasmon shift is a sensitive function of the free electron density and where the plasmon intensity provides information on temperature.

Space-Time Characterization of Laser Plasma Interactions in the Warm Dense Matter Regime

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

Cao, L F; Uschmann, I; Forster, E

2008-04-30

Laser plasma interaction experiments have been performed using a fs Titanium Sapphire laser. Plasmas have been generated from planar PMMA targets using single laser pulses with 3.3 mJ pulse energy, 50 fs pulse duration at 800 nm wavelength. The electron density distributions of the plasmas in different delay times have been characterized by means of Nomarski Interferometry. Experimental data were compared with hydrodynamic simulation. First results to characterize the plasma density and temperature as a function of space and time are obtained. This work aims to generate plasmas in the warm dense matter (WDM) regime at near solid-density in anmore » ultra-fast laser target interaction process. Plasmas under these conditions can serve as targets to develop x-ray Thomson scattering as a plasma diagnostic tool, e.g., using the VUV free-electron laser (FLASH) at DESY Hamburg.« less

High-Energy Density science at the Linac Coherent Light Source

DOE PAGES

Glenzer, S. H.; Fletcher, L. B.; Hastings, J. B.

2016-04-01

The Matter in Extreme Conditions end station at the Linac Coherent Light Source holds great promise for novel pump-probe experiments to make new discoveries in high- energy density science. Recently, our experiments have demonstrated the first spectrally- resolved measurements of plasmons using a seeded 8-keV x-ray laser beam. Forward x-ray Thomson scattering spectra from isochorically heated solid aluminum show a well-resolved plasmon feature that is down-shifted in energy by 19 eV from the incident 8 keV elastic scattering feature. In this spectral range, the simultaneously measured backscatter spectrum shows no spectral features indicating observation of collective plasmon oscillations on amore » scattering length comparable to the screening length. Moreover, this technique is a prerequisite for Thomson scattering measurements in compressed matter where the plasmon shift is a sensitive function of the free electron density and where the plasmon intensity provides information on temperature.« less

Environment-dependent conformation investigation of 3-amino-1,2,4-triazole (3-AT): Raman Spectroscopy and density functional theory

NASA Astrophysics Data System (ADS)

Meng, Shuang; Zhao, Yanying; Xue, Jiadan; Zheng, Xuming

2018-02-01

In the paper, diverse tautomers of 3-amino-1,2,4-triazole (3AT) in solid and polar solvent have been explored by FT-IR, FT-Raman and 488 nm Raman experiments combing with quantum chemical theoretical calculation using PCM solvent model and normal mode analysis. The vibrational spectra prefer the 3-amino-1,2,4-2H-triazole (2H-3AT) dimer in solid, while in a polar solvent 3AT is apt to the 3-amino-1,2,4-2H-triazole (2H-3AT) monomer. The significant wavenumber difference and Raman intensity patterns in solid and different solvents are induced by hydrogen bond perturbation along > NH ⋯ N ≤ hydrogen bonds on five-membered N-heterocyclic ring. The ground state proton transfer reaction mechanism along the five-membered N-heterocyclic ring is supported by intermolecular hydrogen bonding between 3AT and protonic solvent molecules.

FT-IR and FT-Raman spectra of 5-chlorocytosine: Solid state simulation and tautomerism. Effect of the chlorine substitution in the Watson-Crick base pair 5-chlorodeoxycytidine-deoxyguanosine

NASA Astrophysics Data System (ADS)

Alcolea Palafox, M.; Rastogi, V. K.; Singh, S. P.

2018-01-01

The laser Raman and IR spectra of 5-chlorocytosine have been recorded and accurately assigned in the solid state using Density functional calculations (DFT) together with the linear scaling equation procedure (LSE) and the solid state simulation of the crystal unit cell through a tetramer form. These results remarkably improve those reported previously by other authors. Several new scaling equations were proposed to be used in related molecules. The six main tautomers of the biomolecule 5-chlorocytosine were determined and optimized at the MP2 and CCSD levels, using different basis sets. The relative stabilities were compared with those obtained in cytosine and their 5-halo derivatives. Several relationships between energies, geometric parameters and NBO atomic charges were established. The effect of the chlorine substitution in the fifth position was evaluated through the stability of the Watson-Crick (WC) base pair of 5-chlorodeoxycytidine with deoxyguanosine, and through their vibrational spectra.

Synthesis, characterization and theoretical study in gaseous and solid phases of the imine 4-Acetyl-N-(4-methoxybenzylidene)aniline

NASA Astrophysics Data System (ADS)

Batista, J. F. N.; Cruz, J. W.; Doriguetto, A. C.; Torres, C.; de Almeida, E. T.; Camps, I.

2017-11-01

In the present paper we describe the synthesis and characterization of the Schiff's base or imine 4-Acetyl-N-(4-methoxybenzylidene)aniline (1), which provided experimental support for the theoretical calculations. The imine was characterized by infrared spectroscopy and single crystal XRD techniques. The computational studies were performed using the density functional theory (DFT) for the gaseous and solid phases. As similar compounds already shown biological activity, the pharmacokinetic properties of (1) were evaluated. Our results shown that (1), in its gaseous form, it is electronically stable and has pharmacological drug like properties. Due to its structural similarity with commercial drugs, it is a promise candidate to act as a nonsteroidal anti-inflammatory and to treat dementia, sleep disorders, alcohol dependence, and psychosis. From the solid state calculations we obtain that (1) is a low gap semiconductor and can act as an absorber for electromagnetic radiations with energy greater that ∼ 0.9eV .

A statistical approach to the brittle fracture of a multi-phase solid

NASA Technical Reports Server (NTRS)

Liu, W. K.; Lua, Y. I.; Belytschko, T.

1991-01-01

A stochastic damage model is proposed to quantify the inherent statistical distribution of the fracture toughness of a brittle, multi-phase solid. The model, based on the macrocrack-microcrack interaction, incorporates uncertainties in locations and orientations of microcracks. Due to the high concentration of microcracks near the macro-tip, a higher order analysis based on traction boundary integral equations is formulated first for an arbitrary array of cracks. The effects of uncertainties in locations and orientations of microcracks at a macro-tip are analyzed quantitatively by using the boundary integral equations method in conjunction with the computer simulation of the random microcrack array. The short range interactions resulting from surrounding microcracks closet to the main crack tip are investigated. The effects of microcrack density parameter are also explored in the present study. The validity of the present model is demonstrated by comparing its statistical output with the Neville distribution function, which gives correct fits to sets of experimental data from multi-phase solids.

Adequacy of damped dynamics to represent the electron-phonon interaction in solids

DOE PAGES

Caro, A.; Correa, A. A.; Tamm, A.; ...

2015-10-16

Time-dependent density functional theory and Ehrenfest dynamics are used to calculate the electronic excitations produced by a moving Ni ion in a Ni crystal in the case of energetic MeV range (electronic stopping power regime), as well as thermal energy meV range (electron-phonon interaction regime). Results at high energy compare well to experimental databases of stopping power, and at low energy the electron-phonon interaction strength determined in this way is very similar to the linear response calculation and experimental measurements. This approach to electron-phonon interaction as an electronic stopping process provides the basis for a unified framework to perform classicalmore » molecular dynamics of ion-solid interaction with ab initio type nonadiabatic terms in a wide range of energies.« less

High-pressure melting curve of hydrogen.

PubMed

Davis, Sergio M; Belonoshko, Anatoly B; Johansson, Börje; Skorodumova, Natalia V; van Duin, Adri C T

2008-11-21

The melting curve of hydrogen was computed for pressures up to 200 GPa, using molecular dynamics. The inter- and intramolecular interactions were described by the reactive force field (ReaxFF) model. The model describes the pressure-volume equation of state solid hydrogen in good agreement with experiment up to pressures over 150 GPa, however the corresponding equation of state for liquid deviates considerably from density functional theory calculations. Due to this, the computed melting curve, although shares most of the known features, yields considerably lower melting temperatures compared to extrapolations of the available diamond anvil cell data. This failure of the ReaxFF model, which can reproduce many physical and chemical properties (including chemical reactions in hydrocarbons) of solid hydrogen, hints at an important change in the mechanism of interaction of hydrogen molecules in the liquid state.

Turbulence kinetic energy equation for dilute suspensions

NASA Technical Reports Server (NTRS)

Abou-Arab, T. W.; Roco, M. C.

1989-01-01

A multiphase turbulence closure model is presented which employs one transport equation, namely the turbulence kinetic energy equation. The proposed form of this equation is different from the earlier formulations in some aspects. The power spectrum of the carrier fluid is divided into two regions, which interact in different ways and at different rates with the suspended particles as a function of the particle-eddy size ratio and density ratio. The length scale is described algebraically. A mass/time averaging procedure for the momentum and kinetic energy equations is adopted. The resulting turbulence correlations are modeled under less retrictive assumptions comparative to previous work. The closures for the momentum and kinetic energy equations are given. Comparisons of the predictions with experimental results on liquid-solid jet and gas-solid pipe flow show satisfactory agreement.

Fracture Toughness, Mechanical Property, And Chemical Characterization Of A Critical Modification To The NASA SLS Solid Booster Internal Material System

NASA Technical Reports Server (NTRS)

Pancoast, Justin; Garrett, William; Moe, Gulia

2015-01-01

A modified propellant-liner-insulation (PLI) bondline in the Space Launch System (SLS) solid rocket booster required characterization for flight certification. The chemical changes to the PLI bondline and the required additional processing have been correlated to mechanical responses of the materials across the bondline. Mechanical properties testing and analyses included fracture toughness, tensile, and shear tests. Chemical properties testing and analyses included Fourier transform infrared (FTIR) spectroscopy, cross-link density, high-performance liquid chromatography (HPLC), gas chromatography (GC), gel permeation chromatography (GPC), and wave dispersion X-ray fluorescence (WDXRF). The testing identified the presence of the expected new materials and found the functional bondline performance of the new PLI system was not significantly changed from the old system.

Solid state structure and absolute configuration of filifolinol acetate.

PubMed

Muñoz, Marcelo A; Urzúa, Alejandro; Echeverría, Javier; Modak, Brenda; Joseph-Nathan, Pedro

2011-06-01

Careful reevaluation of the 1H and 13C NMR spectroscopic data of filifolinol acetate (4) led to the reassignment of the C-10 and C-11 signals, as well as the gem-dimethyl signals. Single crystal X-ray analysis provided an independent structural confirmation of 4, and comparison of the experimental vibrational circular dichroism spectrum with calculations performed using density functional theory provided the absolute configuration of this 3H-spiro-1-benzofuran-2,1'-cyclohexane and related molecules.

Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

PubMed

Dai, Weili; Wang, Chuanming; Yi, Xianfeng; Zheng, Anmin; Li, Landong; Wu, Guangjun; Guan, Naijia; Xie, Zaiku; Dyballa, Michael; Hunger, Michael

2015-07-20

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement in hardness of soda-lime-silica glass

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

Chakraborty, Riya; De, Moumita; Roy, Sudakshina

2012-06-05

Hardness is a key design parameter for structural application of brittle solids like glass. Here we report for the first time the significant improvement of about 10% in Vicker's hardness of a soda-lime-silica glass with loading rate in the range of 0.1-10 N.s{sup -1}. Corroborative dark field optical and scanning electron microscopy provided clue to this improvement through evidence of variations in spatial density of shear deformation band formation as a function of loading rate.

Electronic excitations and chemistry in Nitromethane and HMX

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

Reed, E J; Manaa, M R; Joannopoulos, J D

2001-06-19

The nature of electronic excitations in crystalline solid nitromethane under conditions of shock loading and static compression are examined. Density functional theory calculations are used to determine the crystal bandgap under hydrostatic stress, uniaxial strain, and shear strain. Bandgap lowering under uniaxial strain due to molecular defects and vacancies is considered. In all cases, the bandgap is not lowered enough to produce a significant population of excited states in the crystal. Preliminary simulations on the formation of detonation product molecules from HMX are discussed.

Modulation Doped GaAs/Al sub xGA sub (1-x)As Layered Structures with Applications to Field Effect Transistors.

DTIC Science & Technology

1982-02-15

function of the doping density at 300 and 77 K for the classical Boltzmann statistics or depletion approximation (solid line) and for the approximate...Fermi-Dirac statistics (equation (19) dotted line)• This comparison demonstrates that the deviation from Boltzmann statistics is quite noticeable...tunneling Schottky barriers cannot be obtained at these doping levels. The dotted lines are obtained when Boltzmann statistics are used in the Al Ga

The Upper Limit of Energy Density of Nanoporous Materials Functionalized Liquid

NASA Astrophysics Data System (ADS)

Han, Aijie; Punyamurtula, Venkata K.; Kim, Taewan; Qiao, Yu

2008-06-01

In this article, we report the experimental result of energy dissipation of a mobil crystalline material (MCM) 41 in mercury. The MCM41 contains a large volume fraction of nanometer-sized pores. As the applied pressure is relatively high, the nanopore surfaces are exposed to mercury. Due to the large nanopore surface area and the large solid-liquid interfacial tension, the energy dissipation effectiveness of this system is ultrahigh, representing the upper limit that can be achieved by the pressure-induced infiltration technique.

Rietveld refinement and electrical properties of Ni-Zn spinel ferrites

NASA Astrophysics Data System (ADS)

Hooda, Ashima; Sanghi, Sujata; Agarwal, Ashish; Khasa, Satish; Hooda, Bhawana

2017-05-01

NiFe2O4, ZnFe2O4, Ni0.5Zn0.5Fe2O4 spinel samples have been synthesized by conventional solid state reaction technique. Powder X-ray diffraction and Rietveld refinement revealed that the samples were single Spinel phase with space group fd3m. The average crystalline size (D), lattice constant (a), X-ray density (ρx), measured density (ρm) and Porosity (P) of prepared samples were determined from XRD data. The dc electrical resistivity (p) was measured as a function of temperature. The variations of ρ were explained on the basis of Verwey and de Bohr mechanism. The value of DC resistivity found to increase with increase Zn concentration.

Density Gradients in Chemistry Teaching

ERIC Educational Resources Information Center

Miller, P. J.

1972-01-01

Outlines experiments in which a density gradient might be used to advantage. A density gradient consists of a column of liquid, the composition and density of which varies along its length. The procedure can be used in analysis of solutions and mixtures and in density measures of solids. (Author/TS)

A monolithic integrated micro direct methanol fuel cell based on sulfo functionalized porous silicon

NASA Astrophysics Data System (ADS)

Wang, M.; Lu, Y. X.; Liu, L. T.; Wang, X. H.

2016-11-01

In this paper, we demonstrate a monolithic integrated micro direct methanol fuel cell (μDMFC) for the first time. The monolithic integrated μDMFC combines proton exchange membrane (PEM) and Pt nanocatalysts, in which PEM is achieved by the functionalized porous silicon membrane and 3D Pt nanoflowers being synthesized in situ on it as catalysts. Sulfo groups functionalized porous silicon membrane serves as a PEM and a catalyst support simultaneously. The μDMFC prototype achieves an open circuit voltage of 0.3 V, a maximum power density of 5.5 mW/cm2. The monolithic integrated μDMFC offers several desirable features such as compatibility with micro fabrication techniques, an undeformable solid PEM and the convenience of assembly.

Resistivity of a simple metal from room temperature to 10 to the 6th K

NASA Astrophysics Data System (ADS)

Milchberg, H. M.; Freeman, R. R.; Davey, S. C.; More, R. M.

1988-11-01

The resistivity of nearly solid-density Al was measured as a function of temperature over 4 orders of magnitude above ambient by observing the self-reflection of an intense, less than 0.5 psec, 308-nm light pulse incident on a planar Al target. As an increasing function of electron temperature, the resistivity is observed initially to increase, reach a maximum which is relatively constant over an extended temperature range, and then decrease at the highest temperatures. The broad maximum is interpreted as resistivity saturation, a condition in which the mean free path of the conduction electrons reaches a minimum value as a function of temperature, regardless of the extent of any further disorder in the material.

Preparation, electronic structure, and chemical bonding of lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3 solid solution

NASA Astrophysics Data System (ADS)

Sasikumar, S.; Saravanan, R.; Saravanakumar, S.; Robert, M. Charles

2018-01-01

Polycrystalline lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3, ((1 - x)KBT- xBT) ( x = 0.00, 0.08, 0.12) ceramics were synthesized via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 - x)KBT- xBT was investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi-O bond and enhancement of covalent nature along Ti-O bond with the addition of BaTiO3. The charge density distribution studies done using maximum entropy method for (1 - x)KBT- xBT have not been done so far. The surface morphology study was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency. The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant ( ɛ) and loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

Materials and other needs for advanced phase change memory (Presentation Recording)

NASA Astrophysics Data System (ADS)

Sosa, Norma E.

2015-09-01

Phase change memory (PCM), with its long history, may now hold its brightest promise to date. This bright future is being fueled by the "push" from big data. PCM is a non-volatile memory technology used to create solid-state random access memory devices that operate based the resistance properties of materials. Employing the electrical resistance differences-as opposed to differences in charge stored-between the amorphous and crystalline phases of the material, PCM can store bits, namely one's and zero's. Indeed, owing to the method of storage, PCM can in fact be designed to hold multiple bits thus leading to a high-density technology twice the storage density and less than half the cost of DRAM, the main kind found in typical personal computers. It has been long known that PCM can fill a need gap that spans 3 decades in performance from DRAM to solid state drive (NAND Flash). Furthermore, PCM devices can lead to performance and reliability improvements essential to enabling significant steps forward to supporting big data centric computing. This talk will focus on the science and challenges of aggressive scaling to realize the density needed, how this scaling challenge is intertwined with materials needs for endurance into the giga-cycles, and the associated forefront research aiming to realizing multi-level functionality into these nanoscale programmable resistor devices.

Dependence of high density nitrogen-vacancy center ensemble coherence on electron irradiation doses and annealing time

NASA Astrophysics Data System (ADS)

Zhang, C.; Yuan, H.; Zhang, N.; Xu, L. X.; Li, B.; Cheng, G. D.; Wang, Y.; Gui, Q.; Fang, J. C.

2017-12-01

Negatively charged nitrogen-vacancy (NV-) center ensembles in diamond have proved to have great potential for use in highly sensitive, small-package solid-state quantum sensors. One way to improve sensitivity is to produce a high-density NV- center ensemble on a large scale with a long coherence lifetime. In this work, the NV- center ensemble is prepared in type-Ib diamond using high energy electron irradiation and annealing, and the transverse relaxation time of the ensemble—T 2—was systematically investigated as a function of the irradiation electron dose and annealing time. Dynamical decoupling sequences were used to characterize T 2. To overcome the problem of low signal-to-noise ratio in T 2 measurement, a coupled strip lines waveguide was used to synchronously manipulate NV- centers along three directions to improve fluorescence signal contrast. Finally, NV- center ensembles with a high concentration of roughly 1015 mm-3 were manipulated within a ~10 µs coherence time. By applying a multi-coupled strip-lines waveguide to improve the effective volume of the diamond, a sub-femtotesla sensitivity for AC field magnetometry can be achieved. The long-coherence high-density large-scale NV- center ensemble in diamond means that types of room-temperature micro-sized solid-state quantum sensors with ultra-high sensitivity can be further developed in the near future.

Method for making a low density polyethylene waste form for safe disposal of low level radioactive material

DOEpatents

Colombo, P.; Kalb, P.D.

1984-06-05

In the method of the invention low density polyethylene pellets are mixed in a predetermined ratio with radioactive particulate material, then the mixture is fed through a screw-type extruder that melts the low density polyethylene under a predetermined pressure and temperature to form a homogeneous matrix that is extruded and separated into solid monolithic waste forms. The solid waste forms are adapted to be safely handled, stored for a short time, and safely disposed of in approved depositories.

High-Density Near-Field Readout over 50 GB Capacity Using Solid Immersion Lens with High Refractive Index

NASA Astrophysics Data System (ADS)

Shinoda, Masataka; Saito, Kimihiro; Kondo, Takao; Ishimoto, Tsutomu; Nakaoki, Ariyoshi

2003-02-01

We have investigated high-density near-field readout using a solid immersion lens with a high refractive index. By using a glass material with a high refractive index of 2.08, we developed an optical pick-up with the effective numerical aperture of 1.8. We could observe a clear eye pattern for a 50 GB capacity disc in 120 mm diameter. We confirmed that the near-field readout system is promising method of realizing a high-density optical disc system.

The effect of riser end geometry on gas-solid hydrodynamics in a CFB riser operating in the core annular and dilute homogeneous flow regimes

DOE PAGES

Breault, Ronald W.; Monazam, Esmail R.; Shadle, Lawrence J.; ...

2017-02-12

Riser hydrodynamics are a function of the flow rates of gas and solids as well as the exit geometry, particularly when operated above the upper transport velocity. This work compares the exit voidage for multiple geometries and two different solids: Geldart group A glass beads and Geldart group B coke. Geometries were changed by modifying the volume of an abrupt T-shaped exit above the lateral riser exit. This was accomplished by positioning a plunger at various heights above the exit from zero to 0.38 m. A dimensionless expression used to predict smooth exit voidage was modified to account for themore » effect of the depth of the blind-T. The new correlation contains the solids-gas load ratio, solids-to-gas density ratio, bed-to-particle diameter ratio, gas Reynolds Number, as well as a term for the exit geometry. This study also found that there was a minimum riser roof height above the blind-T exit beyond which the riser exit voidage was not affected by the exit geometry. A correlation for this minimum riser roof height has also been developed in this study. This study covered riser superficial gas velocities of 4.35 to 7.7 m/s and solids circulation rates of 1.3 to 11.5 kg/s.« less

Solid-support immobilization of a "swing" fusion protein for enhanced glucose oxidase catalytic activity.

PubMed

Takatsuji, Yoshiyuki; Yamasaki, Ryota; Iwanaga, Atsushi; Lienemann, Michael; Linder, Markus B; Haruyama, Tetsuya

2013-12-01

The strategic surface immobilization of a protein can add new functionality to a solid substrate; however, protein activity, e.g., enzymatic activity, can be drastically decreased on immobilization onto a solid surface. The concept of a designed and optimized "molecular interface" is herein introduced in order to address this problem. In this study, molecular interface was designed and constructed with the aim of attaining high enzymatic activity of a solid-surface-immobilized a using the hydrophobin HFBI protein in conjunction with a fusion protein of HFBI attached to glucose oxidase (GOx). The ability of HFBI to form a self-organized membrane on a solid surface in addition to its adhesion properties makes it an ideal candidate for immobilization. The developed fusion protein was also able to form an organized membrane, and its structure and immobilized state on a solid surface were investigated using QCM-D measurements. This method of immobilization showed retention of high enzymatic activity and the ability to control the density of the immobilized enzyme. In this study, we demonstrated the importance of the design and construction of molecular interface for numerous purposes. This method of protein immobilization could be utilized for preparation of high throughput products requiring structurally ordered molecular interfaces, in addition to many other applications. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Assessing the performance of the random phase approximation for exchange and superexchange coupling constants in magnetic crystalline solids

NASA Astrophysics Data System (ADS)

Olsen, Thomas

2017-09-01

The random phase approximation (RPA) for total energies has previously been shown to provide a qualitatively correct description of static correlation in molecular systems, where density functional theory (DFT) with local functionals are bound to fail. This immediately poses the question of whether the RPA is also able to capture the correct physics of strongly correlated solids such as Mott insulators. Due to strong electron localization, magnetic interactions in such systems are dominated by superexchange, which in the simplest picture can be regarded as the analog of static correlation for molecules. In this paper, we investigate the performance of the RPA for evaluating both superexchange and direct exchange interactions in the magnetic solids NiO, MnO, Na3Cu2SbO6,Sr2CuO3,Sr2CuTeO6 , and a monolayer of CrI3, which were chosen to represent a broad variety of magnetic interactions. It is found that the RPA can accurately correct the large errors introduced by Hartree-Fock, independent of the input orbitals used for the perturbative expansion. However, in most cases, accuracies similar to RPA can be obtained with DFT+U, which is significantly simpler from a computational point of view.

Numerical Solution of 3D Poisson-Nernst-Planck Equations Coupled with Classical Density Functional Theory for Modeling Ion and Electron Transport in a Confined Environment

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

Meng, Da; Zheng, Bin; Lin, Guang

2014-08-29

We have developed efficient numerical algorithms for the solution of 3D steady-state Poisson-Nernst-Planck equations (PNP) with excess chemical potentials described by the classical density functional theory (cDFT). The coupled PNP equations are discretized by finite difference scheme and solved iteratively by Gummel method with relaxation. The Nernst-Planck equations are transformed into Laplace equations through the Slotboom transformation. Algebraic multigrid method is then applied to efficiently solve the Poisson equation and the transformed Nernst-Planck equations. A novel strategy for calculating excess chemical potentials through fast Fourier transforms is proposed which reduces computational complexity from O(N2) to O(NlogN) where N is themore » number of grid points. Integrals involving Dirac delta function are evaluated directly by coordinate transformation which yields more accurate result compared to applying numerical quadrature to an approximated delta function. Numerical results for ion and electron transport in solid electrolyte for Li ion batteries are shown to be in good agreement with the experimental data and the results from previous studies.« less

Density functional theory based probe of the affinity interaction of saccharide ligands with extra-cellular sialic acid residues.

PubMed

Patel, Anjali; Tiwari, Sanjay; Jha, Prafulla K

2018-05-10

Changes in glycosylation pattern leads to malignant transformations among the cells. In combination with upregulated actions of sialyltransferases, it ultimately leads to differential expression of sialic acid (SA) at cell surface. Given its negative charge and localization to extracellular domain, SA has been exploited for the development of targeted theranostics using approaches, such as, cationization and appending recognition saccharides on carrier surface. In this study, we have performed quantum mechanical calculations based on density functional theory (DFT) to study the interaction of saccharides with extracellular SA. Gradient-corrected DFT with the three parameter function (B3) was utilized for the calculation of Lee-Yang-Parr (LYP) correlation function. Atomic charge, vibrational frequencies and energy of the optimized structures were calculated through B3LYP. Our calculations demonstrate a stronger galactose-sialic acid interaction at tumour-relevant low pH and hyperthermic condition. These results support the application of pH responsive delivery vehicles and targeted hyperthermic chemotherapy for eradicating solid tumour deposits. These studies, conducted a priori, can guide the formulation scientists over appropriate choice of ligands and their applications in the design of 'smart' theranostic tools.

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

Breault, Ronald W.; Monazam, Esmail R.; Shadle, Lawrence J.

Riser hydrodynamics are a function of the flow rates of gas and solids as well as the exit geometry, particularly when operated above the upper transport velocity. This work compares the exit voidage for multiple geometries and two different solids: Geldart group A glass beads and Geldart group B coke. Geometries were changed by modifying the volume of an abrupt T-shaped exit above the lateral riser exit. This was accomplished by positioning a plunger at various heights above the exit from zero to 0.38 m. A dimensionless expression used to predict smooth exit voidage was modified to account for themore » effect of the depth of the blind-T. The new correlation contains the solids-gas load ratio, solids-to-gas density ratio, bed-to-particle diameter ratio, gas Reynolds Number, as well as a term for the exit geometry. This study also found that there was a minimum riser roof height above the blind-T exit beyond which the riser exit voidage was not affected by the exit geometry. A correlation for this minimum riser roof height has also been developed in this study. This study covered riser superficial gas velocities of 4.35 to 7.7 m/s and solids circulation rates of 1.3 to 11.5 kg/s.« less

Endo-Fullerene and Doped Diamond Nanocrystallite Based Models of Qubits for Solid-State Quantum Computers

NASA Technical Reports Server (NTRS)

Park, Seongjun; Srivastava, Deepak; Cho, Kyeongjae; Biegel, Bryan (Technical Monitor)

2001-01-01

Models of encapsulated 1/2 nuclear spin H-1 and P-31 atoms in fullerene and diamond nanocrystallite, respectively, are proposed and examined with ab-initio local density functional method for possible applications as single quantum bits (qubits) in solid-state quantum computers. A H-1 atom encapsulated in a fully deuterated fullerene, C(sub 20)D(sub 20), forms the first model system and ab-initio calculation shows that H-1 atom is stable in atomic state at the center of the fullerene with a barrier of about 1 eV to escape. A P-31 atom positioned at the center of a diamond nanocrystallite is the second model system, and 3 1P atom is found to be stable at the substitutional site relative to interstitial sites by 15 eV, Vacancy formation energy is 6 eV in diamond so that substitutional P-31 atom will be stable against diffusion during the formation mechanisms within the nanocrystallite. The coupling between the nuclear spin and weakly bound (valance) donor electron coupling in both systems is found to be suitable for single qubit applications, where as the spatial distributions of (valance) donor electron wave functions are found to be preferentially spread along certain lattice directions facilitating two or more qubit applications. The feasibility of the fabrication pathways for both model solid-state qubit systems within practical quantum computers is discussed with in the context of our proposed solid-state qubits.

All-solid-state asymmetric supercapacitors based on Fe-doped mesoporous Co3O4 and three-dimensional reduced graphene oxide electrodes with high energy and power densities.

PubMed

Zhang, Cheng; Wei, Jun; Chen, Leiyi; Tang, Shaolong; Deng, Mingsen; Du, Youwei

2017-10-19

An asymmetric supercapacitor offers opportunities to effectively utilize the full potential of the different potential windows of the two electrodes for a higher operating voltage, resulting in an enhanced specific capacitance and significantly improved energy without sacrificing the power delivery and cycle life. To achieve high energy and power densities, we have synthesized an all-solid-state asymmetric supercapacitor with a wider voltage range using Fe-doped Co 3 O 4 and three-dimensional reduced graphene oxide (3DrGO) as the positive and negative electrodes, respectively. In contrast to undoped Co 3 O 4 , the increased density of states and modified charge spatial separation endow the Fe-doped Co 3 O 4 electrode with greatly improved electrochemical capacitive performance, including high specific capacitance (1997 F g -1 and 1757 F g -1 at current densities of 1 and 20 A g -1 , respectively), excellent rate capability, and superior cycling stability. Remarkably, the optimized all-solid-state asymmetric supercapacitor can be cycled reversibly in a wide range of 0-1.8 V, thus delivering a high energy density (270.3 W h kg -1 ), high power density (9.0 kW kg -1 at 224.2 W h kg -1 ), and excellent cycling stability (91.8% capacitance retention after 10 000 charge-discharge cycles at a constant current density of 10 A g -1 ). The superior capacitive performance suggests that such an all-solid-state asymmetric supercapacitor shows great potential for developing energy storage systems with high levels of energy and power delivery.

Multi-element microelectropolishing method

DOEpatents

Lee, P.J.

1994-10-11

A method is provided for microelectropolishing a transmission electron microscopy nonhomogeneous multi-element compound foil. The foil is electrolyzed at different polishing rates for different elements by rapidly cycling between different current densities. During a first portion of each cycle at a first voltage a first element electrolyzes at a higher current density than a second element such that the material of the first element leaves the anode foil at a faster rate than the second element and creates a solid surface film, and such that the solid surface film is removed at a faster rate than the first element leaves the anode foil. During a second portion of each cycle at a second voltage the second element electrolyzes at a higher current density than the first element, and the material of the second element leaves the anode foil at a faster rate than the first element and creates a solid surface film, and the solid surface film is removed at a slower rate than the second element leaves the foil. The solid surface film is built up during the second portion of the cycle, and removed during the first portion of the cycle. 10 figs.

Anisotropic high-harmonic generation in bulk crystals

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

You, Yong Sing; Reis, David A.; Ghimire, Shambhu

2016-11-21

The microscopic valence electron density determines the optical, electronic, structural and thermal properties of materials. However, current techniques for measuring this electron charge density are limited: for example, scanning tunnelling microscopy is confined to investigations at the surface, and electron diffraction requires very thin samples to avoid multiple scattering. Therefore, an optical method is desirable for measuring the valence charge density of bulk materials. Since the discovery of high-harmonic generation (HHG) in solids, there has been growing interest in using HHG to probe the electronic structure of solids. Here, using single-crystal MgO, we demonstrate that high-harmonic generation in solids ismore » sensitive to interatomic bonding. We find that harmonic efficiency is enhanced (diminished) for semi-classical electron trajectories that connect (avoid) neighbouring atomic sites in the crystal. Finally, these results indicate the possibility of using materials’ own electrons for retrieving the interatomic potential and thus the valence electron density, and perhaps even wavefunctions, in an all-optical setting.« less

Freestanding mesoporous VN/CNT hybrid electrodes for flexible all-solid-state supercapacitors.

PubMed

Xiao, Xu; Peng, Xiang; Jin, Huanyu; Li, Tianqi; Zhang, Chengcheng; Gao, Biao; Hu, Bin; Huo, Kaifu; Zhou, Jun

2013-09-25

High-performance all-solid-state supercapacitors (SCs) are fabricated based on thin, lightweight, and flexible freestanding MVNN/CNT hybrid electrodes. The device shows a high volume capacitance of 7.9 F/cm(3) , volume energy and power density of 0.54 mWh/cm(3) and 0.4 W/cm(3) at a current density of 0.025 A/cm(3) . By being highly flexible, environmentally friendly, and easily connectable in series and parallel, the all-solid-state SCs promise potential applications in portable/wearable electronics. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Propulsion and Power Rapid Response R&D Support Delivery Order 0041: Power Dense Solid Oxide Fuel Cell Systems: High Performance, High Power Density Solid Oxide Fuel Cells - Materials and Load Control

DTIC Science & Technology

2008-12-01

respectively. 2.3.1.2 Brushless DC Motor Brushless direct current ( BLDC ) motors feature high efficiency, ease of control , and astonishingly high power...modeling purposes, we ignore the modeling complexity of the BLDC controller and treat the motor and controller “as commutated”, i.e. we assume the...High Performance, High Power Density Solid Oxide Fuel Cells− Materials and Load Control Stephen W. Sofie, Steven R. Shaw, Peter A. Lindahl, and Lee H

High-Density Near-Field Readout Using Diamond Solid Immersion Lens

NASA Astrophysics Data System (ADS)

Shinoda, Masataka; Saito, Kimihiro; Kondo, Takao; Nakaoki, Ariyoshi; Furuki, Motohiro; Takeda, Minoru; Yamamoto, Masanobu; Schaich, Thomas J.; van Oerle, Bart M.; Godfried, Herman P.; Kriele, Paul A. C.; Houwman, Evert P.; Nelissen, Wim H. M.; Pels, Gert J.; Spaaij, Paul G. M.

2006-02-01

We investigated high-density near-field readout using a diamond solid immersion lens (SIL). A synthetic single-crystal chemical vapor deposition diamond provides a high refractive index and a high transmission for a wide wavelength range. Since the refractive index at a wavelength of 405 nm is 2.458, we could design a solid immersion lens with an effective numerical aperture of 2.34. Using the diamond SIL, we observed the eye pattern of a 150-GB-capacity (104.3 Gbit/in.2) disk with a track pitch of 130 nm and a bit length of 47.6 nm.

Recovery of nonferrous metals from scrap automobiles by magnetic fluid levitation.

NASA Technical Reports Server (NTRS)

Mir, L.; Simard, C.; Grana, D.

1973-01-01

Ferrofluids are colloidal dispersions of subdomain magnetic solids in carrier liquids. In the presence of a non-homogeneous magnetic field, ferrofluids exert a pressure on immersed nonmagnetic objects in the opposite sense of the field gradient. This pressure force can, when opposite to gravity, levitate objects of higher density than the ferrofluid. This levitation technique can be used to separate solids according to density. Its application to the separation of nonferrous metals from shredded automobiles has been demonstrated on a prototype of a full-scale separator. Its use to recover nonferrous metals from municipal solid wastes also seems practical.

Quantum model of a solid-state spin qubit: Ni cluster on a silicon surface by the generalized spin Hamiltonian and X-ray absorption spectroscopy investigations

NASA Astrophysics Data System (ADS)

Farberovich, Oleg V.; Mazalova, Victoria L.; Soldatov, Alexander V.

2015-11-01

We present here the quantum model of a Ni solid-state electron spin qubit on a silicon surface with the use of a density-functional scheme for the calculation of the exchange integrals in the non-collinear spin configurations in the generalized spin Hamiltonian (GSH) with the anisotropic exchange coupling parameters linking the nickel ions with a silicon substrate. In this model the interaction of a spin qubit with substrate is considered in GSH at the calculation of exchange integrals Jij of the nanosystem Ni7-Si in the one-electron approach taking into account chemical bonds of all Si-atoms of a substrate (environment) with atoms of the Ni7-cluster. The energy pattern was found from the effective GSH Hamiltonian acting in the restricted spin space of the Ni ions by the application of the irreducible tensor operators (ITO) technique. In this paper we offer the model of the quantum solid-state N-spin qubit based on the studying of the spin structure and the spin-dynamics simulations of the 3d-metal Ni clusters on the silicon surface. The solution of the problem of the entanglement between spin states in the N-spin systems is becoming more interesting when considering clusters or molecules with a spectral gap in their density of states. For quantifying the distribution of the entanglement between the individual spin eigenvalues (modes) in the spin structure of the N-spin system we use the density of entanglement (DOE). In this study we have developed and used the advanced high-precision numerical techniques to accurately assess the details of the decoherence process governing the dynamics of the N-spin qubits interacting with a silicon surface. We have studied the Rabi oscillations to evaluate the N-spin qubits system as a function of the time and the magnetic field. We have observed the stabilized Rabi oscillations and have stabilized the quantum dynamical qubit state and Rabi driving after a fixed time (0.327 μs). The comparison of the energy pattern with the anisotropic exchange models conventionally used for the analysis of this system and, with the results of the experimental XANES spectra, shows that our complex investigations provide a good description of the pattern of the spin levels and the spin structures of the nanomagnetic Ni7 qubit. The results are discussed in the view of the general problem of the solid-state spin qubits and the spin structure of the Ni cluster.

Development of 3D Urchin-Shaped Coaxial Manganese Dioxide@Polyaniline (MnO2@PANI) Composite and Self-Assembled 3D Pillared Graphene Foam for Asymmetric All-Solid-State Flexible Supercapacitor Application.

PubMed

Ghosh, Kalyan; Yue, Chee Yoon; Sk, Md Moniruzzaman; Jena, Rajeeb Kumar

2017-05-10

We have fabricated high-energy-density all-solid-state flexible asymmetric supercapacitor by using a facile novel 3D hollow urchin-shaped coaxial manganese dioxide@polyaniline (MnO 2 @PANI) composite as positive electrode and 3D graphene foam (GF) as negative electrode materials with polyvinyl alcohol (PVA)/KOH gel electrolyte. The coaxial MnO 2 @PANI composite was fabricated by hydrothermal route followed by oxidation without use of an external oxidant. The formation mechanism of the 3D hollow MnO 2 @PANI composite occurs first by nucleation and growth of the MnO 2 crystal species via dissolution-recrystallization and oriented attachment mechanisms followed by the oxidation of aniline monomers on the MnO 2 crystalline template. The self-assembled 3D graphene block was synthesized by hydrothermal route using vitamin C as a reducing agent. The microstructures of the composites are analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The morphology is characterized by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), which clearly showed the formation of urchin-shaped coaxial MnO 2 @PANI composite. The electrochemical studies are explored by cyclic voltammetry, electrochemical impedance spectrometry, and cyclic charge-discharge tests. The symmetric all-solid-state flexible MnO 2 @PANI//MnO 2 @PANI and GF//GF supercapacitors exhibit the specific capacitance of 129.2 and 82.1 F g -1 at 0.5 A/g current density, respectively. The solid-state asymmetric supercapacitor shows higher energy density (37 Wh kg -1 ) with respect to the solid-state symmetric supercapacitors MnO 2 @PANI//MnO 2 @PANI and GF//GF, where the obtained energy density are found to be 17.9 and 11.4 Wh kg -1 , respectively, at 0.5 A/g current density. Surprisingly, the asymmetric supercapacitor shows a high energy density of 22.3 Wh kg -1 at a high current density of 5 A g -1 . The solid-state asymmetric supercapacitor shows a good cyclic stability in which ∼11% capacitance loss was observed after 5000 cycles.

Properties of MgO to 1.2 TPa from high-precision experiments on Sandia's Z machine and first-principles simulations using QMC and DFT

NASA Astrophysics Data System (ADS)

Shulenburger, Luke

2015-11-01

MgO is a major constituent of Earth's mantle, the rocky cores of gas giants and is a likely component of the interiors of many exoplanets. The high pressure - high temperature behavior of MgO directly affects equation of state models for planetary structure and formation. In this work, we examine MgO under extreme conditions using experimental and theoretical methods to determine the phase diagram and transport properties. Using plate impact experiments on Sandia's Z facility a low entropy solid-solid phase transition from B1 to B2 is clearly determined. The melting transition, on the other hand, is subtle, involving little to no signal in us-up space. Theoretical work utilizing density functional theory (DFT) provides a complementary picture of the phase diagram. The solid-solid phase transition is identified through a series of quasi-harmonic phonon calculations and thermodynamic integration, while the melt boundary is found using phase coexistence calculations. The calculation of reflectivity along the Hugoniot and the influence of the ionic structure on the transport properties requires particular care because of the underestimation of the band gap and attendant overestimation of transport properties due to the use of semi-local density functional theory. We will explore the impact of this theoretical challenge and its potential solutions in this talk. Finally, understanding the behavior of MgO as the pressure releases from the Hugoniot state is a key ingredient to modeling giant impact events. We explore this regime both through additional DFT calculations and by observing the release state of the MgO into lower impedance materials. The integrated use of DFT simulations and high-accuracy shock experiments together provide a comprehensive understanding of MgO under extreme conditions. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Results of Characterization and Retrieval Testing on Tank 241-C-110 Heel Solids

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

Callaway, William S.

2013-09-30

Nine samples of heel solids from tank 241-C-110 were delivered to the 222-S Laboratory for characterization and dissolution testing. After being drained thoroughly, the sample solids were primarily white to light-brown with minor dark-colored inclusions. The maximum dimension of the majority of the solids was <2 mm; however, numerous pieces of aggregate, microcrystalline, and crystalline solids with maximum dimensions ranging from 5-70 mm were observed. In general, the larger pieces of aggregate solids were strongly cemented. Natrophosphate [Na{sub 7}F(PO{sub 4}){sub 2}°19H{sub 2}O] was the dominant solid phase identified in the heel solids. Results of chemical analyses suggested that 85-87 wt%more » of the heel solids were the fluoridephosphate double salt. The average bulk density measured for the heel solids was 1.689 g/mL; the reference density of natrophosphate is 1.71 g/mL. Dissolution tests on composite samples indicate that 94 to 97 wt% of the tank 241-C-110 heel solids can be retrieved by dissolution in water. Dissolution and recovery of the soluble components in 1 kg (0.59 L) of the heel solids required the addition of ≈9.5 kg (9.5 L) of water at 15 °C and ≈4.4 kg (4.45 L) of water at 45 °C. Calculations performed using the Environmental Simulation Program indicate that dissolution of the ≈0.86 kg of natrophosphate in each kilogram of the tank 241-C-110 heel solids would require ≈9.45 kg of water at 15 °C and ≈4.25 kg of water at 45 °C. The slightly larger quantities of water determined to be required to retrieve the soluble components in 1 kg of the heel solids are consistent with that required for the dissolution of solids composed mainly of natrophosphate with a major portion of the balance consisting of highly soluble sodium salts. At least 98% of the structural water, soluble phosphate, sodium, fluoride, nitrate, carbonate, nitrite, sulfate, oxalate, and chloride in the test composites was dissolved and recovered in the dissolution tests. Most of the {sup 99}Tc and {sup 137}Cs present in the initial heel solids composites was removed in the water dissolution tests. The estimated activities/weights of {sup 129}I, {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U in the dry residual solids were <25% of the weights/activities in the initial composite solids. Gibbsite and nordstrandite [both Al(OH){sub 3}] were the major solid phases identified in the solids remaining after completion of the dissolution tests. Chemical analysis indicated that the residual solids may have contained up to 62 wt% Al(OH){sub 3}. Significant quantities of unidentified phosphate-, iron-, bismuth-, silicon-, and strontium- bearing species were also present in the residual solids. The reference density of gibbsite (and nordstrandite) is 2.42 g/mL. The measured density of the residual solids, 2.65 g/mL, would be a reasonable value for solids containing gibbsite as the major component with minor quantities of other, higher density solids. Sieve analysis indicated that 22.2 wt% of the residual solids were discrete particles >710 μm in size, and 77.8 wt% were particulates <710 μm in size. Light-scattering measurements suggested that nearly all of the <710-μm particulates with diameters >12 μm were weakly bound aggregates of particles with diameters <2 μm. The <710-μm residual solids settled very slowly when dispersed in reagent water. The physical appearance of a suspension containing ≈0.4 vol% of the solids in pure water changed very little over a period of 46.5 hours. It should be noted that the distribution of particle sizes in the residual solids and the observed settling behavior were both strongly influenced by the procedures followed in the dissolution tests.« less

Ground state structure of high-energy-density polymeric carbon monoxide

NASA Astrophysics Data System (ADS)

Xia, Kang; Sun, Jian; Pickard, Chris J.; Klug, Dennis D.; Needs, Richard J.

2017-04-01

Crystal structure prediction methods and first-principles calculations have been used to explore low-energy structures of carbon monoxide (CO). Contrary to the standard wisdom, the most stable structure of CO at ambient pressure was found to be a polymeric structure of P n a 21 symmetry rather than a molecular solid. This phase is formed from six-membered (four carbon + two oxygen) rings connected by C=C double bonds with two double-bonded oxygen atoms attached to each ring. Interestingly, the polymeric P n a 21 phase of CO has a much higher energy density than trinitrotoluene (TNT). On compression to about 7 GPa, P n a 21 is found to transform into another chainlike phase of C c symmetry which has similar ring units to P n a 21 . On compression to 12 GPa, it is energetically favorable for CO to polymerize into a purely single bonded C m c a phase, which is stable over a wide pressure range and transforms into the previously known C m c m phase at around 100 GPa. Thermodynamic stability of these structures was verified using calculations with different density functionals, including hybrid and van der Waals corrected functionals.

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

Equation of State for Detonation Product Gases

NASA Astrophysics Data System (ADS)

Nagayama, Kunihito; Kubota, Shiro

2013-06-01

Based on the empirical linear relationship between detonation velocity and loading density, an approximate description for the Chapman-Jouguet state for detonation product gases of solid phase high explosives has been developed. Provided that the Grüneisen parameter is a function only of volume, systematic and closed system of equations for the Grüneisen parameter and CJ volume have been formulated. These equations were obtained by combining this approximation with the Jones-Stanyukovich-Manson relation together with JWL isentrope for detonation of crystal density PETN. A thermodynamic identity between the Grüneisen parameter and another non-dimensional material parameter introduced by Wu and Jing can be used to derive the enthalpy-pressure-volume equation of state for detonation gases. This Wu-Jing parameter is found to be the ratio of the Grüneisen parameter and the adiabatic index. Behavior of this parameter as a function of pressure was calculated and revealed that their change with pressure is very gradual. By using this equation of state, several isentropes down from the Chapman-Jouguet states reached by four different lower initial density PETN have been calculated and compared with available cylinder expansion tests.

Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Fabrizio, Eve F.; Ilhan, Faysal; Dass, Amala; Zhang, Guo-Hui; Vassilaras, Plousia; Johnston, J. Chris; Leventis, Nicholas

2005-01-01

The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

Impact of thermal energy storage properties on solar dynamic space power conversion system mass

NASA Technical Reports Server (NTRS)

Juhasz, Albert J.; Coles-Hamilton, Carolyn E.; Lacy, Dovie E.

1987-01-01

A 16 parameter solar concentrator/heat receiver mass model is used in conjunction with Stirling and Brayton Power Conversion System (PCS) performance and mass computer codes to determine the effect of thermal energy storage (TES) material property changes on overall PCS mass as a function of steady state electrical power output. Included in the PCS mass model are component masses as a function of thermal power for: concentrator, heat receiver, heat exchangers (source unless integral with heat receiver, heat sink, regenerator), heat engine units with optional parallel redundancy, power conditioning and control (PC and C), PC and C radiator, main radiator, and structure. Critical TES properties are: melting temperature, heat of fusion, density of the liquid phase, and the ratio of solid-to-liquid density. Preliminary results indicate that even though overalll system efficiency increases with TES melting temperature up to 1400 K for concentrator surface accuracies of 1 mrad or better, reductions in the overall system mass beyond that achievable with lithium fluoride (LiF) can be accomplished only if the heat of fusion is at least 800 kJ/kg and the liquid density is comparable to that of LiF (1880 kg/cu m.

Impact of thermal energy storage properties on solar dynamic space power conversion system mass

NASA Technical Reports Server (NTRS)

Juhasz, Albert J.; Coles-Hamilton, Carolyn E.; Lacy, Dovie E.

1987-01-01

A 16 parameter solar concentrator/heat receiver mass model is used in conjunction with Stirling and Brayton Power Conversion System (PCS) performance and mass computer codes to determine the effect of thermal energy storage (TES) material property changes on overall PCS mass as a function of steady state electrical power output. Included in the PCS mass model are component masses as a function of thermal power for: concentrator, heat receiver, heat exchangers (source unless integral with heat receiver, heat sink, regenerator), heat engine units with optional parallel redundancy, power conditioning and control (PC and C), PC and C radiator, main radiator, and structure. Critical TES properties are: melting temperature, heat of fusion, density of the liquid phase, and the ratio of solid-to-liquid density. Preliminary results indicate that even though overall system efficiency increases with TES melting temperature up to 1400 K for concentrator surface accuracies of 1 mrad or better, reductions in the overall system mass beyond that achievable with lithium fluoride (LiF) can be accomplished only if the heat of fusion is at least 800 kJ/kg and the liquid density is comparable to that of LiF (1800 kg/cu m).

Wetting of heterogeneous substrates. A classical density-functional-theory approach

NASA Astrophysics Data System (ADS)

Yatsyshin, Peter; Parry, Andrew O.; Rascón, Carlos; Duran-Olivencia, Miguel A.; Kalliadasis, Serafim

2017-11-01

Wetting is a nucleation of a third phase (liquid) on the interface between two different phases (solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid-fluid and fluid-substrate intermolecular interactions leads to the appearance of a whole ``zoo'' of exciting interface phase transitions, associated with the formation of nano-droplets/bubbles, and thin films. Practical applications of wetting at small scales are numerous and include the design of lab-on-a-chip devices and superhydrophobic surfaces. In this talk, we will use a fully microscopic approach to explore the phase space of a planar wall, decorated with patches of different hydrophobicity, and demonstrate the highly non-trivial behaviour of the liquid-gas interface near the substrate. We will present fluid density profiles, adsorption isotherms and wetting phase diagrams. Our analysis is based on a formulation of statistical mechanics, commonly known as classical density-functional theory. It provides a computationally-friendly and rigorous framework, suitable for probing small-scale physics of classical fluids and other soft-matter systems. EPSRC Grants No. EP/L027186,EP/K503733;ERC Advanced Grant No. 247031.

Reversible Immobilization of Proteins in Sensors and Solid-State Nanopores.

PubMed

Ananth, Adithya; Genua, María; Aissaoui, Nesrine; Díaz, Leire; Eisele, Nico B; Frey, Steffen; Dekker, Cees; Richter, Ralf P; Görlich, Dirk

2018-05-01

The controlled functionalization of surfaces with proteins is crucial for many analytical methods in life science research and biomedical applications. Here, a coating for silica-based surfaces is established which enables stable and selective immobilization of proteins with controlled orientation and tunable surface density. The coating is reusable, retains functionality upon long-term storage in air, and is applicable to surfaces of complex geometry. The protein anchoring method is validated on planar surfaces, and then a method is developed to measure the anchoring process in real time using silicon nitride solid-state nanopores. For surface attachment, polyhistidine tags that are site specifically introduced into recombinant proteins are exploited, and the yeast nucleoporin Nsp1 is used as model protein. Contrary to the commonly used covalent thiol chemistry, the anchoring of proteins via polyhistidine tag is reversible, permitting to take proteins off and replace them by other ones. Such switching in real time in experiments on individual nanopores is monitored using ion conductivity. Finally, it is demonstrated that silica and gold surfaces can be orthogonally functionalized to accommodate polyhistidine-tagged proteins on silica but prevent protein binding to gold, which extends the applicability of this surface functionalization method to even more complex sensor devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A model for wave propagation in a porous solid saturated by a three-phase fluid.

PubMed

Santos, Juan E; Savioli, Gabriela B

2016-02-01

This paper presents a model to describe the propagation of waves in a poroelastic medium saturated by a three-phase viscous, compressible fluid. Two capillary relations between the three fluid phases are included in the model by introducing Lagrange multipliers in the principle of virtual complementary work. This approach generalizes that of Biot for single-phase fluids and allows to determine the strain energy density, identify the generalized strains and stresses, and derive the constitutive relations of the system. The kinetic and dissipative energy density functions are obtained assuming that the relative flow within the pore space is of laminar type and obeys Darcy's law for three-phase flow in porous media. After deriving the equations of motion, a plane wave analysis predicts the existence of four compressional waves, denoted as type I, II, III, and IV waves, and one shear wave. Numerical examples showing the behavior of all waves as function of saturation and frequency are presented.

An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

NASA Astrophysics Data System (ADS)

Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

2018-05-01

This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures.

PubMed

Yang, Huayan; Wang, Yu; Huang, Huaqi; Gell, Lars; Lehtovaara, Lauri; Malola, Sami; Häkkinen, Hannu; Zheng, Nanfeng

2013-01-01

Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4(-) per nanoparticle, and density functional theory calculations explain the stability as an 18-electron superatom shell closure in the metal core. Highly featured optical absorption spectra in the ultraviolet-visible region are analysed using time-dependent density functional perturbation theory. This work forms a basis for further understanding, engineering and controlling of stability as well as electronic and optical properties of these novel nanomaterials.

Uncovering the Connection Between Low-Frequency Dynamics and Phase Transformation Phenomena in Molecular Solids

NASA Astrophysics Data System (ADS)

Ruggiero, Michael T.; Zhang, Wei; Bond, Andrew D.; Mittleman, Daniel M.; Zeitler, J. Axel

2018-05-01

The low-frequency motions of molecules in the condensed phase have been shown to be vital to a large number of physical properties and processes. However, in the case of disordered systems, it is often difficult to elucidate the atomic-level details surrounding these phenomena. In this work, we have performed an extensive experimental and computational study on the molecular solid camphor, which exhibits a rich and complex structure-dynamics relationship, and undergoes an order-disorder transition near ambient conditions. The combination of x-ray diffraction, variable temperature and pressure terahertz time-domain spectroscopy, ab initio molecular dynamics, and periodic density functional theory calculations enables a complete picture of the phase transition to be obtained, inclusive of mechanistic, structural, and thermodynamic phenomena. Additionally, the low-frequency vibrations of a disordered solid are characterized for the first time with atomic-level precision, uncovering a clear link between such motions and the phase transformation. Overall, this combination of methods allows for significant details to be obtained for disordered solids and the associated transformations, providing a framework that can be directly applied for a wide range of similar systems.

Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

PubMed

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-07-30

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

PubMed Central

Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

2012-01-01

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

Uncovering the Connection Between Low-Frequency Dynamics and Phase Transformation Phenomena in Molecular Solids.

PubMed

Ruggiero, Michael T; Zhang, Wei; Bond, Andrew D; Mittleman, Daniel M; Zeitler, J Axel

2018-05-11

The low-frequency motions of molecules in the condensed phase have been shown to be vital to a large number of physical properties and processes. However, in the case of disordered systems, it is often difficult to elucidate the atomic-level details surrounding these phenomena. In this work, we have performed an extensive experimental and computational study on the molecular solid camphor, which exhibits a rich and complex structure-dynamics relationship, and undergoes an order-disorder transition near ambient conditions. The combination of x-ray diffraction, variable temperature and pressure terahertz time-domain spectroscopy, ab initio molecular dynamics, and periodic density functional theory calculations enables a complete picture of the phase transition to be obtained, inclusive of mechanistic, structural, and thermodynamic phenomena. Additionally, the low-frequency vibrations of a disordered solid are characterized for the first time with atomic-level precision, uncovering a clear link between such motions and the phase transformation. Overall, this combination of methods allows for significant details to be obtained for disordered solids and the associated transformations, providing a framework that can be directly applied for a wide range of similar systems.

Combined Approach for the Structural Characterization of Alkali Fluoroscandates: Solid-State NMR, Powder X-ray Diffraction, and Density Functional Theory Calculations.

PubMed

Rakhmatullin, Aydar; Polovov, Ilya B; Maltsev, Dmitry; Allix, Mathieu; Volkovich, Vladimir; Chukin, Andrey V; Boča, Miroslav; Bessada, Catherine

2018-02-05

The structures of several fluoroscandate compounds are presented here using a characterization approach combining powder X-ray diffraction and solid-state NMR. The structure of K 5 Sc 3 F 14 was fully determined from Rietveld refinement performed on powder X-ray diffraction data. Moreover, the local structures of NaScF 4 , Li 3 ScF 6 , KSc 2 F 7 , and Na 3 ScF 6 compounds were studied in detail from solid-state 19 F and 45 Sc NMR experiments. The 45 Sc chemical shift ranges for six- and seven-coordinated scandium environments were defined. The 19 F chemical shift ranges for bridging and terminal fluorine atoms were also determined. First-principles calculations of the 19 F and 45 Sc NMR parameters were carried out using plane-wave basis sets and periodic boundary conditions (CASTEP), and the results were compared with the experimental data. A good agreement between the calculated shielding constants and experimental chemical shifts was obtained. This demonstrates the good potential of computational methods in spectroscopic assignments of solid-state 45 Sc NMR spectroscopy.

High energy density redox flow device

DOEpatents

Chiang, Yet-Ming; Carter, W. Craig; Ho, Bryan Y; Duduta, Mihai; Limthongkul, Pimpa

2014-05-13

Redox flow devices are described in which at least one of the positive electrode or negative electrode-active materials is a semi-solid or is a condensed ion-storing electroactive material, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. The electronic conductivity of the semi-solid is increased by the addition of conductive particles to suspensions and/or via the surface modification of the solid in semi-solids (e.g., by coating the solid with a more electron conductive coating material to increase the power of the device). High energy density and high power redox flow devices are disclosed. The redox flow devices described herein can also include one or more inventive design features. In addition, inventive chemistries for use in redox flow devices are also described.

Theoretical studies on a new furazan compound bis[4-nitramino-furazanyl-3-azoxy]azofurazan (ADNAAF).

PubMed

Zheng, Chunmei; Chu, Yuting; Xu, Liwen; Wang, Fengyun; Lei, Wu; Xia, Mingzhu; Gong, Xuedong

2016-06-01

Bis[4-nitraminofurazanyl-3-azoxy]azofurazan (ADNAAF), synthesized in our previous work [1], contains four furazan units connected to the linkage of the azo-group and azoxy-group. For further research, some theoretical characters were studied by the density functional theoretical (DFT) method. The optimized structures and the energy gaps between the HOMO and LUMO were studied at the B3LYP/6-311++G** level. The isodesmic reaction method was used for estimating the enthalpy of formation. The detonation performances were estimated with Kamlet-Jacobs equations based on the predicted density and enthalpy of formation in the solid state. ADAAF was also calculated by the same method for comparison. It was found that the nitramino group of ADNAAF can elongate the length of adjacent C-N bonds than the amino group of ADAAF. The gas-phase and solid-phase enthalpies of formation of ADNAAF are larger than those of ADAAF. The detonation performances of ADNAAF are better than ADAAF and RDX, and similar to HMX. The trigger bond of ADNAAF is the N-N bonds in the nitramino groups, and the nitramino group is more active than the amino group (-NH2).

Maximum value of the pulse energy of a passively Q-switched laser as a function of the pump power.

PubMed

Li, Jianlang; Ueda, Ken-ichi; Dong, Jun; Musha, Mitsuru; Shirakawa, Akira

2006-07-20

The finite recovery time Ts of the bleached absorber is presented as one of the possible mechanisms accounting for the increase-maximum-decrease in pulse energy E with the pumping rate Wp in cw-pumped passively Q-switched solid-state lasers, by analytically evaluating the sign of the derivative partial differentialE/ partial differentialWP. The results show that, in the low pump regime (T>Ts, T is the interpulse period), the initial population density ni remains constant, the final population density nf decreases with Wp, and this results in a monotonic increase of E with Wp. In the high pump regime (T

Picosecond Streaked K-Shell Spectroscopy of Near Solid-Density Aluminum Plasmas

NASA Astrophysics Data System (ADS)

Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.; Mileham, C.; Froula, D. H.; Golovkin, I. E.

2016-10-01

The thermal x-ray emission from rapidly heated solid targets containing a buried-aluminum layer was measured. The targets were driven by high-contrast 1 ω or 2 ω laser pulses at focused intensities up to 1 ×1019W/Wcm2 cm2 . A streaked x-ray spectrometer recorded the Al Heα and lithium-like satellite lines with 2-ps temporal resolution and moderate resolving power (E/E ΔE 700). Time-integrated measurements over the same spectral range were used to correct the streaked data for variations in photocathode sensitivity. Line widths and intensity ratios from the streaked data were interpreted using a collisional radiative atomic model to provide the average plasma conditions in the buried layer as a function of time. It was observed that the resonance line tends toward lower photon energies at high electron densities. The measured shifts will be compared to predicted shifts from Stark-operator calculations at the inferred plasma conditions. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944, the office of Fusion Energy Sciences Award Number DE-SC0012317, and the Stewardship Science Graduate Fellowship Grant Number DE-NA0002135.

First-Principles Characterization of the Unknown Crystal Structure and Ionic Conductivity of Li7P2S8I as a Solid Electrolyte for High-Voltage Li Ion Batteries.

PubMed

Kang, Joonhee; Han, Byungchan

2016-07-21

Using first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate the crystal structure of the Li7P2S8I (LPSI) and Li ionic conductivity at room temperature with its atomic-level mechanism. By successively applying three rigorous conceptual approaches, we identify that the LPSI has a similar symmetry class as Li10GeP2S12 (LGPS) material and estimate the Li ionic conductivity to be 0.3 mS cm(-1) with an activation energy of 0.20 eV, similar to the experimental value of 0.63 mS cm(-1). Iodine ions provide an additional path for Li ion diffusion, but a strong Li-I attractive interaction degrades the Li ionic transport. Calculated density of states (DOS) for LPSI indicate that electrochemical instability can be substantially improved by incorporating iodine at the Li metallic anode via forming a LiI compound. Our methods propose the computational design concept for a sulfide-based solid electrolyte with heteroatom doping for high-voltage Li ion batteries.

Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

PubMed Central

Chen, Yun; Gerdes, Kirk; Song, Xueyan

2016-01-01

Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1−xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C. PMID:27605121

Experimental and theoretical spectroscopic studies of anticancer drug rosmarinic acid using HF and density functional theory.

PubMed

Mariappan, G; Sundaraganesan, N; Manoharan, S

2012-11-01

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of anticancer drug of rosmarinic acid. The optimized molecular structure, atomic charges, vibrational frequencies, natural bond orbital analysis and ultraviolet-visible spectral interpretation of rosmarinic acid have been studied by performing HF and DFT/B3LYP/6-31G(d,p) level of theory. The FT-IR (solid and solution phase), FT-Raman (solid phase) spectra were recorded in the region 4000-400 and 3500-50 cm(-1), respectively. The UV-Visible absorption spectra of the compound that dissolved in ethanol were recorded in the range of 200-800 nm. The scaled wavenumbers are compared with the experimental values. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis were investigated using theoretical calculations. Copyright © 2012 Elsevier B.V. All rights reserved.

Implementation and validation of fully relativistic GW calculations: Spin–orbit coupling in molecules, nanocrystals, and solids

DOE PAGES

Scherpelz, Peter; Govoni, Marco; Hamada, Ikutaro; ...

2016-06-22

We present an implementation of G 0W 0 calculations including spin–orbit coupling (SOC) enabling investigations of large systems, with thousands of electrons, and we discuss results for molecules, solids, and nanocrystals. Using a newly developed set of molecules with heavy elements (called GW-SOC81), we find that, when based upon hybrid density functional calculations, fully relativistic (FR) and scalar-relativistic (SR) G 0W 0 calculations of vertical ionization potentials both yield excellent performance compared to experiment, with errors below 1.9%. We demonstrate that while SR calculations have higher random errors, FR calculations systematically underestimate the VIP by 0.1 to 0.2 eV. Wemore » further verify that SOC effects may be well approximated at the FR density functional level and then added to SR G 0W 0 results for a broad class of systems. We also address the use of different root-finding algorithms for the G 0W 0 quasiparticle equation and the significant influence of including d electrons in the valence partition of the pseudopotential for G 0W 0 calculations. Lastly, we present statistical analyses of our data, highlighting the importance of separating definitive improvements from those that may occur by chance due to a limited number of samples. We suggest the statistical analyses used here will be useful in the assessment of the accuracy of a large variety of electronic structure methods« less

Mechanochemical spinodal decomposition: a phenomenological theory of phase transformations in multi-component, crystalline solids

DOE PAGES

Rudraraju, Shiva; Van der Ven, Anton; Garikipati, Krishna

2016-06-10

Here, we present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain-composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition aremore » variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH 2-2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics.« less

Implementation and validation of fully relativistic GW calculations: Spin–orbit coupling in molecules, nanocrystals, and solids

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

Scherpelz, Peter; Govoni, Marco; Hamada, Ikutaro

We present an implementation of G 0W 0 calculations including spin–orbit coupling (SOC) enabling investigations of large systems, with thousands of electrons, and we discuss results for molecules, solids, and nanocrystals. Using a newly developed set of molecules with heavy elements (called GW-SOC81), we find that, when based upon hybrid density functional calculations, fully relativistic (FR) and scalar-relativistic (SR) G 0W 0 calculations of vertical ionization potentials both yield excellent performance compared to experiment, with errors below 1.9%. We demonstrate that while SR calculations have higher random errors, FR calculations systematically underestimate the VIP by 0.1 to 0.2 eV. Wemore » further verify that SOC effects may be well approximated at the FR density functional level and then added to SR G 0W 0 results for a broad class of systems. We also address the use of different root-finding algorithms for the G 0W 0 quasiparticle equation and the significant influence of including d electrons in the valence partition of the pseudopotential for G 0W 0 calculations. Lastly, we present statistical analyses of our data, highlighting the importance of separating definitive improvements from those that may occur by chance due to a limited number of samples. We suggest the statistical analyses used here will be useful in the assessment of the accuracy of a large variety of electronic structure methods« less

Syntheses, X-ray structures, solid state high-field electron paramagnetic resonance, and density-functional theory investigations on chloro and aqua Mn(II) mononuclear complexes with amino-pyridine pentadentate ligands.

PubMed

Hureau, Christelle; Groni, Sihem; Guillot, Régis; Blondin, Geneviève; Duboc, Carole; Anxolabéhère-Mallart, Elodie

2008-10-20

The two pentadentate amino-pyridine ligands L5(2) and L5(3) (L5(2) and L5(3) stand for the N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine and the N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine, respectively) were used to synthesize four mononuclear Mn(II) complexes, namely [(L5(2))MnCl](PF6) (1(PF6)), [(L5(3))MnCl](PF6) (2(PF6)), [(L5(2))Mn(OH2)](BPh4)2 (3(BPh4)2), and [(L5(3))Mn(OH2)](BPh4)2 (4(BPh4)2). The X-ray diffraction studies revealed different configurations for the ligand L5(n) (n = 2, 3) depending on the sixth exogenous ligand and/or the counterion. Solid state high-field electron paramagnetic resonance spectra were recorded on complexes 1-4 as on previously described mononuclear Mn(II) systems with tetra- or hexadentate amino-pyridine ligands. Positive and negative axial zero-field splitting (ZFS) parameters D were determined whose absolute values ranged from 0.090 to 0.180 cm(-1). Density-functional theory calculations were performed unraveling that, in contrast with chloro systems, the spin-spin and spin-orbit coupling contributions to the D-parameter are comparable for mixed N,O-coordination sphere complexes.

Direct modeling of the electrochemistry in the three-phase boundary of solid oxide fuel cell anodes by density functional theory: a critical overview.

PubMed

Shishkin, M; Ziegler, T

2014-02-07

The first principles modeling of electrochemical reactions has proven useful for the development of efficient, durable and low cost solid oxide full cells (SOFCs). In this account we focus on recent advances in modeling of structural, electronic and catalytic properties of the SOFC anodes based on density functional theory (DFT) first principle calculations. As a starting point, we highlight that the adequate analysis of cell electrochemistry generally requires modeling of chemical reactions at the metal/oxide interface rather than on individual metal or oxide surfaces. The atomic models of Ni/YSZ and Ni/CeO2 interfaces, required for DFT simulations of reactions on SOFC anodes are discussed next, together with the analysis of the electronic structure of these interfaces. Then we proceed to DFT-based findings on charge transfer mechanisms during redox reactions on these two anodes. We provide a comparison of the electronic properties of Ni/YSZ and Ni/CeO2 interfaces and present an interpretation of their different chemical performances. Subsequently we discuss the computed energy pathways of fuel oxidation mechanisms, obtained by various groups to date. We also discuss the results of DFT studies combined with microkinetic modeling as well as the results of kinetic Monte Carlo simulations. In conclusion we summarize the key findings of DFT modeling of metal/oxide interfaces to date and highlight possible directions in the future modeling of SOFC anodes.

Orbital evolution and accretion of protoplanets tidally interacting with a gas disk. II. Solid surface density evolution with type-I migration

NASA Astrophysics Data System (ADS)

Daisaka, Junko K.; Tanaka, Hidekazu; Ida, Shigeru

2006-12-01

This paper investigates the surface density evolution of a planetesimal disk due to the effect of type-I migration by carrying out N-body simulation and through analytical method, focusing on terrestrial planet formation. The coagulation and the growth of the planetesimals take place in the abundant gas disk except for a final stage. A protoplanet excites density waves in the gas disk, which causes the torque on the protoplanet. The torque imbalance makes the protoplanet suffer radial migration, which is known as type-I migration. Type-I migration time scale derived by the linear theory may be too short for the terrestrial planets to survive, which is one of the major problems in the planet formation scenario. Although the linear theory assumes a protoplanet being in a gas disk alone, Kominami et al. [Kominami, J., Tanaka, H., Ida, S., 2005. Icarus 167, 231-243] showed that the effect of the interaction with the planetesimal disk and the neighboring protoplanets on type-I migration is negligible. The migration becomes pronounced before the planet's mass reaches the isolation mass, and decreases the solid component in the disk. Runaway protoplanets form again in the planetesimal disk with decreased surface density. In this paper, we present the analytical formulas that describe the evolution of the solid surface density of the disk as a function of gas-to-dust ratio, gas depletion time scale and semimajor axis, which agree well with our results of N-body simulations. In general, significant depletion of solid material is likely to take place in inner regions of disks. This might be responsible for the fact that there is no planet inside Mercury's orbit in our Solar System. Our most important result is that the final surface density of solid components ( Σ) and mass of surviving planets depend on gas surface density ( Σ) and its depletion time scale ( τ) but not on initial Σ; they decrease with increase in Σ and τ. For a fixed gas-to-dust ratio and τ, larger initial Σ results in smaller final Σ and smaller surviving planets, because of larger Σ. To retain a specific amount of Σ, the efficient disk condition is not an initially large Σ but the initial Σ as small as the specified final one and a smaller gas-to-dust ratio. To retain Σ comparable to that of the minimum mass solar nebula (MMSN), a disk must have the same Σ and a gas-to-dust ratio that is smaller than that of MMSN by a factor of 1.3×(τ/1 Myr) at ˜1 AU. (Equivalently, type-I migration speed is slower than that predicted by the linear theory by the same factor.) The surviving planets are Mars-sized ones in this case; in order to form Earth-sized planets, their eccentricities must be pumped up to start orbit crossing and coagulation among them. At ˜5 AU, Σ of MMSN is retained under the same condition, but to form a core massive enough to start runaway gas accretion, a gas-to-dust ratio must be smaller than that of MMSN by a factor of 3×τ/1 Myr.

Influence of xc functional on thermal-elastic properties of Ceria: A DFT-based Debye-Grüneisen model approach

NASA Astrophysics Data System (ADS)

Lee, Ji-Hwan; Tak, Youngjoo; Lee, Taehun; Soon, Aloysius

Ceria (CeO2-x) is widely studied as a choice electrolyte material for intermediate-temperature (~ 800 K) solid oxide fuel cells. At this temperature, maintaining its chemical stability and thermal-mechanical integrity of this oxide are of utmost importance. To understand their thermal-elastic properties, we firstly test the influence of various approximations to the density-functional theory (DFT) xc functionals on specific thermal-elastic properties of both CeO2 and Ce2O3. Namely, we consider the local-density approximation (LDA), the generalized gradient approximation (GGA-PBE) with and without additional Hubbard U as applied to the 4 f electron of Ce, as well as the recently popularized hybrid functional due to Heyd-Scuseria-Ernzehof (HSE06). Next, we then couple this to a volume-dependent Debye-Grüneisen model to determine the thermodynamic quantities of ceria at arbitrary temperatures. We find an explicit description of the strong correlation (e.g. via the DFT + U and hybrid functional approach) is necessary to have a good agreement with experimental values, in contrast to the mean-field treatment in standard xc approximations (such as LDA or GGA-PBE). We acknowledge support from Samsung Research Funding Center of Samsung Electronics (SRFC-MA1501-03).

A Quasi-Solid-State Sodium-Ion Capacitor with High Energy Density.

PubMed

Wang, Faxing; Wang, Xiaowei; Chang, Zheng; Wu, Xiongwei; Liu, Xiang; Fu, Lijun; Zhu, Yusong; Wu, Yuping; Huang, Wei

2015-11-18

A quasi-solid-state sodium-ion capacitor is demonstrated with nanoporous disordered carbon and macroporous graphene as the negative and positive electrodes, respectively, using a sodium-ion-conducting gel polymer electrolyte. It can operate at a cell voltage as high as 4.2 V with an energy density of record high 168 W h kg(-1). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Production of Biodiesel by Esterification of Free Fatty Acid over Solid Catalyst from Biomass Waste

NASA Astrophysics Data System (ADS)

Mukti, N. I. F.; Sutrisno, B.; Hidayat, A.

2018-05-01

Recently, low cost feedstocks have been utilized to replace vegetable oils in order to improve the economic feasibility of biodiesel. The esterification of free fatty acid (FFA) on Palm Fatty Acid Distillate (PFAD) with methanol using solid catalyst generated from bagasse fly ash is a promising method to convert FFA into biodiesel. In this research, the esterification of FFA on PFAD using the sulfonated bagasse fly ash catalyst was studied. The performances of the catalysts were evaluated in terms of the reaction temperatures, the molar ratios of methanol to PFAD, and the catalyst loading. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimum conditions were methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%wt. of PFAD, and reaction temperature of 6°C. The reusability of the solid acid carbon catalysts was also studied in this work. The catalytic activity decreased up to 38% after third cycle. The significant decline in catalyst esterification activity was due to acid site leaching. The physico-characteristics and acid site densities were analyzed by Nitrogen gas adsorption, surface functional groups by Fourier transform infrared spectroscopy (FT-IR), elemental analysis using X-ray fluorescent (XRF), and acid-base back titration methods for determination of acid density.

Enhancement of DFT-calculations at petascale: Nuclear Magnetic Resonance, Hybrid Density Functional Theory and Car-Parrinello calculations

NASA Astrophysics Data System (ADS)

Varini, Nicola; Ceresoli, Davide; Martin-Samos, Layla; Girotto, Ivan; Cavazzoni, Carlo

2013-08-01

One of the most promising techniques used for studying the electronic properties of materials is based on Density Functional Theory (DFT) approach and its extensions. DFT has been widely applied in traditional solid state physics problems where periodicity and symmetry play a crucial role in reducing the computational workload. With growing compute power capability and the development of improved DFT methods, the range of potential applications is now including other scientific areas such as Chemistry and Biology. However, cross disciplinary combinations of traditional Solid-State Physics, Chemistry and Biology drastically improve the system complexity while reducing the degree of periodicity and symmetry. Large simulation cells containing of hundreds or even thousands of atoms are needed to model these kind of physical systems. The treatment of those systems still remains a computational challenge even with modern supercomputers. In this paper we describe our work to improve the scalability of Quantum ESPRESSO (Giannozzi et al., 2009 [3]) for treating very large cells and huge numbers of electrons. To this end we have introduced an extra level of parallelism, over electronic bands, in three kernels for solving computationally expensive problems: the Sternheimer equation solver (Nuclear Magnetic Resonance, package QE-GIPAW), the Fock operator builder (electronic ground-state, package PWscf) and most of the Car-Parrinello routines (Car-Parrinello dynamics, package CP). Final benchmarks show our success in computing the Nuclear Magnetic Response (NMR) chemical shift of a large biological assembly, the electronic structure of defected amorphous silica with hybrid exchange-correlation functionals and the equilibrium atomic structure of height Porphyrins anchored to a Carbon Nanotube, on many thousands of CPU cores.

Terahertz Spectroscopy and Solid-State Density Functional Theory Calculations of Cyanobenzaldehyde Isomers.

PubMed

Dash, Jyotirmayee; Ray, Shaumik; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin; Gonnade, Rajesh G; Ambade, Ashootosh V; Joshi, Kavita; Pesala, Bala

2015-07-23

Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

Cermet materials prepared by combustion synthesis and metal infiltration

DOEpatents

Holt, Joseph B.; Dunmead, Stephen D.; Halverson, Danny C.; Landingham, Richard L.

1991-01-01

Ceramic-metal composites (cermets) are made by a combination of self-propagating high temperature combustion synthesis and molten metal infiltration. Solid-gas, solid-solid and solid-liquid reactions of a powder compact produce a porous ceramic body which is infiltrated by molten metal to produce a composite body of higher density. AlN-Al and many other materials can be produced.

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

Chauhan, Aditya; Patel, Satyanarayan; Vaish, Rahul, E-mail: rahul@iitmandi.ac.in

With the advent of modern power electronics, embedded circuits and non-conventional energy harvesting, the need for high performance capacitors is bound to become indispensible. The current state-of-art employs ferroelectric ceramics and linear dielectrics for solid state capacitance. However, lead-free ferroelectric ceramics propose to offer significant improvement in the field of electrical energy storage owing to their high discharge efficiency and energy storage density. In this regards, the authors have investigated the effects of compressive stress as a means of improving the energy storage density of lead-free ferroelectric ceramics. The energy storage density of 0.91(Bi{sub 0.5}Na{sub 0.5})TiO{sub 3}-0.07BaTiO{sub 3}-0.02(K{sub 0.5}Na{sub 0.5})NbO{submore » 3} ferroelectric bulk ceramic was analyzed as a function of varying levels of compressive stress and operational temperature .It was observed that a peak energy density of 387 mJ.cm{sup -3} was obtained at 100 MPa applied stress (25{sup o}C). While a maximum energy density of 568 mJ.cm{sup -3} was obtained for the same stress at 80{sup o}C. These values are indicative of a significant, 25% and 84%, improvement in the value of stored energy compared to an unloaded material. Additionally, material's discharge efficiency has also been discussed as a function of operational parameters. The observed phenomenon has been explained on the basis of field induced structural transition and competitive domain switching theory.« less

Achieving Ultrahigh Energy Density and Long Durability in a Flexible Rechargeable Quasi-Solid-State Zn-MnO2 Battery.

PubMed

Zeng, Yinxiang; Zhang, Xiyue; Meng, Yue; Yu, Minghao; Yi, Jianan; Wu, Yiqiang; Lu, Xihong; Tong, Yexiang

2017-07-01

Advanced flexible batteries with high energy density and long cycle life are an important research target. Herein, the first paradigm of a high-performance and stable flexible rechargeable quasi-solid-state Zn-MnO 2 battery is constructed by engineering MnO 2 electrodes and gel electrolyte. Benefiting from a poly(3,4-ethylenedioxythiophene) (PEDOT) buffer layer and a Mn 2+ -based neutral electrolyte, the fabricated Zn-MnO 2 @PEDOT battery presents a remarkable capacity of 366.6 mA h g -1 and good cycling performance (83.7% after 300 cycles) in aqueous electrolyte. More importantly, when using PVA/ZnCl 2 /MnSO 4 gel as electrolyte, the as-fabricated quasi-solid-state Zn-MnO 2 @PEDOT battery remains highly rechargeable, maintaining more than 77.7% of its initial capacity and nearly 100% Coulombic efficiency after 300 cycles. Moreover, this flexible quasi-solid-state Zn-MnO 2 battery achieves an admirable energy density of 504.9 W h kg -1 (33.95 mW h cm -3 ), together with a peak power density of 8.6 kW kg -1 , substantially higher than most recently reported flexible energy-storage devices. With the merits of impressive energy density and durability, this highly flexible rechargeable Zn-MnO 2 battery opens new opportunities for powering portable and wearable electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental measure theory for the inhomogeneous hard-sphere system based on Santos' consistent free energy.

PubMed

Hansen-Goos, Hendrik; Mortazavifar, Mostafa; Oettel, Martin; Roth, Roland

2015-05-01

Based on Santos' general solution for the scaled-particle differential equation [Phys. Rev. E 86, 040102(R) (2012)], we construct a free-energy functional for the hard-sphere system. The functional is obtained by a suitable generalization and extension of the set of scaled-particle variables using the weighted densities from Rosenfeld's fundamental measure theory for the hard-sphere mixture [Phys. Rev. Lett. 63, 980 (1989)]. While our general result applies to the hard-sphere mixture, we specify remaining degrees of freedom by requiring the functional to comply with known properties of the pure hard-sphere system. Both for mixtures and pure systems, the functional can be systematically extended following the lines of our derivation. We test the resulting functionals regarding their behavior upon dimensional reduction of the fluid as well as their ability to accurately describe the hard-sphere crystal and the liquid-solid transition.

Computational Modeling of Mixed Solids for CO2 CaptureSorbents

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

Duan, Yuhua

2015-01-01

Since current technologies for capturing CO2 to fight global climate change are still too energy intensive, there is a critical need for development of new materials that can capture CO2 reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO2 capture applications through a reversible chemical transformation. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO2 sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculated thermodynamic properties of differentmore » classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO2 adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO2 capture reactions by the solids of interest, we were able to screen only those solid materials for which lower capture energy costs are expected at the desired pressure and temperature conditions. Only those selected CO2 sorbent candidates were further considered for experimental validations. The ab initio thermodynamic technique has the advantage of identifying thermodynamic properties of CO2 capture reactions without any experimental input beyond crystallographic structural information of the solid phases involved. Such methodology not only can be used to search for good candidates from existing database of solid materials, but also can provide some guidelines for synthesis new materials. In this presentation, we apply our screening methodology to mixing solid systems to adjust the turnover temperature to help on developing CO2 capture Technologies.« less

The Effects of Experimental Conditions on the Refractive Index and Density of Low-Temperature Ices: Solid Carbon Dioxide

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Moore, M. H.; Gerakines, P. A.

2016-01-01

We present the first study on the effects of the deposition technique on the measurements of the visible refractive index and the density of a low-temperature ice using solid carbon dioxide (CO2) at 14-70 K as an example. While our measurements generally agree with previous studies that show a dependence of index and density on temperature below 50 K, we also find that the measured values depend on the method used to create each sample. Below 50 K, we find that the refractive index varied by as much as 4% and the density by as much as 16% at a single temperature depending on the deposition method. We also show that the Lorentz-Lorenz approximation is valid for solid CO2 across the full 14-70 K temperature range, regardless of the deposition method used. Since the refractive index and density are important in calculations of optical constants and infrared (IR) band strengths of materials, our results suggest that the deposition method must be considered in cases where nvis and ? are not measured in the same experimental setup where the IR spectral measurements are made.