Density functional theory and an experimentally-designed energy functional of electron density.

PubMed

Miranda, David A; Bueno, Paulo R

2016-09-21

We herein demonstrate that capacitance spectroscopy (CS) experimentally allows access to the energy associated with the quantum mechanical ground state of many-electron systems. Priorly, electrochemical capacitance, C [small mu, Greek, macron] [ρ], was previously understood from conceptual and computational density functional theory (DFT) calculations. Thus, we herein propose a quantum mechanical experiment-based variational method for electron charging processes based on an experimentally-designed functional of the ground state electron density. In this methodology, the electron state density, ρ, and an energy functional of the electron density, E [small mu, Greek, macron] [ρ], can be obtained from CS data. CS allows the derivative of the electrochemical potential with respect to the electron density, (δ[small mu, Greek, macron][ρ]/δρ), to be obtained as a unique functional of the energetically minimised system, i.e., β/C [small mu, Greek, macron] [ρ], where β is a constant (associated with the size of the system) and C [small mu, Greek, macron] [ρ] is an experimentally observable quantity. Thus the ground state energy (at a given fixed external potential) can be obtained simply as E [small mu, Greek, macron] [ρ], from the experimental measurement of C [small mu, Greek, macron] [ρ]. An experimental data-set was interpreted to demonstrate the potential of this quantum mechanical experiment-based variational principle.

Augmented potential, energy densities, and virial relations in the weak- and strong-interaction limits of DFT

NASA Astrophysics Data System (ADS)

Vuckovic, Stefan; Levy, Mel; Gori-Giorgi, Paola

2017-12-01

The augmented potential introduced by Levy and Zahariev [Phys. Rev. Lett. 113, 113002 (2014)] is shifted with respect to the standard exchange-correlation potential of the Kohn-Sham density functional theory by a density-dependent constant that makes the total energy become equal to the sum of the occupied orbital energies. In this work, we analyze several features of this approach, focusing on the limit of infinite coupling strength and studying the shift and the corresponding energy density at different correlation regimes. We present and discuss coordinate scaling properties of the augmented potential, study its connection to the response potential, and use the shift to analyze the classical jellium and uniform gas models. We also study other definitions of the energy densities in relation to the functional construction by local interpolations along the adiabatic connection. Our findings indicate that the energy density that is defined in terms of the electrostatic potential of the exchange-correlation hole is particularly well suited for this purpose.

Nonlocal kinetic energy functionals by functional integration.

PubMed

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-14

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, T s [ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δT s [ρ]δρ(r), yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for T s [ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

Nonlocal kinetic energy functionals by functional integration

NASA Astrophysics Data System (ADS)

Mi, Wenhui; Genova, Alessandro; Pavanello, Michele

2018-05-01

Since the seminal studies of Thomas and Fermi, researchers in the Density-Functional Theory (DFT) community are searching for accurate electron density functionals. Arguably, the toughest functional to approximate is the noninteracting kinetic energy, Ts[ρ], the subject of this work. The typical paradigm is to first approximate the energy functional and then take its functional derivative, δ/Ts[ρ ] δ ρ (r ) , yielding a potential that can be used in orbital-free DFT or subsystem DFT simulations. Here, this paradigm is challenged by constructing the potential from the second-functional derivative via functional integration. A new nonlocal functional for Ts[ρ] is prescribed [which we dub Mi-Genova-Pavanello (MGP)] having a density independent kernel. MGP is constructed to satisfy three exact conditions: (1) a nonzero "Kinetic electron" arising from a nonzero exchange hole; (2) the second functional derivative must reduce to the inverse Lindhard function in the limit of homogenous densities; (3) the potential is derived from functional integration of the second functional derivative. Pilot calculations show that MGP is capable of reproducing accurate equilibrium volumes, bulk moduli, total energy, and electron densities for metallic (body-centered cubic, face-centered cubic) and semiconducting (crystal diamond) phases of silicon as well as of III-V semiconductors. The MGP functional is found to be numerically stable typically reaching self-consistency within 12 iterations of a truncated Newton minimization algorithm. MGP's computational cost and memory requirements are low and comparable to the Wang-Teter nonlocal functional or any generalized gradient approximation functional.

Revised Thomas-Fermi approximation for singular potentials

NASA Astrophysics Data System (ADS)

Dufty, James W.; Trickey, S. B.

2016-08-01

Approximations for the many-fermion free-energy density functional that include the Thomas-Fermi (TF) form for the noninteracting part lead to singular densities for singular external potentials (e.g., attractive Coulomb). This limitation of the TF approximation is addressed here by a formal map of the exact Euler equation for the density onto an equivalent TF form characterized by a modified Kohn-Sham potential. It is shown to be a "regularized" version of the Kohn-Sham potential, tempered by convolution with a finite-temperature response function. The resulting density is nonsingular, with the equilibrium properties obtained from the total free-energy functional evaluated at this density. This new representation is formally exact. Approximate expressions for the regularized potential are given to leading order in a nonlocality parameter, and the limiting behavior at high and low temperatures is described. The noninteracting part of the free energy in this approximation is the usual Thomas-Fermi functional. These results generalize and extend to finite temperatures the ground-state regularization by R. G. Parr and S. Ghosh [Proc. Natl. Acad. Sci. U.S.A. 83, 3577 (1986), 10.1073/pnas.83.11.3577] and by L. R. Pratt, G. G. Hoffman, and R. A. Harris [J. Chem. Phys. 88, 1818 (1988), 10.1063/1.454105] and formally systematize the finite-temperature regularization given by the latter authors.

Density functional theory calculations of the water interactions with ZrO2 nanoparticles Y2O3 doped

NASA Astrophysics Data System (ADS)

Subhoni, Mekhrdod; Kholmurodov, Kholmirzo; Doroshkevich, Aleksandr; Asgerov, Elmar; Yamamoto, Tomoyuki; Lyubchyk, Andrei; Almasan, Valer; Madadzada, Afag

2018-03-01

Development of a new electricity generation techniques is one of the most relevant tasks, especially nowadays under conditions of extreme growth in energy consumption. The exothermic heterogeneous electrochemical energy conversion to the electric energy through interaction of the ZrO2 based nanopowder system with atmospheric moisture is one of the ways of electric energy obtaining. The questions of conversion into the electric form of the energy of water molecules adsorption in 3 mol% Y2O3 doped ZrO2 nanopowder systems were investigated using the density functional theory calculations. The density functional theory calculations has been realized as in the Kohn-Sham formulation, where the exchange-correlation potential is approximated by a functional of the electronic density. The electronic density, total energy and band structure calculations are carried out using the all-electron, full potential, linear augmented plane wave method of the electronic density and related approximations, i.e. the local density, the generalized gradient and their hybrid approximations.

Orbital nodal surfaces: Topological challenges for density functionals

NASA Astrophysics Data System (ADS)

Aschebrock, Thilo; Armiento, Rickard; Kümmel, Stephan

2017-06-01

Nodal surfaces of orbitals, in particular of the highest occupied one, play a special role in Kohn-Sham density-functional theory. The exact Kohn-Sham exchange potential, for example, shows a protruding ridge along such nodal surfaces, leading to the counterintuitive feature of a potential that goes to different asymptotic limits in different directions. We show here that nodal surfaces can heavily affect the potential of semilocal density-functional approximations. For the functional derivatives of the Armiento-Kümmel (AK13) [Phys. Rev. Lett. 111, 036402 (2013), 10.1103/PhysRevLett.111.036402] and Becke88 [Phys. Rev. A 38, 3098 (1988), 10.1103/PhysRevA.38.3098] energy functionals, i.e., the corresponding semilocal exchange potentials, as well as the Becke-Johnson [J. Chem. Phys. 124, 221101 (2006), 10.1063/1.2213970] and van Leeuwen-Baerends (LB94) [Phys. Rev. A 49, 2421 (1994), 10.1103/PhysRevA.49.2421] model potentials, we explicitly demonstrate exponential divergences in the vicinity of nodal surfaces. We further point out that many other semilocal potentials have similar features. Such divergences pose a challenge for the convergence of numerical solutions of the Kohn-Sham equations. We prove that for exchange functionals of the generalized gradient approximation (GGA) form, enforcing correct asymptotic behavior of the potential or energy density necessarily leads to irregular behavior on or near orbital nodal surfaces. We formulate constraints on the GGA exchange enhancement factor for avoiding such divergences.

Density-functional theory of spherical electric double layers and zeta potentials of colloidal particles in restricted-primitive-model electrolyte solutions.

PubMed

Yu, Yang-Xin; Wu, Jianzhong; Gao, Guang-Hua

2004-04-15

A density-functional theory is proposed to describe the density profiles of small ions around an isolated colloidal particle in the framework of the restricted primitive model where the small ions have uniform size and the solvent is represented by a dielectric continuum. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for the hard-sphere repulsion and a quadratic functional Taylor expansion for the electrostatic interactions. The theoretical predictions are in good agreement with the results from Monte Carlo simulations and from previous investigations using integral-equation theory for the ionic density profiles and the zeta potentials of spherical particles at a variety of solution conditions. Like the integral-equation approaches, the density-functional theory is able to capture the oscillatory density profiles of small ions and the charge inversion (overcharging) phenomena for particles with elevated charge density. In particular, our density-functional theory predicts the formation of a second counterion layer near the surface of highly charged spherical particle. Conversely, the nonlinear Poisson-Boltzmann theory and its variations are unable to represent the oscillatory behavior of small ion distributions and charge inversion. Finally, our density-functional theory predicts charge inversion even in a 1:1 electrolyte solution as long as the salt concentration is sufficiently high. (c) 2004 American Institute of Physics.

New approach to canonical partition functions computation in Nf=2 lattice QCD at finite baryon density

NASA Astrophysics Data System (ADS)

Bornyakov, V. G.; Boyda, D. L.; Goy, V. A.; Molochkov, A. V.; Nakamura, Atsushi; Nikolaev, A. A.; Zakharov, V. I.

2017-05-01

We propose and test a new approach to computation of canonical partition functions in lattice QCD at finite density. We suggest a few steps procedure. We first compute numerically the quark number density for imaginary chemical potential i μq I . Then we restore the grand canonical partition function for imaginary chemical potential using the fitting procedure for the quark number density. Finally we compute the canonical partition functions using high precision numerical Fourier transformation. Additionally we compute the canonical partition functions using the known method of the hopping parameter expansion and compare results obtained by two methods in the deconfining as well as in the confining phases. The agreement between two methods indicates the validity of the new method. Our numerical results are obtained in two flavor lattice QCD with clover improved Wilson fermions.

A Density Functional for Liquid 3He Based on the Aziz Potential

NASA Astrophysics Data System (ADS)

Barranco, M.; Hernández, E. S.; Mayol, R.; Navarro, J.; Pi, M.; Szybisz, L.

2006-09-01

We propose a new class of density functionals for liquid 3He based on the Aziz helium-helium interaction screened at short distances by the microscopically calculated two-body distribution function g(r). Our aim is to reduce to a minumum the unavoidable phenomenological ingredients inherent to any density functional approach. Results for the homogeneous liquid and droplets are presented and discussed.

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

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

Sundararaman, Ravishankar; Goddard, III, William A.; Arias, Tomas A.

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry.

PubMed

Sundararaman, Ravishankar; Goddard, William A; Arias, Tomas A

2017-03-21

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Finally, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

DOE PAGES

Sundararaman, Ravishankar; Goddard, III, William A.; Arias, Tomas A.

2017-03-16

First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solvemore » the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.« less

Self consistent solution of Schrödinger Poisson equations and some electronic properties of ZnMgO/ZnO hetero structures

NASA Astrophysics Data System (ADS)

Uslu, Salih; Yarar, Zeki

2017-02-01

The epitaxial growth of quantum wells composed of high quality allows the production and application to their device of new structures in low dimensions. The potential profile at the junction is determined by free carriers and by the level of doping. Therefore, the shape of potential is obtained by the electron density. Energy level determines the number of electrons that can be occupied at every level. Energy levels and electron density values of each level must be calculated self consistently. Starting with V(z) test potential, wave functions and electron densities for each energy levels can be calculated to solve Schrödinger equation. If Poisson's equation is solved with the calculated electron density, the electrostatic potential can be obtained. The new V(z) potential can be calculated with using electrostatic potential found beforehand. Thus, the obtained values are calculated self consistently to a certain error criterion. In this study, the energy levels formed in the interfacial potential, electron density in each level and the wave function dependence of material parameters were investigated self consistently.

Density-functional expansion methods: Grand challenges.

PubMed

Giese, Timothy J; York, Darrin M

2012-03-01

We discuss the source of errors in semiempirical density functional expansion (VE) methods. In particular, we show that VE methods are capable of well-reproducing their standard Kohn-Sham density functional method counterparts, but suffer from large errors upon using one or more of these approximations: the limited size of the atomic orbital basis, the Slater monopole auxiliary basis description of the response density, and the one- and two-body treatment of the core-Hamiltonian matrix elements. In the process of discussing these approximations and highlighting their symptoms, we introduce a new model that supplements the second-order density-functional tight-binding model with a self-consistent charge-dependent chemical potential equalization correction; we review our recently reported method for generalizing the auxiliary basis description of the atomic orbital response density; and we decompose the first-order potential into a summation of additive atomic components and many-body corrections, and from this examination, we provide new insights and preliminary results that motivate and inspire new approximate treatments of the core-Hamiltonian.

On the v-representability of ensemble densities of electron systems

NASA Astrophysics Data System (ADS)

Gonis, A.; Däne, M.

2018-05-01

Analogously to the case at zero temperature, where the density of the ground state of an interacting many-particle system determines uniquely (within an arbitrary additive constant) the external potential acting on the system, the thermal average of the density over an ensemble defined by the Boltzmann distribution at the minimum of the thermodynamic potential, or the free energy, determines the external potential uniquely (and not just modulo a constant) acting on a system described by this thermodynamic potential or free energy. The paper describes a formal procedure that generates the domain of a constrained search over general ensembles (at zero or elevated temperatures) that lead to a given density, including as a special case a density thermally averaged at a given temperature, and in the case of a v-representable density determines the external potential leading to the ensemble density. As an immediate consequence of the general formalism, the concept of v-representability is extended beyond the hitherto discussed case of ground state densities to encompass excited states as well. Specific application to thermally averaged densities solves the v-representability problem in connection with the Mermin functional in a manner analogous to that in which this problem was recently settled with respect to the Hohenberg and Kohn functional. The main formalism is illustrated with numerical results for ensembles of one-dimensional, non-interacting systems of particles under a harmonic potential.

On the v-representability of ensemble densities of electron systems

DOE PAGES

Gonis, A.; Dane, M.

2017-12-30

Analogously to the case at zero temperature, where the density of the ground state of an interacting many-particle system determines uniquely (within an arbitrary additive constant) the external potential acting on the system, the thermal average of the density over an ensemble defined by the Boltzmann distribution at the minimum of the thermodynamic potential, or the free energy, determines the external potential uniquely (and not just modulo a constant) acting on a system described by this thermodynamic potential or free energy. The study describes a formal procedure that generates the domain of a constrained search over general ensembles (at zeromore » or elevated temperatures) that lead to a given density, including as a special case a density thermally averaged at a given temperature, and in the case of a v-representable density determines the external potential leading to the ensemble density. As an immediate consequence of the general formalism, the concept of v-representability is extended beyond the hitherto discussed case of ground state densities to encompass excited states as well. Specific application to thermally averaged densities solves the v-representability problem in connection with the Mermin functional in a manner analogous to that in which this problem was recently settled with respect to the Hohenberg and Kohn functional. Finally, the main formalism is illustrated with numerical results for ensembles of one-dimensional, non-interacting systems of particles under a harmonic potential.« less

Violation of the continuity equation in the Krieger-Li-Iafrate approximation for current-density functional theory

NASA Astrophysics Data System (ADS)

Siegmund, Marc; Pankratov, Oleg

2011-01-01

We show that the exchange-correlation scalar and vector potentials obtained from the optimized effective potential (OEP) equations and from the Krieger-Li-Iafrate (KLI) approximation for the current-density functional theory (CDFT) change under a gauge transformation such that the energy functional remains invariant. This alone does not assure, however, the theory’s compliance with the continuity equation. Using the model of a quantum ring with a broken angular symmetry which is penetrated by a magnetic flux we demonstrate that the physical current density calculated with the exact-exchange CDFT in the KLI approximation violates the continuity condition. In contrast, the current found from a solution of the full OEP equations satisfies this condition. We argue that the continuity violation stems from the fact that the KLI potentials are not (in general) the exact functional derivatives of a gauge-invariant exchange-correlation functional.

Characterizing the potential energy surface of the water dimer with DFT: failures of some popular functionals for hydrogen bonding.

PubMed

Anderson, Julie A; Tschumper, Gregory S

2006-06-08

Ten stationary points on the water dimer potential energy surface have been examined with ten density functional methods (X3LYP, B3LYP, B971, B98, MPWLYP, PBE1PBE, PBE, MPW1K, B3P86, and BHandHLYP). Geometry optimizations and vibrational frequency calculations were carried out with the TZ2P(f,d)+dif basis set. All ten of the density functionals correctly describe the relative energies of the ten stationary points. However, correctly describing the curvature of the potential energy surface is far more difficult. Only one functional (BHandHLYP) reproduces the number of imaginary frequencies from CCSD(T) calculations. The other nine density functionals fail to correctly characterize the nature of at least one of the ten (H(2)O)(2) stationary points studied here.

Real-Space Multiple-Scattering Theory and Its Applications at Exascale

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

Eisenbach, Markus; Wang, Yang

In recent decades, the ab initio methods based on density functional theory (DFT) (Hohenberg and Kohn 1964, Kohn and Sham 1965) have become a widely used tool in computational materials science, which allows theoretical prediction of physical properties of materials from the first principles and theoretical interpretation of new physical phenomena found in experiments. In the framework of DFT, the original problem that requires solving a quantum mechanical equation for a many-electron system is reduced to a one-electron problem that involves an electron moving in an effective field, while the effective field potential is made up of an electrostatic potential,more » also known as Hartree potential, arising from the electronic and ion charge distribution in space and an exchange–correlation potential, which is a function of the electron density and encapsulates the exchange and correlation effects of the many-electron system. Even though the exact functional form of the exchange-correlation potential is formally unknown, a local density approximation (LDA) or a generalized gradient approximation (GGA) is usually applied so that the calculation of the exchange–correlation potential, as well as the exchange–correlation energy, becomes tractable while a required accuracy is retained. Based on DFT, ab initio electronic structure calculations for a material generally involve a self-consistent process that iterates between two computational tasks: (1) solving an one-electron Schrödinger equation, also known as Kohn–Sham equation, to obtain the electron density and, if needed, the magnetic moment density, and (2) solving the Poisson equation to obtain the electrostatic potential corresponding to the electron density and constructing the effective potential by adding the exchange–correlation potential to the electrostatic potential. This self-consistent process proceeds until a convergence criteria is reached.« less

Density-functional expansion methods: evaluation of LDA, GGA, and meta-GGA functionals and different integral approximations.

PubMed

Giese, Timothy J; York, Darrin M

2010-12-28

We extend the Kohn-Sham potential energy expansion (VE) to include variations of the kinetic energy density and use the VE formulation with a 6-31G* basis to perform a "Jacob's ladder" comparison of small molecule properties using density functionals classified as being either LDA, GGA, or meta-GGA. We show that the VE reproduces standard Kohn-Sham DFT results well if all integrals are performed without further approximation, and there is no substantial improvement in using meta-GGA functionals relative to GGA functionals. The advantages of using GGA versus LDA functionals becomes apparent when modeling hydrogen bonds. We furthermore examine the effect of using integral approximations to compute the zeroth-order energy and first-order matrix elements, and the results suggest that the origin of the short-range repulsive potential within self-consistent charge density-functional tight-binding methods mainly arises from the approximations made to the first-order matrix elements.

Simulation Of Wave Function And Probability Density Of Modified Poschl Teller Potential Derived Using Supersymmetric Quantum Mechanics

NASA Astrophysics Data System (ADS)

Angraini, Lily Maysari; Suparmi, Variani, Viska Inda

2010-12-01

SUSY quantum mechanics can be applied to solve Schrodinger equation for high dimensional system that can be reduced into one dimensional system and represented in lowering and raising operators. Lowering and raising operators can be obtained using relationship between original Hamiltonian equation and the (super) potential equation. In this paper SUSY quantum mechanics is used as a method to obtain the wave function and the energy level of the Modified Poschl Teller potential. The graph of wave function equation and probability density is simulated by using Delphi 7.0 programming language. Finally, the expectation value of quantum mechanics operator could be calculated analytically using integral form or probability density graph resulted by the programming.

Self-consistent many-electron theory of electron work functions and surface potential characteristics for selected metals

NASA Technical Reports Server (NTRS)

Smith, J. R.

1969-01-01

Electron work functions, surface potentials, and electron number density distributions and electric fields in the surface region of 26 metals were calculated from first principles within the free electron model. Calculation proceeded from an expression of the total energy as a functional of the electron number density, including exchange and correlation energies, as well as a first inhomogeneity term. The self-consistent solution was obtained via a variational procedure. Surface barriers were due principally to many-body effects; dipole barriers were small only for some alkali metals, becoming quite large for the transition metals. Surface energies were inadequately described by this model, which neglects atomistic effects. Reasonable results were obtained for electron work functions and surface potential characteristics, maximum electron densities varying by a factor of over 60.

Self-consistent calculations for the electronic structure of a vacancy in copper. A solution of the embedding problem

NASA Astrophysics Data System (ADS)

Zeller, R.; Braspenning, P. J.

1982-06-01

The charge density and the local density of states for a vacancy in Cu and for the first shell of Cu neighbours are calculated by the KKR-Green's function technique. The muffin-tin potentials for the vacancy and the neighbour shell atoms are determined self-consistently in the local density approximation of density functional theory. By the use of the proper host Green's function the embedding of this cluster of 13 perturbed muffin-tins into the infinite array of bulk Cu muffin-tin potentials is described rigorously, thus representing a solution of the embedding problem. The calculations demonstrate a rather large charge transfer of 1.1 electrons from the first neighbour shell to the vacancy.

Accurately predicting the structure, density, and hydrostatic compression of crystalline β-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane based on its wave-function-based potential

NASA Astrophysics Data System (ADS)

Song, H.-J.; Huang, F.

2011-09-01

A wave-function-based intermolecular potential of the β phase 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) molecule has been constructed from first principles using the Williams-Stone-Misquitta method and the symmetry-adapted perturbation theory. Using the potential and its derivatives, we have accurately predicted not only the structure and lattice energy of the crystalline β-HMX at 0 K, but also its densities at temperatures of 0-403 K within an accuracy of 1% of density. The calculated densities at pressures within 0-6 GPa excellently agree with the results from the experiments on hydrostatic compression.

Relativistic density functional theory with picture-change corrected electron density based on infinite-order Douglas-Kroll-Hess method

NASA Astrophysics Data System (ADS)

Oyama, Takuro; Ikabata, Yasuhiro; Seino, Junji; Nakai, Hiromi

2017-07-01

This Letter proposes a density functional treatment based on the two-component relativistic scheme at the infinite-order Douglas-Kroll-Hess (IODKH) level. The exchange-correlation energy and potential are calculated using the electron density based on the picture-change corrected density operator transformed by the IODKH method. Numerical assessments indicated that the picture-change uncorrected density functional terms generate significant errors, on the order of hartree for heavy atoms. The present scheme was found to reproduce the energetics in the four-component treatment with high accuracy.

Coarse-grained density functional theories for metallic alloys: Generalized coherent-potential approximations and charge-excess functional theory

NASA Astrophysics Data System (ADS)

Bruno, Ezio; Mammano, Francesco; Fiorino, Antonino; Morabito, Emanuela V.

2008-04-01

The class of the generalized coherent-potential approximations (GCPAs) to the density functional theory (DFT) is introduced within the multiple scattering theory formalism with the aim of dealing with ordered or disordered metallic alloys. All GCPA theories are based on a common ansatz for the kinetic part of the Hohenberg-Kohn functional and each theory of the class is specified by an external model concerning the potential reconstruction. Most existing DFT implementations of CPA-based theories belong to the GCPA class. The analysis of the formal properties of the density functional defined by GCPA theories shows that it consists of marginally coupled local contributions. Furthermore, it is shown that the GCPA functional does not depend on the details of the charge density and that it can be exactly rewritten as a function of the appropriate charge multipole moments to be associated with each lattice site. A general procedure based on the integration of the qV laws is described that allows for the explicit construction of the same function. The coarse-grained nature of the GCPA density functional implies a great deal of computational advantages and is connected with the O(N) scalability of GCPA algorithms. Moreover, it is shown that a convenient truncated series expansion of the GCPA functional leads to the charge-excess functional (CEF) theory [E. Bruno , Phys. Rev. Lett. 91, 166401 (2003)], which here is offered in a generalized version that includes multipolar interactions. CEF and the GCPA numerical results are compared with status of art linearized augmented plane wave (LAPW) full-potential density functional calculations for 62 bcc- and fcc-based ordered CuZn alloys, in all the range of concentrations. Two facts clearly emerge from these extensive tests. In the first place, the discrepancies between GCPA and CEF results are always within the numerical accuracy of the calculations, both for the site charges and the total energies. In the second place, the GCPA (or the CEF) is able to very carefully reproduce the LAPW site charges and a good agreement is obtained also about the total energies.

Density-functional theory based on the electron distribution on the energy coordinate

NASA Astrophysics Data System (ADS)

Takahashi, Hideaki

2018-03-01

We developed an electronic density functional theory utilizing a novel electron distribution n(ɛ) as a basic variable to compute ground state energy of a system. n(ɛ) is obtained by projecting the electron density n({\\boldsymbol{r}}) defined on the space coordinate {\\boldsymbol{r}} onto the energy coordinate ɛ specified with the external potential {\\upsilon }ext}({\\boldsymbol{r}}) of interest. It was demonstrated that the Kohn-Sham equation can also be formulated with the exchange-correlation functional E xc[n(ɛ)] that employs the density n(ɛ) as an argument. It turned out an exchange functional proposed in our preliminary development suffices to describe properly the potential energies of several types of chemical bonds with comparable accuracies to the corresponding functional based on local density approximation. As a remarkable feature of the distribution n(ɛ) it inherently involves the spatially non-local information of the exchange hole at the bond dissociation limit in contrast to conventional approximate functionals. By taking advantage of this property we also developed a prototype of the static correlation functional E sc including no empirical parameters, which showed marked improvements in describing the dissociations of covalent bonds in {{{H}}}2,{{{C}}}2{{{H}}}4 and {CH}}4 molecules.

In search of the Hohenberg-Kohn theorem

NASA Astrophysics Data System (ADS)

Lammert, Paul E.

2018-04-01

The Hohenberg-Kohn theorem, a cornerstone of electronic density functional theory, concerns uniqueness of external potentials yielding given ground densities of an N -body system. The problem is rigorously explored in a universe of three-dimensional Kato-class potentials, with emphasis on trade-offs between conditions on the density and conditions on the potential sufficient to ensure uniqueness. Sufficient conditions range from none on potentials coupled with everywhere strict positivity of the density to none on the density coupled with something a little weaker than local 3 N /2 -power integrability of the potential on a connected full-measure set. A second theme is localizability, that is, the possibility of uniqueness over subsets of R3 under less stringent conditions.

Explicit polarization (X-Pol) potential using ab initio molecular orbital theory and density functional theory.

PubMed

Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali

2009-10-29

The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.

Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.

PubMed

Chen, Zehua; Zhang, Du; Jin, Ye; Yang, Yang; Su, Neil Qiang; Yang, Weitao

2017-09-21

To describe static correlation, we develop a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We show that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn-Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle-particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical results show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

Steady-State Density Functional Theory for Finite Bias Conductances.

PubMed

Stefanucci, G; Kurth, S

2015-12-09

In the framework of density functional theory, a formalism to describe electronic transport in the steady state is proposed which uses the density on the junction and the steady current as basic variables. We prove that, in a finite window around zero bias, there is a one-to-one map between the basic variables and both local potential on as well as bias across the junction. The resulting Kohn-Sham system features two exchange-correlation (xc) potentials, a local xc potential, and an xc contribution to the bias. For weakly coupled junctions the xc potentials exhibit steps in the density-current plane which are shown to be crucial to describe the Coulomb blockade diamonds. At small currents these steps emerge as the equilibrium xc discontinuity bifurcates. The formalism is applied to a model benzene junction, finding perfect agreement with the orthodox theory of Coulomb blockade.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

DOE PAGES

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

2017-11-20

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

NASA Astrophysics Data System (ADS)

Tao, Jianmin; Ye, Lin-Hui; Duan, Yuhua

2017-12-01

The primary goal of Kohn-Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao-Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE), Tao-Perdew-Staroverov-Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree-Fock density yields the exchange and correlation energies in good agreement with the Optimized Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Finally, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.

Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density

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

Tao, Jianmin; Ye, Lin -Hui; Duan, Yuhua

The primary goal of Kohn–Sham density functional theory is to evaluate the exchange-correlation contribution to electronic properties. However, the accuracy of a density functional can be affected by the electron density. Here we apply the nonempirical Tao–Mo (TM) semilocal functional to study the influence of the electron density on the exchange and correlation energies of atoms and ions, and compare the results with the commonly used nonempirical semilocal functionals local spin-density approximation (LSDA), Perdew–Burke–Ernzerhof (PBE), Tao–Perdew–Staroverov–Scuseria (TPSS), and hybrid functional PBE0. We find that the spin-restricted Hartree–Fock density yields the exchange and correlation energies in good agreement with the Optimizedmore » Effective Potential method, particularly for spherical atoms and ions. However, the errors of these semilocal and hybrid functionals become larger for self-consistent densities. We further find that the quality of the electron density have greater effect on the exchange-correlation energies of kinetic energy density-dependent meta-GGA functionals TPSS and TM than on those of the LSDA and GGA, and therefore, should have greater influence on the performance of meta-GGA functionals. Lastly, we show that the influence of the density quality on PBE0 is slightly reduced, compared to that of PBE, due to the exact mixing.« less

Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters using Density Functional Theory

DTIC Science & Technology

2017-05-05

dependent density functional theory (TD-DFT). The size of the clusters considered is relatively large compared to those considered in previous studies...are characterized by many different geometries, which potentially can be optimized with respect to specific materials design criteria, i.e., molecular...SixOy molecular clusters using density functional theory (DFT). The size of the clusters considered, however, is relatively large compared to those

Density functional theory of electron transfer beyond the Born-Oppenheimer approximation: Case study of LiF

NASA Astrophysics Data System (ADS)

Li, Chen; Requist, Ryan; Gross, E. K. U.

2018-02-01

We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an abrupt change in the ground state electronic distribution due to an electron transfer at a critical bond length R = Rc, where an avoided crossing of the lowest adiabatic potential energy surfaces calls the validity of the Born-Oppenheimer approximation into doubt. Modeling the R-dependent electronic structure of LiF within a two-site Hubbard model, we find that nonadiabatic electron-nuclear coupling produces a sizable elongation of the critical Rc by 0.5 bohr. This effect is very accurately captured by a simple and rigorously derived correction, with an M-1 prefactor, to the exchange-correlation potential in density functional theory, M = reduced nuclear mass. Since this nonadiabatic term depends on gradients of the nuclear wave function and conditional electronic density, ∇Rχ(R) and ∇Rn(r, R), it couples the Kohn-Sham equations at neighboring R points. Motivated by an observed localization of nonadiabatic effects in nuclear configuration space, we propose a local conditional density approximation—an approximation that reduces the search for nonadiabatic density functionals to the search for a single function y(n).

Dynamic kinetic energy potential for orbital-free density functional theory.

PubMed

Neuhauser, Daniel; Pistinner, Shlomo; Coomar, Arunima; Zhang, Xu; Lu, Gang

2011-04-14

A dynamic kinetic energy potential (DKEP) is developed for time-dependent orbital-free (TDOF) density function theory applications. This potential is constructed to affect only the dynamical (ω ≠ 0) response of an orbital-free electronic system. It aims at making the orbital-free simulation respond in the same way as that of a noninteracting homogenous electron gas (HEG), as required by a correct kinetic energy, therefore enabling extension of the success of orbital-free density functional theory in the static case (e.g., for embedding and description of processes in bulk materials) to dynamic processes. The potential is constructed by expansions of terms, each of which necessitates only simple time evolution (concurrent with the TDOF evolution) and a spatial convolution at each time-step. With 14 such terms a good fit is obtained to the response of the HEG at a large range of frequencies, wavevectors, and densities. The method is demonstrated for simple jellium spheres, approximating Na(9)(+) and Na(65)(+) clusters. It is applicable both to small and large (even ultralarge) excitations and the results converge (i.e., do not blow up) as a function of time. An extension to iterative frequency-resolved extraction is briefly outlined, as well as possibly numerically simpler expansions. The approach could also be extended to fit, instead of the HEG susceptibility, either an experimental susceptibility or a theoretically derived one for a non-HEG system. The DKEP potential should be a powerful tool for embedding a dynamical system described by a more accurate method (such as time-dependent density functional theory, TDDFT) in a large background described by TDOF with a DKEP potential. The type of expansions used and envisioned should be useful for other approaches, such as memory functionals in TDDFT. Finally, an appendix details the formal connection between TDOF and TDDFT.

Functional differentiability in time-dependent quantum mechanics.

PubMed

Penz, Markus; Ruggenthaler, Michael

2015-03-28

In this work, we investigate the functional differentiability of the time-dependent many-body wave function and of derived quantities with respect to time-dependent potentials. For properly chosen Banach spaces of potentials and wave functions, Fréchet differentiability is proven. From this follows an estimate for the difference of two solutions to the time-dependent Schrödinger equation that evolve under the influence of different potentials. Such results can be applied directly to the one-particle density and to bounded operators, and present a rigorous formulation of non-equilibrium linear-response theory where the usual Lehmann representation of the linear-response kernel is not valid. Further, the Fréchet differentiability of the wave function provides a new route towards proving basic properties of time-dependent density-functional theory.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

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

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

Functional response of wolves preying on barren-ground caribou in a multiple-prey ecosystem

USGS Publications Warehouse

Dale, B.W.; Adams, Layne G.; Bowyer, R.T.

1994-01-01

1. We investigated the functional response of wolves (Canis lupus) to varying abundance of ungulate prey to test the hypothesis that switching from alternate prey to preferred prey results in regulation of a caribou (Rangifer tarandus) population at low densities. 2. We determined prey selection, kill rates, and prey abundance for four wolf packs during three 30-day periods in March 1989, March 1990, November 1990, and created a simple discrete model to evaluate the potential for the expected numerical and observed functional responses of wolves to regulate caribou populations. 3. We observed a quickly decelerating type II functional response that, in the absence of numerical response, implicates an anti-regulatory effect of wolf predation on barren-ground caribou dynamics. 4. There was little potential for regulation caused by the multiplicative effect of increasing functional and numerical responses because of presence of alternative prey. This resulted in high wolf:caribou ratios at low prey densities which precluded the effects of an increasing functional response. 5. Inversely density-dependent predation by other predators, such as bears, reduces the potential for predators to regulate caribou populations at low densities, and small reductions in predation by one predator may have disproportionately large effects on the total predation rate.

Ionic fluids with r-6 pair interactions have power-law electrostatic screening

NASA Astrophysics Data System (ADS)

Kjellander, Roland; Forsberg, Björn

2005-06-01

The decay behaviour of radial distribution functions for large distances r is investigated for classical Coulomb fluids where the ions interact with an r-6 potential (e.g. a dispersion interaction) in addition to the Coulombic and the short-range repulsive potentials (e.g. a hard core). The pair distributions and the density-density (NN), charge-density (QN) and charge-charge (QQ) correlation functions are investigated analytically and by Monte Carlo simulations. It is found that the NN correlation function ultimately decays like r-6 for large r, just as it does for fluids of electroneutral particles interacting with an r-6 potential. The prefactor is proportional to the squared compressibility in both cases. The QN correlations decay in general like r-8 and the QQ correlations like r-10 in the ionic fluid. The average charge density around an ion decays generally like r-8 and the average electrostatic potential like r-6. This behaviour is in stark contrast to the decay behaviour for classical Coulomb fluids in the absence of the r-6 potential, where all these functions decay exponentially for large r. The power-law decays are, however, the same as for quantum Coulomb fluids. This indicates that the inclusion of the dispersion interaction as an effective r-6 interaction potential in classical systems yields the same decay behaviour for the pair correlations as in quantum ionic systems. An exceptional case is the completely symmetric binary electrolyte for which only the NN correlation has a power-law decay but not the QQ correlations. These features are shown by an analysis of the bridge function.

Colloids exposed to random potential energy landscapes: From particle number density to particle-potential and particle-particle interactions

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

Bewerunge, Jörg; Capellmann, Ronja F.; Platten, Florian

2016-07-28

Colloidal particles were exposed to a random potential energy landscape that has been created optically via a speckle pattern. The mean particle density as well as the potential roughness, i.e., the disorder strength, were varied. The local probability density of the particles as well as its main characteristics were determined. For the first time, the disorder-averaged pair density correlation function g{sup (1)}(r) and an analogue of the Edwards-Anderson order parameter g{sup (2)}(r), which quantifies the correlation of the mean local density among disorder realisations, were measured experimentally and shown to be consistent with replica liquid state theory results.

Efficient construction of exchange and correlation potentials by inverting the Kohn-Sham equations.

PubMed

Kananenka, Alexei A; Kohut, Sviataslau V; Gaiduk, Alex P; Ryabinkin, Ilya G; Staroverov, Viktor N

2013-08-21

Given a set of canonical Kohn-Sham orbitals, orbital energies, and an external potential for a many-electron system, one can invert the Kohn-Sham equations in a single step to obtain the corresponding exchange-correlation potential, vXC(r). For orbitals and orbital energies that are solutions of the Kohn-Sham equations with a multiplicative vXC(r) this procedure recovers vXC(r) (in the basis set limit), but for eigenfunctions of a non-multiplicative one-electron operator it produces an orbital-averaged potential. In particular, substitution of Hartree-Fock orbitals and eigenvalues into the Kohn-Sham inversion formula is a fast way to compute the Slater potential. In the same way, we efficiently construct orbital-averaged exchange and correlation potentials for hybrid and kinetic-energy-density-dependent functionals. We also show how the Kohn-Sham inversion approach can be used to compute functional derivatives of explicit density functionals and to approximate functional derivatives of orbital-dependent functionals.

BRIEF COMMUNICATION: A note on the Coulomb collision operator in curvilinear coordinates

NASA Astrophysics Data System (ADS)

Goncharov, P. R.

2010-10-01

The dynamic friction force, diffusion tensor, flux density in velocity space and Coulomb collision term are expressed in curvilinear coordinates via Trubnikov potential functions corresponding to each species of a background plasma. For comparison, explicit formulae are given for the dynamic friction force, diffusion tensor and collisional flux density in velocity space in curvilinear coordinates via Rosenbluth potential functions summed over all species of the background plasma.

Testing the nonlocal kinetic energy functional of an inhomogeneous, two-dimensional degenerate Fermi gas within the average density approximation

NASA Astrophysics Data System (ADS)

Towers, J.; van Zyl, B. P.; Kirkby, W.

2015-08-01

In a recent paper [B. P. van Zyl et al., Phys. Rev. A 89, 022503 (2014), 10.1103/PhysRevA.89.022503], the average density approximation (ADA) was implemented to develop a parameter-free, nonlocal kinetic energy functional to be used in the orbital-free density functional theory of an inhomogeneous, two-dimensional (2D) Fermi gas. In this work, we provide a detailed comparison of self-consistent calculations within the ADA with the exact results of the Kohn-Sham density functional theory and the elementary Thomas-Fermi (TF) approximation. We demonstrate that the ADA for the 2D kinetic energy functional works very well under a wide variety of confinement potentials, even for relatively small particle numbers. Remarkably, the TF approximation for the kinetic energy functional, without any gradient corrections, also yields good agreement with the exact kinetic energy for all confining potentials considered, although at the expense of the spatial and kinetic energy densities exhibiting poor pointwise agreement, particularly near the TF radius. Our findings illustrate that the ADA kinetic energy functional yields accurate results for both the local and global equilibrium properties of an inhomogeneous 2D Fermi gas, without the need for any fitting parameters.

Size-dependent error of the density functional theory ionization potential in vacuum and solution

DOE PAGES

Sosa Vazquez, Xochitl A.; Isborn, Christine M.

2015-12-22

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

Size-dependent error of the density functional theory ionization potential in vacuum and solution

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

Sosa Vazquez, Xochitl A.; Isborn, Christine M., E-mail: cisborn@ucmerced.edu

2015-12-28

Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potentialmore » for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. In vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.« less

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.

Beyond Kohn-Sham Approximation: Hybrid Multistate Wave Function and Density Functional Theory.

PubMed

Gao, Jiali; Grofe, Adam; Ren, Haisheng; Bao, Peng

2016-12-15

A multistate density functional theory (MSDFT) is presented in which the energies and densities for the ground and excited states are treated on the same footing using multiconfigurational approaches. The method can be applied to systems with strong correlation and to correctly describe the dimensionality of the conical intersections between strongly coupled dissociative potential energy surfaces. A dynamic-then-static framework for treating electron correlation is developed to first incorporate dynamic correlation into contracted state functions through block-localized Kohn-Sham density functional theory (KSDFT), followed by diagonalization of the effective Hamiltonian to include static correlation. MSDFT can be regarded as a hybrid of wave function and density functional theory. The method is built on and makes use of the current approximate density functional developed in KSDFT, yet it retains its computational efficiency to treat strongly correlated systems that are problematic for KSDFT but too large for accurate WFT. The results presented in this work show that MSDFT can be applied to photochemical processes involving conical intersections.

Thermodynamic and redox properties of graphene oxides for lithium-ion battery applications: a first principles density functional theory modeling approach.

PubMed

Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

2016-07-27

Understanding the thermodynamic stability and redox properties of oxygen functional groups on graphene is critical to systematically design stable graphene-based positive electrode materials with high potential for lithium-ion battery applications. In this work, we study the thermodynamic and redox properties of graphene functionalized with carbonyl and hydroxyl groups, and the evolution of these properties with the number, types and distribution of functional groups by employing the density functional theory method. It is found that the redox potential of the functionalized graphene is sensitive to the types, number, and distribution of oxygen functional groups. First, the carbonyl group induces higher redox potential than the hydroxyl group. Second, more carbonyl groups would result in higher redox potential. Lastly, the locally concentrated distribution of the carbonyl group is more beneficial to have higher redox potential compared to the uniformly dispersed distribution. In contrast, the distribution of the hydroxyl group does not affect the redox potential significantly. Thermodynamic investigation demonstrates that the incorporation of carbonyl groups at the edge of graphene is a promising strategy for designing thermodynamically stable positive electrode materials with high redox potentials.

Why do ultrasoft repulsive particles cluster and crystallize? Analytical results from density-functional theory.

PubMed

Likos, Christos N; Mladek, Bianca M; Gottwald, Dieter; Kahl, Gerhard

2007-06-14

We demonstrate the accuracy of the hypernetted chain closure and of the mean-field approximation for the calculation of the fluid-state properties of systems interacting by means of bounded and positive pair potentials with oscillating Fourier transforms. Subsequently, we prove the validity of a bilinear, random-phase density functional for arbitrary inhomogeneous phases of the same systems. On the basis of this functional, we calculate analytically the freezing parameters of the latter. We demonstrate explicitly that the stable crystals feature a lattice constant that is independent of density and whose value is dictated by the position of the negative minimum of the Fourier transform of the pair potential. This property is equivalent with the existence of clusters, whose population scales proportionally to the density. We establish that regardless of the form of the interaction potential and of the location on the freezing line, all cluster crystals have a universal Lindemann ratio Lf=0.189 at freezing. We further make an explicit link between the aforementioned density functional and the harmonic theory of crystals. This allows us to establish an equivalence between the emergence of clusters and the existence of negative Fourier components of the interaction potential. Finally, we make a connection between the class of models at hand and the system of infinite-dimensional hard spheres, when the limits of interaction steepness and space dimension are both taken to infinity in a particularly described fashion.

Density functional theory of electron transfer beyond the Born-Oppenheimer approximation: Case study of LiF.

PubMed

Li, Chen; Requist, Ryan; Gross, E K U

2018-02-28

We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an abrupt change in the ground state electronic distribution due to an electron transfer at a critical bond length R = R c , where an avoided crossing of the lowest adiabatic potential energy surfaces calls the validity of the Born-Oppenheimer approximation into doubt. Modeling the R-dependent electronic structure of LiF within a two-site Hubbard model, we find that nonadiabatic electron-nuclear coupling produces a sizable elongation of the critical R c by 0.5 bohr. This effect is very accurately captured by a simple and rigorously derived correction, with an M -1 prefactor, to the exchange-correlation potential in density functional theory, M = reduced nuclear mass. Since this nonadiabatic term depends on gradients of the nuclear wave function and conditional electronic density, ∇ R χ(R) and ∇ R n(r, R), it couples the Kohn-Sham equations at neighboring R points. Motivated by an observed localization of nonadiabatic effects in nuclear configuration space, we propose a local conditional density approximation-an approximation that reduces the search for nonadiabatic density functionals to the search for a single function y(n).

Density-Functional Theory with Optimized Effective Potential and Self-Interaction Correction for the Double Ionization of He and Be Atoms

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2012-06-01

We present a self-interaction-free (SIC) time-dependent density-functional theory (TDDFT) for the treatment of double ionization processes of many-electron systems. The method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed 3D calculations of double ionization of He and Be atoms by strong near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double ionization process. We found that proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the spin particle numbers (SPN) only. The results for the intensity-dependent probabilities of single and double ionization are presented and reproduce the famous ``knee'' structure.

Molecular simulation of disjoining-pressure isotherms for free liquid , Lennard-Jones thin films

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

Bhatt, Divesh; Newman, John; Radke, C.J.

2001-10-01

We present canonical-ensemble molecular-dynamics simulations of disjoining-pressure isotherms in Lennard-Jones free liquid films. Thermodynamics demands that the disjoining pressure is determined uniquely as a function of the chemical potential purely from the phase diagram of the fluid. Our results from molecular dynamics validate this argument. The inverse-sixth-power distance term in the Lennard-Jones intermolecular potential represents van der Waals dispersion forces. Hence, we compare our results with classical Hamaker theory that is based on dispersion forces but assumes a slab geometry for the density profile and completely neglects fluid structure and entropy. We find that the Hamaker constant obtained from ourmore » simulations is about an order of magnitude larger than that from classical theory. To investigate the origin of this discrepancy, we calculate the disjoining-pressure isotherm using a density-functional theory relaxing the inherent assumptions in the Hamaker theory and imparting to the fluid an approximate structure. For disjoining pressure as a function of chemical potential, the results of density-functional theory and molecular dynamics are very close. Even for disjoining-pressure isotherms, and the subsequently calculated Hamaker constant, results of the density-functional theory are closer to the molecular-dynamics simulations by about a factor of 4 compared to Hamaker theory. [References: 44]« less

Density-functional theory for fluid-solid and solid-solid phase transitions.

PubMed

Bharadwaj, Atul S; Singh, Yashwant

2017-03-01

We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u(r)=ε(σ/r)^{n}, where parameter n measures softness of the potential. We find that for 1/n<0.154 systems freeze into the face centered cubic (fcc) structure while for 1/n≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.

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.

Adsorbate Diffusion on Transition Metal Nanoparticles

DTIC Science & Technology

2015-01-01

different sizes and shapes using density functional theory calculations. We show that nanoparticles bind adsorbates more strongly than the...structure theoretical methods, a quantitative study with accurate density functional theory (DFT) calculations is still missing. Here, we perform a...functional theory . The projector augmented wave (PAW) potentials29,30 were used for electron- ion interactions and the generalized gradient approximation

Population Density Modulates Drug Inhibition and Gives Rise to Potential Bistability of Treatment Outcomes for Bacterial Infections.

PubMed

Karslake, Jason; Maltas, Jeff; Brumm, Peter; Wood, Kevin B

2016-10-01

The inoculum effect (IE) is an increase in the minimum inhibitory concentration (MIC) of an antibiotic as a function of the initial size of a microbial population. The IE has been observed in a wide range of bacteria, implying that antibiotic efficacy may depend on population density. Such density dependence could have dramatic effects on bacterial population dynamics and potential treatment strategies, but explicit measures of per capita growth as a function of density are generally not available. Instead, the IE measures MIC as a function of initial population size, and population density changes by many orders of magnitude on the timescale of the experiment. Therefore, the functional relationship between population density and antibiotic inhibition is generally not known, leaving many questions about the impact of the IE on different treatment strategies unanswered. To address these questions, here we directly measured real-time per capita growth of Enterococcus faecalis populations exposed to antibiotic at fixed population densities using multiplexed computer-automated culture devices. We show that density-dependent growth inhibition is pervasive for commonly used antibiotics, with some drugs showing increased inhibition and others decreased inhibition at high densities. For several drugs, the density dependence is mediated by changes in extracellular pH, a community-level phenomenon not previously linked with the IE. Using a simple mathematical model, we demonstrate how this density dependence can modulate population dynamics in constant drug environments. Then, we illustrate how time-dependent dosing strategies can mitigate the negative effects of density-dependence. Finally, we show that these density effects lead to bistable treatment outcomes for a wide range of antibiotic concentrations in a pharmacological model of antibiotic treatment. As a result, infections exceeding a critical density often survive otherwise effective treatments.

Population Density Modulates Drug Inhibition and Gives Rise to Potential Bistability of Treatment Outcomes for Bacterial Infections

PubMed Central

Maltas, Jeff; Brumm, Peter; Wood, Kevin B.

2016-01-01

The inoculum effect (IE) is an increase in the minimum inhibitory concentration (MIC) of an antibiotic as a function of the initial size of a microbial population. The IE has been observed in a wide range of bacteria, implying that antibiotic efficacy may depend on population density. Such density dependence could have dramatic effects on bacterial population dynamics and potential treatment strategies, but explicit measures of per capita growth as a function of density are generally not available. Instead, the IE measures MIC as a function of initial population size, and population density changes by many orders of magnitude on the timescale of the experiment. Therefore, the functional relationship between population density and antibiotic inhibition is generally not known, leaving many questions about the impact of the IE on different treatment strategies unanswered. To address these questions, here we directly measured real-time per capita growth of Enterococcus faecalis populations exposed to antibiotic at fixed population densities using multiplexed computer-automated culture devices. We show that density-dependent growth inhibition is pervasive for commonly used antibiotics, with some drugs showing increased inhibition and others decreased inhibition at high densities. For several drugs, the density dependence is mediated by changes in extracellular pH, a community-level phenomenon not previously linked with the IE. Using a simple mathematical model, we demonstrate how this density dependence can modulate population dynamics in constant drug environments. Then, we illustrate how time-dependent dosing strategies can mitigate the negative effects of density-dependence. Finally, we show that these density effects lead to bistable treatment outcomes for a wide range of antibiotic concentrations in a pharmacological model of antibiotic treatment. As a result, infections exceeding a critical density often survive otherwise effective treatments. PMID:27764095

Electron dynamics inside a vacuum tube diode through linear differential equations

NASA Astrophysics Data System (ADS)

González, Gabriel; Orozco, Fco. Javier González; Orozco

2014-04-01

In this paper we analyze the motion of charged particles in a vacuum tube diode by solving linear differential equations. Our analysis is based on expressing the volume charge density as a function of the current density and coordinates only, i.e. ρ=ρ(J,z), while in the usual scheme the volume charge density is expressed as a function of the current density and electrostatic potential, i.e. ρ=ρ(J,V). We show that, in the case of slow varying charge density, the space-charge-limited current is reduced up to 50%. Our approach gives the well-known behavior of the classical current density proportional to the three-halves power of the bias potential and inversely proportional to the square of the gap distance between electrodes, and does not require the solution of the nonlinear differential equation normally associated with the Child-Langmuir formulation.

Subsystem real-time time dependent density functional theory.

PubMed

Krishtal, Alisa; Ceresoli, Davide; Pavanello, Michele

2015-04-21

We present the extension of Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) to real-time Time Dependent Density Functional Theory (rt-TDDFT). FDE is a DFT-in-DFT embedding method that allows to partition a larger Kohn-Sham system into a set of smaller, coupled Kohn-Sham systems. Additional to the computational advantage, FDE provides physical insight into the properties of embedded systems and the coupling interactions between them. The extension to rt-TDDFT is done straightforwardly by evolving the Kohn-Sham subsystems in time simultaneously, while updating the embedding potential between the systems at every time step. Two main applications are presented: the explicit excitation energy transfer in real time between subsystems is demonstrated for the case of the Na4 cluster and the effect of the embedding on optical spectra of coupled chromophores. In particular, the importance of including the full dynamic response in the embedding potential is demonstrated.

Excited State Charge Transfer reaction with dual emission from 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile: Spectral measurement and theoretical density functional theory calculation

NASA Astrophysics Data System (ADS)

Jana, Sankar; Dalapati, Sasanka; Ghosh, Shalini; Kar, Samiran; Guchhait, Nikhil

2011-07-01

The excited state intramolecular charge transfer process in donor-chromophore-acceptor system 5-(4-dimethylamino-phenyl)-penta-2,4-dienenitrile (DMAPPDN) has been investigated by steady state absorption and emission spectroscopy in combination with Density Functional Theory (DFT) calculations. This flexible donor acceptor molecule DMAPPDN shows dual fluorescence corresponding to emission from locally excited and charge transfer state in polar solvent. Large solvatochromic emission shift, effect of variation of pH and HOMO-LUMO molecular orbital pictures support excited state intramolecular charge transfer process. The experimental findings have been correlated with the calculated structure and potential energy surfaces based on the Twisted Intramolecular Charge Transfer (TICT) model obtained at DFT level using B3LYP functional and 6-31+G( d, p) basis set. The theoretical potential energy surfaces for the excited states have been generated in vacuo and acetonitrile solvent using Time Dependent Density Functional Theory (TDDFT) and Time Dependent Density Functional Theory Polarized Continuum Model (TDDFT-PCM) method, respectively. All the theoretical results show well agreement with the experimental observations.

Benchmark study of ionization potentials and electron affinities of armchair single-walled carbon nanotubes using density functional theory

NASA Astrophysics Data System (ADS)

Zhou, Bin; Hu, Zhubin; Jiang, Yanrong; He, Xiao; Sun, Zhenrong; Sun, Haitao

2018-05-01

The intrinsic parameters of carbon nanotubes (CNTs) such as ionization potential (IP) and electron affinity (EA) are closely related to their unique properties and associated applications. In this work, we demonstrated the success of optimal tuning method based on range-separated (RS) density functionals for both accurate and efficient prediction of vertical IPs and electron affinities (EAs) of a series of armchair single-walled carbon nanotubes C20n H20 (n  =  2–6) compared to the high-level IP/EA equation-of-motion coupled-cluster method with single and double substitutions (IP/EA-EOM-CCSD). Notably, the resulting frontier orbital energies (–ε HOMO and –ε LUMO) from the tuning method exhibit an excellent approximation to the corresponding IPs and EAs, that significantly outperform other conventional density functionals. In addition, it is suggested that the RS density functionals that possess both a fixed amount of exact exchange in the short-range and a correct long-range asymptotic behavior are suitable for calculating electronic structures of finite-sized CNTs. Next the performance of density functionals for description of various molecular properties such as chemical potential, hardness and electrophilicity are assessed as a function of tube length. Thanks to the efficiency and accuracy of this tuning method, the related behaviors of much longer armchair single-walled CNTs until C200H20 were studied. Lastly, the present work is proved to provide an efficient theoretical tool for future materials design and reliable characterization of other interesting properties of CNT-based systems.

A Density Functional Approach to Polarizable Models: A Kim-Gordon-Response Density Interaction Potential for Molecular Simulations

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

Tabacchi, G; Hutter, J; Mundy, C

2005-04-07

A combined linear response--frozen electron density model has been implemented in a molecular dynamics scheme derived from an extended Lagrangian formalism. This approach is based on a partition of the electronic charge distribution into a frozen region described by Kim-Gordon theory, and a response contribution determined by the instaneous ionic configuration of the system. The method is free from empirical pair-potentials and the parameterization protocol involves only calculations on properly chosen subsystems. They apply this method to a series of alkali halides in different physical phases and are able to reproduce experimental structural and thermodynamic properties with an accuracy comparablemore » to Kohn-Sham density functional calculations.« less

Effect of short-range correlations on the single proton 3s1/2 wave function in 206Pb

NASA Astrophysics Data System (ADS)

Shlomo, S.; Talmi, I.; Anders, M. R.; Bonasera, G.

2018-02-01

We consider the experimental data for difference, Δρc (r), between the charge density distributions of the isotones 206Pb - 205Tl, deduced by analysis of elastic electron scattering measurements and corresponds to the shell model 3s1/2 proton orbit. We investigate the effects of two-body short-range correlations. This is done by: (a) Determining the corresponding single particle potential (mean-field), employing a novel method, directly from the single particle proton density and its first and second derivatives. We also carried out least-square fits to parametrized single particle potentials; (b) Determining the short-range correlations effect by employing the Jastrow correlated many-body wave function to derive a correlation factor for the single particle density distribution. The 3s 1/2 wave functions of the determined potentials reproduce fairly well the experimental data within the quoted errors. The calculated charge density difference, Δρc (r), obtained with the inclusion of the short-range correlation effect does not reproduce the experimental data.

In search of a viable reaction pathway in the chelation of a metallo-protein

NASA Astrophysics Data System (ADS)

Rose, Frisco; Hodak, Miroslav; Bernholc, Jerry

2010-03-01

Misfolded metallo-proteins are potential causal agents in the onset of neuro-degenerative diseases, such as Alzheimer's and Parkinson's Diseases (PD). Experimental results involving metal chelation have shown significant promise in symptom reduction and misfolding reversal. We explore, through atomistic simulations, potential reaction pathways for the chelation of Cu^2+ from the metal binding site in our representation of a partially misfolded α-synuclein, the protein implicated in PD. Our ab initio simulations use Density Functional Theory (DFT) and nudged elastic band to obtain the minimized energy coordinates of this reaction. Our simulations include ab initio water at the interaction site and in its first solvation shells, while the remainder is fully solvated with orbital-free DFT water representation [1]. Our ongoing studies of viable chelation agents include nicotine, caffeine and other potential reagents, we will review the best case agents in this presentation. [4pt] [1] Hodak M, Lu W, Bernholc J. Hybrid ab initio Kohn-Sham density functional theory/frozen-density orbital-free density functional theory simulation method suitable for biological systems. J. Chem. Phys. 2008 Jan;128(1):014101-9.

Kinetic Energy of Hydrocarbons as a Function of Electron Density and Convolutional Neural Networks.

PubMed

Yao, Kun; Parkhill, John

2016-03-08

We demonstrate a convolutional neural network trained to reproduce the Kohn-Sham kinetic energy of hydrocarbons from an input electron density. The output of the network is used as a nonlocal correction to conventional local and semilocal kinetic functionals. We show that this approximation qualitatively reproduces Kohn-Sham potential energy surfaces when used with conventional exchange correlation functionals. The density which minimizes the total energy given by the functional is examined in detail. We identify several avenues to improve on this exploratory work, by reducing numerical noise and changing the structure of our functional. Finally we examine the features in the density learned by the neural network to anticipate the prospects of generalizing these models.

Kohn-Sham approach to quantum electrodynamical density-functional theory: Exact time-dependent effective potentials in real space.

PubMed

Flick, Johannes; Ruggenthaler, Michael; Appel, Heiko; Rubio, Angel

2015-12-15

The density-functional approach to quantum electrodynamics extends traditional density-functional theory and opens the possibility to describe electron-photon interactions in terms of effective Kohn-Sham potentials. In this work, we numerically construct the exact electron-photon Kohn-Sham potentials for a prototype system that consists of a trapped electron coupled to a quantized electromagnetic mode in an optical high-Q cavity. Although the effective current that acts on the photons is known explicitly, the exact effective potential that describes the forces exerted by the photons on the electrons is obtained from a fixed-point inversion scheme. This procedure allows us to uncover important beyond-mean-field features of the effective potential that mark the breakdown of classical light-matter interactions. We observe peak and step structures in the effective potentials, which can be attributed solely to the quantum nature of light; i.e., they are real-space signatures of the photons. Our findings show how the ubiquitous dipole interaction with a classical electromagnetic field has to be modified in real space to take the quantum nature of the electromagnetic field fully into account.

Multiconfiguration Pair-Density Functional Theory.

PubMed

Li Manni, Giovanni; Carlson, Rebecca K; Luo, Sijie; Ma, Dongxia; Olsen, Jeppe; Truhlar, Donald G; Gagliardi, Laura

2014-09-09

We present a new theoretical framework, called Multiconfiguration Pair-Density Functional Theory (MC-PDFT), which combines multiconfigurational wave functions with a generalization of density functional theory (DFT). A multiconfigurational self-consistent-field (MCSCF) wave function with correct spin and space symmetry is used to compute the total electronic density, its gradient, the on-top pair density, and the kinetic and Coulomb contributions to the total electronic energy. We then use a functional of the total density, its gradient, and the on-top pair density to calculate the remaining part of the energy, which we call the on-top-density-functional energy in contrast to the exchange-correlation energy of Kohn-Sham DFT. Because the on-top pair density is an element of the two-particle density matrix, this goes beyond the Hohenberg-Kohn theorem that refers only to the one-particle density. To illustrate the theory, we obtain first approximations to the required new type of density functionals by translating conventional density functionals of the spin densities using a simple prescription, and we perform post-SCF density functional calculations using the total density, density gradient, and on-top pair density from the MCSCF calculations. Double counting of dynamic correlation or exchange does not occur because the MCSCF energy is not used. The theory is illustrated by applications to the bond energies and potential energy curves of H2, N2, F2, CaO, Cr2, and NiCl and the electronic excitation energies of Be, C, N, N(+), O, O(+), Sc(+), Mn, Co, Mo, Ru, N2, HCHO, C4H6, c-C5H6, and pyrazine. The method presented has a computational cost and scaling similar to MCSCF, but a quantitative accuracy, even with the present first approximations to the new types of density functionals, that is comparable to much more expensive multireference perturbation theory methods.

Density functional study of double ionization energies

NASA Astrophysics Data System (ADS)

Chong, D. P.

2008-02-01

In this paper, double ionization energies (DIEs) of gas-phase atoms and molecules are calculated by energy difference method with density functional theory. To determine the best functional for double ionization energies, we first study 24 main group atoms in the second, third, and fourth periods. An approximation is used in which the electron density is first obtained from a density functional computation with the exchange-correlation potential Vxc known as statistical average of orbital potentials, after which the energy is computed from that density with 59 different exchange-correlation energy functionals Exc. For the 24 atoms, the two best Exc functional providing DIEs with average absolute deviation (AAD) of only 0.25eV are the Perdew-Burke-Ernzerhof functional modified by Hammer et al. [Phys. Rev. B 59, 6413 (1999)] and one known as the Krieger-Chen-Iafrate-Savin functional modified by Krieger et al. (unpublished). Surprisingly, none of the 20 available hybrid functionals is among the top 15 functionals for the DIEs of the 24 atoms. A similar procedure is then applied to molecules, with opposite results: Only hybrid functionals are among the top 15 functionals for a selection of 29molecules. The best Exc functional for the 29molecules is found to be the Becke 1997 functional modified by Wilson et al. [J. Chem. Phys. 115, 9233 (2001)]. With that functional, the AAD from experiment for DIEs of 29molecules is just under 0.5eV. If the two suspected values for C2H2 and Fe(CO)5 are excluded, the AAD improves to 0.32eV. Many other hybrid functionals perform almost as well.

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

Sahu, Sivabrata, E-mail: siva1987@iopb.res.in; Parashar, S. K. S., E-mail: sksparashar@yahoo.com; Rout, G. C., E-mail: gcr@iopb.res.in

We address here a tight-binding theoretical model calculation for AA-stacked bi-layer graphene taking into account of a biased potential between two layers to study the density of states and the band dispersion within the total Brillouin zone. We have calculated the electronic Green’s function for electron operator corresponding to A and B sub lattices by Zubarev’s Green’s function technique from which the electronic density of states and the electron band energy dispersion are calculated. The numerically computed density of states and band energy dispersions are investigated by tuning the biased potential to exhibit the band gap by varying the differentmore » physical parameters.« less

Analysis of density effects in plasmas and their influence on electron-impact cross sections

NASA Astrophysics Data System (ADS)

Belkhiri, M.; Poirier, M.

2014-12-01

Density effects in plasmas are analyzed using a Thomas-Fermi approach for free electrons. First, scaling properties are determined for the free-electron potential and density. For hydrogen-like ions, the first two terms of an analytical expansion of this potential as a function of the plasma coupling parameter are obtained. In such ions, from these properties and numerical calculations, a simple analytical fit is proposed for the plasma potential, which holds for any electron density, temperature, and atomic number, at least assuming that Maxwell-Boltzmann statistics is applicable. This allows one to analyze perturbatively the influence of the plasma potential on energies, wave functions, transition rates, and electron-impact collision rates for single-electron ions. Second, plasmas with an arbitrary charge state are considered, using a modified version of the Flexible Atomic Code (FAC) package with a plasma potential based on a Thomas-Fermi approach. Various methods for the collision cross-section calculations are reviewed. The influence of plasma density on these cross sections is analyzed in detail. Moreover, it is demonstrated that, in a given transition, the radiative and collisional-excitation rates are differently affected by the plasma density. Some analytical expressions are proposed for hydrogen-like ions in the limit where the Born or Lotz approximation applies and are compared to the numerical results from the FAC.

Uniform magnetic fields in density-functional theory

NASA Astrophysics Data System (ADS)

Tellgren, Erik I.; Laestadius, Andre; Helgaker, Trygve; Kvaal, Simen; Teale, Andrew M.

2018-01-01

We construct a density-functional formalism adapted to uniform external magnetic fields that is intermediate between conventional density functional theory and Current-Density Functional Theory (CDFT). In the intermediate theory, which we term linear vector potential-DFT (LDFT), the basic variables are the density, the canonical momentum, and the paramagnetic contribution to the magnetic moment. Both a constrained-search formulation and a convex formulation in terms of Legendre-Fenchel transformations are constructed. Many theoretical issues in CDFT find simplified analogs in LDFT. We prove results concerning N-representability, Hohenberg-Kohn-like mappings, existence of minimizers in the constrained-search expression, and a restricted analog to gauge invariance. The issue of additivity of the energy over non-interacting subsystems, which is qualitatively different in LDFT and CDFT, is also discussed.

Uniform magnetic fields in density-functional theory.

PubMed

Tellgren, Erik I; Laestadius, Andre; Helgaker, Trygve; Kvaal, Simen; Teale, Andrew M

2018-01-14

We construct a density-functional formalism adapted to uniform external magnetic fields that is intermediate between conventional density functional theory and Current-Density Functional Theory (CDFT). In the intermediate theory, which we term linear vector potential-DFT (LDFT), the basic variables are the density, the canonical momentum, and the paramagnetic contribution to the magnetic moment. Both a constrained-search formulation and a convex formulation in terms of Legendre-Fenchel transformations are constructed. Many theoretical issues in CDFT find simplified analogs in LDFT. We prove results concerning N-representability, Hohenberg-Kohn-like mappings, existence of minimizers in the constrained-search expression, and a restricted analog to gauge invariance. The issue of additivity of the energy over non-interacting subsystems, which is qualitatively different in LDFT and CDFT, is also discussed.

Combining Density Functional Theory and Green's Function Theory: Range-Separated, Nonlocal, Dynamic, and Orbital-Dependent Hybrid Functional.

PubMed

Kananenka, Alexei A; Zgid, Dominika

2017-11-14

We present a rigorous framework which combines single-particle Green's function theory with density functional theory based on a separation of electron-electron interactions into short- and long-range components. Short-range contribution to the total energy and exchange-correlation potential is provided by a density functional approximation, while the long-range contribution is calculated using an explicit many-body Green's function method. Such a hybrid results in a nonlocal, dynamic, and orbital-dependent exchange-correlation functional of a single-particle Green's function. In particular, we present a range-separated hybrid functional called srSVWN5-lrGF2 which combines the local-density approximation and the second-order Green's function theory. We illustrate that similarly to density functional approximations, the new functional is weakly basis-set dependent. Furthermore, it offers an improved description of the short-range dynamic correlation. The many-body contribution to the functional mitigates the many-electron self-interaction error present in many density functional approximations and provides a better description of molecular properties. Additionally, we illustrate that the new functional can be used to scale down the self-energy and, therefore, introduce an additional sparsity to the self-energy matrix that in the future can be exploited in calculations for large molecules or periodic systems.

Bypassing the Kohn-Sham equations with machine learning.

PubMed

Brockherde, Felix; Vogt, Leslie; Li, Li; Tuckerman, Mark E; Burke, Kieron; Müller, Klaus-Robert

2017-10-11

Last year, at least 30,000 scientific papers used the Kohn-Sham scheme of density functional theory to solve electronic structure problems in a wide variety of scientific fields. Machine learning holds the promise of learning the energy functional via examples, bypassing the need to solve the Kohn-Sham equations. This should yield substantial savings in computer time, allowing larger systems and/or longer time-scales to be tackled, but attempts to machine-learn this functional have been limited by the need to find its derivative. The present work overcomes this difficulty by directly learning the density-potential and energy-density maps for test systems and various molecules. We perform the first molecular dynamics simulation with a machine-learned density functional on malonaldehyde and are able to capture the intramolecular proton transfer process. Learning density models now allows the construction of accurate density functionals for realistic molecular systems.Machine learning allows electronic structure calculations to access larger system sizes and, in dynamical simulations, longer time scales. Here, the authors perform such a simulation using a machine-learned density functional that avoids direct solution of the Kohn-Sham equations.

Towards time-dependent current-density-functional theory in the non-linear regime

NASA Astrophysics Data System (ADS)

Escartín, J. M.; Vincendon, M.; Romaniello, P.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.

2015-02-01

Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT. This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na2. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.

Towards time-dependent current-density-functional theory in the non-linear regime.

PubMed

Escartín, J M; Vincendon, M; Romaniello, P; Dinh, P M; Reinhard, P-G; Suraud, E

2015-02-28

Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT. This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na2. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.

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.

Interaction potential for indium phosphide: a molecular dynamics and first-principles study of the elastic constants, generalized stacking fault and surface energies.

PubMed

Branicio, Paulo Sergio; Rino, José Pedro; Gan, Chee Kwan; Tsuzuki, Hélio

2009-03-04

Indium phosphide is investigated using molecular dynamics (MD) simulations and density-functional theory calculations. MD simulations use a proposed effective interaction potential for InP fitted to a selected experimental dataset of properties. The potential consists of two- and three-body terms that represent atomic-size effects, charge-charge, charge-dipole and dipole-dipole interactions as well as covalent bond bending and stretching. Predictions are made for the elastic constants as a function of density and temperature, the generalized stacking fault energy and the low-index surface energies.

Effect of impurity doping on tunneling conductance in AB-stacked bi-layer graphene: A tight-binding study

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

Rout, G. C., E-mail: siva1987@iopb.res.in, E-mail: skp@iopb.res.in, E-mail: gcr@iopb.res.in; Sahu, Sivabrata; Panda, S. K.

2016-04-13

We report here a microscopic tight-binding model calculation for AB-stacked bilayer graphene in presence of biasing potential between the two layers and the impurity effects to study the evolution of the total density of states with special emphasis on opening of band gap near Dirac point. We have calculated the electron Green’s functions for both the A and B sub-lattices by Zubarev technique. The imaginary part of the Green’s function gives the partial and total density of states of electrons. The density of states are computed numerically for 1000 × 1000 grid points of the electron momentum. The evolution ofmore » the opening of band gap near van-Hove singularities as well as near Dirac point is investigated by varying the different interlayer hoppings and the biasing potentials. The inter layer hopping splits the density of states at van-Hove singularities and produces a V-shaped gap near Dirac point. Further the biasing potential introduces a U shaped gap near Dirac point with a density minimum at the applied potential(i.e. at V/2).« less

Force-field functor theory: classical force-fields which reproduce equilibrium quantum distributions

PubMed Central

Babbush, Ryan; Parkhill, John; Aspuru-Guzik, Alán

2013-01-01

Feynman and Hibbs were the first to variationally determine an effective potential whose associated classical canonical ensemble approximates the exact quantum partition function. We examine the existence of a map between the local potential and an effective classical potential which matches the exact quantum equilibrium density and partition function. The usefulness of such a mapping rests in its ability to readily improve Born-Oppenheimer potentials for use with classical sampling. We show that such a map is unique and must exist. To explore the feasibility of using this result to improve classical molecular mechanics, we numerically produce a map from a library of randomly generated one-dimensional potential/effective potential pairs then evaluate its performance on independent test problems. We also apply the map to simulate liquid para-hydrogen, finding that the resulting radial pair distribution functions agree well with path integral Monte Carlo simulations. The surprising accessibility and transferability of the technique suggest a quantitative route to adapting Born-Oppenheimer potentials, with a motivation similar in spirit to the powerful ideas and approximations of density functional theory. PMID:24790954

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

Gledhill, Jonathan D.; Tozer, David J., E-mail: d.j.tozer@durham.ac.uk

Density scaling considerations are used to derive an exchange–correlation explicit density functional that is appropriate for the electron deficient side of the integer and which recovers the exact r → ∞ asymptotic behaviour of the exchange–correlation potential. The functional has an unconventional mathematical form with parameters that are system-dependent; the parameters for an N-electron system are determined in advance from generalised gradient approximation (GGA) calculations on the N- and (N − 1)-electron systems. Compared to GGA results, the functional yields similar exchange–correlation energies, but HOMO energies that are an order of magnitude closer to the negative of the vertical ionisationmore » potential; for anions, the HOMO energies are negative, as required. Rydberg excitation energies are also notably improved and the exchange–correlation potential is visibly lowered towards the near-exact potential. Further development is required to improve valence excitations, static isotropic polarisabilities, and the shape of the potential in non-asymptotic regions. The functional is fundamentally different to conventional approximations.« less

Time-dependent density-functional theory with optimized effective potential and self-interaction correction and derivative discontinuity for the treatment of double ionization of He and Be atoms in intense laser fields

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry A.; Chu, Shih-I.

2013-05-01

We present a self-interaction-free time-dependent density-functional theory (TDDFT) for the treatment of double-ionization processes of many-electron systems. The method is based on the extension of the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential (OEP) theory and the incorporation of an explicit self-interaction correction (SIC) term. In the framework of the time-dependent density functional theory, we have performed three-dimensional (3D) calculations of double ionization of He and Be atoms by intense near-infrared laser fields. We make use of the exchange-correlation potential with the integer discontinuity which improves the description of the double-ionization process. We found that a proper description of the double ionization requires the TDDFT exchange-correlation potential with the discontinuity with respect to the variation of the total particle number (TPN). The results for the intensity-dependent rates of double ionization of He and Be atoms are presented.

Density functional theory calculations of III-N based semiconductors with mBJLDA

NASA Astrophysics Data System (ADS)

Gürel, Hikmet Hakan; Akıncı, Özden; Ünlü, Hilmi

2017-02-01

In this work, we present first principles calculations based on a full potential linear augmented plane-wave method (FP-LAPW) to calculate structural and electronic properties of III-V based nitrides such as GaN, AlN, InN in a zinc-blende cubic structure. First principles calculation using the local density approximation (LDA) and generalized gradient approximation (GGA) underestimate the band gap. We proposed a new potential called modified Becke-Johnson local density approximation (MBJLDA) that combines modified Becke-Johnson exchange potential and the LDA correlation potential to get better band gap results compared to experiment. We compared various exchange-correlation potentials (LSDA, GGA, HSE, and MBJLDA) to determine band gaps and structural properties of semiconductors. We show that using MBJLDA density potential gives a better agreement with experimental data for band gaps III-V nitrides based semiconductors.

The structure, energetics, and nature of the chemical bonding of phenylthiol adsorbed on the Au(111) surface: implications for density-functional calculations of molecular-electronic conduction.

PubMed

Bilić, Ante; Reimers, Jeffrey R; Hush, Noel S

2005-03-01

The adsorption of phenylthiol on the Au(111) surface is modeled using Perdew and Wang density-functional calculations. Both direct molecular physisorption and dissociative chemisorption via S-H bond cleavage are considered as well as dimerization to form disulfides. For the major observed product, the chemisorbed thiol, an extensive potential-energy surface is produced as a function of both the azimuthal orientation of the adsorbate and the linear translation of the adsorbate through the key fcc, hcp, bridge, and top binding sites. Key structures are characterized, the lowest-energy one being a broad minimum of tilted orientation ranging from the bridge structure halfway towards the fcc one. The vertically oriented threefold binding sites, often assumed to dominate molecular electronics measurements, are identified as transition states at low coverage but become favored in dense monolayers. A similar surface is also produced for chemisorption of phenylthiol on Ag(111); this displays significant qualitative differences, consistent with the qualitatively different observed structures for thiol chemisorption on Ag and Au. Full contours of the minimum potential energy as a function of sulfur translation over the crystal face are described, from which the barrier to diffusion is deduced to be 5.8 kcal mol(-1), indicating that the potential-energy surface has low corrugation. The calculated bond lengths, adsorbate charge and spin density, and the density of electronic states all indicate that, at all sulfur locations, the adsorbate can be regarded as a thiyl species that forms a net single covalent bond to the surface of strength 31 kcal mol(-1). No detectable thiolate character is predicted, however, contrary to experimental results for alkyl thiols that indicate up to 20%-30% thiolate involvement. This effect is attributed to the asymptotic-potential error of all modern density functionals that becomes manifest through a 3-4 eV error in the lineup of the adsorbate and substrate bands. Significant implications are described for density-functional calculations of through-molecule electron transport in molecular electronics.

Exchange-correlation approximations for reduced-density-matrix-functional theory at finite temperature: Capturing magnetic phase transitions in the homogeneous electron gas

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

Baldsiefen, Tim; Cangi, Attila; Eich, F. G.

Here, we derive an intrinsically temperature-dependent approximation to the correlation grand potential for many-electron systems in thermodynamical equilibrium in the context of finite-temperature reduced-density-matrix-functional theory (FT-RDMFT). We demonstrate its accuracy by calculating the magnetic phase diagram of the homogeneous electron gas. We compare it to known limits from highly accurate quantum Monte Carlo calculations as well as to phase diagrams obtained within existing exchange-correlation approximations from density functional theory and zero-temperature RDMFT.

Connection formulas for thermal density functional theory

DOE PAGES

Pribram-Jones, A.; Burke, K.

2016-05-23

We show that the adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upward from the system's physical temperature. We also show how to relate different correlation components to each other, either in terms of temperature or coupling-constant integrations. Lastly, we illustrate our results on the uniform electron gas.

Exchange-correlation approximations for reduced-density-matrix-functional theory at finite temperature: Capturing magnetic phase transitions in the homogeneous electron gas

DOE PAGES

Baldsiefen, Tim; Cangi, Attila; Eich, F. G.; ...

2017-12-18

Here, we derive an intrinsically temperature-dependent approximation to the correlation grand potential for many-electron systems in thermodynamical equilibrium in the context of finite-temperature reduced-density-matrix-functional theory (FT-RDMFT). We demonstrate its accuracy by calculating the magnetic phase diagram of the homogeneous electron gas. We compare it to known limits from highly accurate quantum Monte Carlo calculations as well as to phase diagrams obtained within existing exchange-correlation approximations from density functional theory and zero-temperature RDMFT.

Optimized effective potential in real time: Problems and prospects in time-dependent density-functional theory

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

Mundt, Michael; Kuemmel, Stephan

2006-08-15

The integral equation for the time-dependent optimized effective potential (TDOEP) in time-dependent density-functional theory is transformed into a set of partial-differential equations. These equations only involve occupied Kohn-Sham orbitals and orbital shifts resulting from the difference between the exchange-correlation potential and the orbital-dependent potential. Due to the success of an analog scheme in the static case, a scheme that propagates orbitals and orbital shifts in real time is a natural candidate for an exact solution of the TDOEP equation. We investigate the numerical stability of such a scheme. An approximation beyond the Krieger-Li-Iafrate approximation for the time-dependent exchange-correlation potential ismore » analyzed.« less

Gurtin-Murdoch surface elasticity theory revisit: An orbital-free density functional theory perspective

NASA Astrophysics Data System (ADS)

Zhu, Yichao; Wei, Yihai; Guo, Xu

2017-12-01

In the present paper, the well-established Gurtin-Murdoch theory of surface elasticity (Gurtin and Murdoch, 1975, 1978) is revisited from an orbital-free density functional theory (OFDFT) perspective by taking the boundary layer into consideration. Our analysis indicates that firstly, the quantities introduced in the Gurtin-Murdoch theory of surface elasticity can all find their explicit expressions in the derived OFDFT-based theoretical model. Secondly, the derived expression for surface energy density captures a competition between the surface normal derivatives of the electron density and the electrostatic potential, which well rationalises the onset of signed elastic constants that are observed both experimentally and computationally. Thirdly, the established model naturally yields an inversely linear relationship between the materials surface stiffness and its size, which conforms to relevant findings in literature. Since the proposed OFDFT-based model is established under arbitrarily imposed boundary condition of electron density, electrostatic potential and external load, it also has the potential of being used to investigate the electro-mechanical behaviour of nanoscale materials manifesting surface effect.

Constraints on physiological function associated with branch architecture and wood density in tropical forest trees

Treesearch

Frederick C. Meinzer; Paula I. Campanello; Jean-Christophe Domec; M. Genoveva Gatti; Guillermo Goldstein; Randol Villalobos-Vega; David R. Woodruff

2008-01-01

This study examined how leaf and stem functional traits related to gas exchange and water balance scale with two potential proxies for tree hydraulic architecture: the leaf area:sapwood area ratio (AL:AS) and wood density (W). We studied the upper crowns of individuals of 15 tropical forest...

An EQT-cDFT approach to determine thermodynamic properties of confined fluids.

PubMed

Mashayak, S Y; Motevaselian, M H; Aluru, N R

2015-06-28

We present a continuum-based approach to predict the structure and thermodynamic properties of confined fluids at multiple length-scales, ranging from a few angstroms to macro-meters. The continuum approach is based on the empirical potential-based quasi-continuum theory (EQT) and classical density functional theory (cDFT). EQT is a simple and fast approach to predict inhomogeneous density and potential profiles of confined fluids. We use EQT potentials to construct a grand potential functional for cDFT. The EQT-cDFT-based grand potential can be used to predict various thermodynamic properties of confined fluids. In this work, we demonstrate the EQT-cDFT approach by simulating Lennard-Jones fluids, namely, methane and argon, confined inside slit-like channels of graphene. We show that the EQT-cDFT can accurately predict the structure and thermodynamic properties, such as density profiles, adsorption, local pressure tensor, surface tension, and solvation force, of confined fluids as compared to the molecular dynamics simulation results.

Immigration Rates during Population Density Reduction in a Coral Reef Fish

PubMed Central

Turgeon, Katrine; Kramer, Donald L.

2016-01-01

Although the importance of density-dependent dispersal has been recognized in theory, few empirical studies have examined how immigration changes over a wide range of densities. In a replicated experiment using a novel approach allowing within-site comparison, we examined changes in immigration rate following the gradual removal of territorial damselfish from a limited area within a much larger patch of continuous habitat. In all sites, immigration occurred at intermediate densities but did not occur before the start of removals and only rarely as density approached zero. In the combined data and in 5 of 7 sites, the number of immigrants was a hump-shaped function of density. This is the first experimental evidence for hump-shaped, density-dependent immigration. This pattern may be more widespread than previously recognized because studies over more limited density ranges have identified positive density dependence at low densities and negative density dependence at high densities. Positive density dependence at low density can arise from limits to the number of potential immigrants and from behavioral preferences for settling near conspecifics. Negative density dependence at high density can arise from competition for resources, especially high quality territories. The potential for non-linear effects of local density on immigration needs to be recognized for robust predictions of conservation reserve function, harvest impacts, pest control, and the dynamics of fragmented populations. PMID:27271081

From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties.

PubMed

Xu, Xin; Goddard, William A

2004-03-02

We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA.

From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties

NASA Astrophysics Data System (ADS)

Xu, Xin; Goddard, William A., III

2004-03-01

We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee-Yang-Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee-Yang-Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA.

The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties

PubMed Central

Xu, Xin; Goddard, William A.

2004-01-01

We derive the form for an exact exchange energy density for a density decaying with Gaussian-like behavior at long range. Based on this, we develop the X3LYP (extended hybrid functional combined with Lee–Yang–Parr correlation functional) extended functional for density functional theory to significantly improve the accuracy for hydrogen-bonded and van der Waals complexes while also improving the accuracy in heats of formation, ionization potentials, electron affinities, and total atomic energies [over the most popular and accurate method, B3LYP (Becke three-parameter hybrid functional combined with Lee–Yang–Parr correlation functional)]. X3LYP also leads to a good description of dipole moments, polarizabilities, and accurate excitation energies from s to d orbitals for transition metal atoms and ions. We suggest that X3LYP will be useful for predicting ligand binding in proteins and DNA. PMID:14981235

Surface effects on mean inner potentials studied using density functional theory.

PubMed

Pennington, Robert S; Boothroyd, Chris B; Dunin-Borkowski, Rafal E

2015-12-01

Quantitative materials characterization using electron holography frequently requires knowledge of the mean inner potential, but reported experimental mean inner potential measurements can vary widely. Using density functional theory, we have simulated the mean inner potential for materials with a range of different surface conditions and geometries. We use both "thin-film" and "nanowire" specimen geometries. We consider clean bulk-terminated surfaces with different facets and surface reconstructions using atom positions from both structural optimization and experimental data and we also consider surfaces both with and without adsorbates. We find that the mean inner potential is surface-dependent, with the strongest dependency on surface adsorbates. We discuss the outlook and perspective for future mean inner potential measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Multiconfiguration Pair-Density Functional Theory: A New Way To Treat Strongly Correlated Systems.

PubMed

Gagliardi, Laura; Truhlar, Donald G; Li Manni, Giovanni; Carlson, Rebecca K; Hoyer, Chad E; Bao, Junwei Lucas

2017-01-17

The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than being a function of the spin-up and spin-down densities. In work carried out so far, the multiconfigurational wave function is a multiconfiguration self-consistent-field wave function. The new formulation has the advantage that the reference wave function has the correct spatial and spin symmetry and can describe bond dissociation (of both single and multiple bonds) and electronic excitations in a formally and physically correct way. We then review the formulation of density functionals in terms of the on-top pair density. Finally we review successful applications of the theory to bond energies and bond dissociation potential energy curves of main-group and transition metal bonds, to barrier heights (including pericyclic reactions), to proton affinities, to the hydrogen bond energy of water dimer, to ground- and excited-state charge transfer, to valence and Rydberg excitations of molecules, and to singlet-triplet splittings of radicals. We find that that MC-PDFT can give accurate results not only with complete-active-space multiconfiguration wave functions but also with generalized-active-space multiconfiguration wave functions, which are practical for larger numbers of active electrons and active orbitals than are complete-active-space wave functions. The separated-pair approximation, which is a special case of generalized active space self-consistent-field theory, is especially promising. MC-PDFT, because it requires much less computer time and storage than pure WFT methods, has the potential to open larger and more complex strongly correlated systems to accurate simulation.

Qualitative breakdown of the unrestricted Hartree-Fock energy

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

Mori-Sánchez, Paula, E-mail: paula.mori@uam.es; Cohen, Aron J., E-mail: ajc54@cam.ac.uk

2014-10-28

The stretching of closed-shell molecules is a qualitative problem for restricted Hartree-Fock that is usually circumvented by the use of unrestricted Hartree-Fock (UHF). UHF is well known to break the spin symmetry at the Coulson-Fischer point, leading to a discontinuous derivative in the potential energy surface and incorrect spin density. However, this is generally not considered as a major drawback. In this work, we present a set of two electron molecules which magnify the problem of symmetry breaking and lead to drastically incorrect potential energy surfaces with UHF. These molecules also fail with unrestricted density-functional calculations where a functional suchmore » as B3LYP gives both symmetry breaking and an unphysically low energy due to the delocalization error. The implications for density functional theory are also discussed.« less

Relations among several nuclear and electronic density functional reactivity indexes

NASA Astrophysics Data System (ADS)

Torrent-Sucarrat, Miquel; Luis, Josep M.; Duran, Miquel; Toro-Labbé, Alejandro; Solà, Miquel

2003-11-01

An expansion of the energy functional in terms of the total number of electrons and the normal coordinates within the canonical ensemble is presented. A comparison of this expansion with the expansion of the energy in terms of the total number of electrons and the external potential leads to new relations among common density functional reactivity descriptors. The formulas obtained provide explicit links between important quantities related to the chemical reactivity of a system. In particular, the relation between the nuclear and the electronic Fukui functions is recovered. The connection between the derivatives of the electronic energy and the nuclear repulsion energy with respect to the external potential offers a proof for the "Quantum Chemical le Chatelier Principle." Finally, the nuclear linear response function is defined and the relation of this function with the electronic linear response function is given.

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

Escartín, J. M.; CNRS, UMR5152, F-31062 Toulouse Cedex; Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, J.J. Thomson Avenue, Cambridge CB3 0HE

Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT.more » This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na{sub 2}. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.« less

Strong-field ionization of Li and Be: a time-dependent density functional theory with self-interaction correction

NASA Astrophysics Data System (ADS)

Telnov, Dmitry A.; Heslar, John T.; Chu, Shih-I.

2011-11-01

In the framework of the time-dependent density functional theory, we have performed 3D calculations of multiphoton ionization of Li and Be atoms by strong near-infrared laser fields. The results for the intensity-dependent probabilities of single and double ionization are presented. We make use of the time-dependent Krieger-Li-Iafrate exchange-correlation potential with self-interaction correction (TD-KLI-SIC). Such a potential possesses an integer discontinuity which improves description of the ionization process. However, we have found that the discontinuity of the TD-KLI-SIC potential is not sufficient to reproduce characteristic feature of double ionization.

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.

A density functional theory study of the influence of exchange-correlation functionals on the properties of FeAs.

PubMed

Griffin, Sinéad M; Spaldin, Nicola A

2017-06-01

We use density functional theory within the local density approximation (LDA), LDA  +  U, generalised gradient approximation (GGA), GGA  +  U, and hybrid-functional methods to calculate the properties of iron monoarsenide. FeAs, which forms in the MnP structure, is of current interest for potential spintronic applications as well as being the parent compound for the pnictide superconductors. We compare the calculated structural, magnetic and electronic properties obtained using the different functionals to each other and to experiment, and investigate the origin of a recently reported magnetic spiral. Our results indicate the appropriateness or otherwise of the various functionals for describing FeAs and the related Fe-pnictide superconductors.

Note: The performance of new density functionals for a recent blind test of non-covalent interactions

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

Mardirossian, Narbe; Head-Gordon, Martin

Benchmark datasets of non-covalent interactions are essential for assessing the performance of density functionals and other quantum chemistry approaches. In a recent blind test, Taylor et al. benchmarked 14 methods on a new dataset consisting of 10 dimer potential energy curves calculated using coupled cluster with singles, doubles, and perturbative triples (CCSD(T)) at the complete basis set (CBS) limit (80 data points in total). Finally, the dataset is particularly interesting because compressed, near-equilibrium, and stretched regions of the potential energy surface are extensively sampled.

Note: The performance of new density functionals for a recent blind test of non-covalent interactions

DOE PAGES

Mardirossian, Narbe; Head-Gordon, Martin

2016-11-09

Benchmark datasets of non-covalent interactions are essential for assessing the performance of density functionals and other quantum chemistry approaches. In a recent blind test, Taylor et al. benchmarked 14 methods on a new dataset consisting of 10 dimer potential energy curves calculated using coupled cluster with singles, doubles, and perturbative triples (CCSD(T)) at the complete basis set (CBS) limit (80 data points in total). Finally, the dataset is particularly interesting because compressed, near-equilibrium, and stretched regions of the potential energy surface are extensively sampled.

Nonadiabatic Dynamics in Single-Electron Tunneling Devices with Time-Dependent Density-Functional Theory

NASA Astrophysics Data System (ADS)

Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

2018-04-01

We simulate the dynamics of a single-electron source, modeled as a quantum dot with on-site Coulomb interaction and tunnel coupling to an adjacent lead in time-dependent density-functional theory. Based on this system, we develop a time-nonlocal exchange-correlation potential by exploiting analogies with quantum-transport theory. The time nonlocality manifests itself in a dynamical potential step. We explicitly link the time evolution of the dynamical step to physical relaxation timescales of the electron dynamics. Finally, we discuss prospects for simulations of larger mesoscopic systems.

Methanol clusters (CH3OH)n: putative global minimum-energy structures from model potentials and dispersion-corrected density functional theory.

PubMed

Kazachenko, Sergey; Bulusu, Satya; Thakkar, Ajit J

2013-06-14

Putative global minima are reported for methanol clusters (CH3OH)n with n ≤ 15. The predictions are based on global optimization of three intermolecular potential energy models followed by local optimization and single-point energy calculations using two variants of dispersion-corrected density functional theory. Recurring structural motifs include folded and/or twisted rings, folded rings with a short branch, and stacked rings. Many of the larger structures are stabilized by weak C-H···O bonds.

Nonadiabatic Dynamics in Single-Electron Tunneling Devices with Time-Dependent Density-Functional Theory.

PubMed

Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

2018-04-13

We simulate the dynamics of a single-electron source, modeled as a quantum dot with on-site Coulomb interaction and tunnel coupling to an adjacent lead in time-dependent density-functional theory. Based on this system, we develop a time-nonlocal exchange-correlation potential by exploiting analogies with quantum-transport theory. The time nonlocality manifests itself in a dynamical potential step. We explicitly link the time evolution of the dynamical step to physical relaxation timescales of the electron dynamics. Finally, we discuss prospects for simulations of larger mesoscopic systems.

Hydrogen bonding in malonaldehyde: a density functional and reparametrized semiempirical approach

NASA Astrophysics Data System (ADS)

Kovačević, Goran; Hrenar, Tomica; Došlić, Nadja

2003-08-01

Intramolecular proton transfer in malonaldehyde (MA) has been investigated by density functional theory (DFT). The DFT results were used for the construction of a high quality semiempirical potential energy surface with a reparametrized PM3 Hamiltonian. A two-step reparameterization procedure is proposed in which (i) the PM3-MAIS core-core functions for the O-H and H-H interactions were used and a new functional form for the O-O correction function was proposed and (ii) a set of specific reaction parameters (SRP) has been obtained via genetic algorithm optimization. The quality of the reparametrized semiempirical potential energy surfaces was tested by calculating the tunneling splitting of vibrational levels and the anharmonic vibrational frequencies of the system. The applicability to multi-dimensional dynamics in large molecular systems is discussed.

Chemical-potential flow equations for graphene with Coulomb interactions

NASA Astrophysics Data System (ADS)

Fräßdorf, Christian; Mosig, Johannes E. M.

2018-06-01

We calculate the chemical potential dependence of the renormalized Fermi velocity and static dielectric function for Dirac quasiparticles in graphene nonperturbatively at finite temperature. By reinterpreting the chemical potential as a flow parameter in the spirit of the functional renormalization group (fRG) we obtain a set of flow equations, which describe the change of these functions upon varying the chemical potential. In contrast to the fRG the initial condition of the flow is nontrivial and has to be calculated separately. Our results are consistent with a charge carrier-independent Fermi velocity v (k ) for small densities n ≲k2/π , supporting the comparison of the zero-density fRG calculation of Bauer et al. [Phys. Rev. B 92, 121409 (2015), 10.1103/PhysRevB.92.121409], with the experiment of Elias et al. [Nat. Phys. 7, 701 (2011), 10.1038/nphys2049].

New optimization scheme to obtain interaction potentials for oxide glasses

NASA Astrophysics Data System (ADS)

Sundararaman, Siddharth; Huang, Liping; Ispas, Simona; Kob, Walter

2018-05-01

We propose a new scheme to parameterize effective potentials that can be used to simulate atomic systems such as oxide glasses. As input data for the optimization, we use the radial distribution functions of the liquid and the vibrational density of state of the glass, both obtained from ab initio simulations, as well as experimental data on the pressure dependence of the density of the glass. For the case of silica, we find that this new scheme facilitates finding pair potentials that are significantly more accurate than the previous ones even if the functional form is the same, thus demonstrating that even simple two-body potentials can be superior to more complex three-body potentials. We have tested the new potential by calculating the pressure dependence of the elastic moduli and found a good agreement with the corresponding experimental data.

A density difference based analysis of orbital-dependent exchange-correlation functionals

NASA Astrophysics Data System (ADS)

Grabowski, Ireneusz; Teale, Andrew M.; Fabiano, Eduardo; Śmiga, Szymon; Buksztel, Adam; Della Sala, Fabio

2014-03-01

We present a density difference based analysis for a range of orbital-dependent Kohn-Sham functionals. Results for atoms, some members of the neon isoelectronic series and small molecules are reported and compared with ab initio wave function calculations. Particular attention is paid to the quality of approximations to the exchange-only optimised effective potential (OEP) approach: we consider both the localised Hartree-Fock as well as the Krieger-Li-Iafrate methods. Analysis of density differences at the exchange-only level reveals the impact of the approximations on the resulting electronic densities. These differences are further quantified in terms of the ground state energies, frontier orbital energy differences and highest occupied orbital energies obtained. At the correlated level, an OEP approach based on a perturbative second-order correlation energy expression is shown to deliver results comparable with those from traditional wave function approaches, making it suitable for use as a benchmark against which to compare standard density functional approximations.

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

Peierls potential of screw dislocations in bcc transition metals: Predictions from density functional theory

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

Weinberger, Christopher R.; Tucker, Garritt J.; Foiles, Stephen M.

2013-02-01

It is well known that screw dislocation motion dominates the plastic deformation in body-centered-cubic metals at low temperatures. The nature of the nonplanar structure of screw dislocations gives rise to high lattice friction, which results in strong temperature and strain rate dependence of plastic flow. Thus the nature of the Peierls potential, which is responsible for the high lattice resistance, is an important physical property of the material. However, current empirical potentials give a complicated picture of the Peierls potential. Here, we investigate the nature of the Peierls potential using density functional theory in the bcc transition metals. The resultsmore » show that the shape of the Peierls potential is sinusoidal for every material investigated. Furthermore, we show that the magnitude of the potential scales strongly with the energy per unit length of the screw dislocation in the material.« less

Ensemble density variational methods with self- and ghost-interaction-corrected functionals

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

Pastorczak, Ewa; Pernal, Katarzyna, E-mail: pernalk@gmail.com

2014-05-14

Ensemble density functional theory (DFT) offers a way of predicting excited-states energies of atomic and molecular systems without referring to a density response function. Despite a significant theoretical work, practical applications of the proposed approximations have been scarce and they do not allow for a fair judgement of the potential usefulness of ensemble DFT with available functionals. In the paper, we investigate two forms of ensemble density functionals formulated within ensemble DFT framework: the Gross, Oliveira, and Kohn (GOK) functional proposed by Gross et al. [Phys. Rev. A 37, 2809 (1988)] alongside the orbital-dependent eDFT form of the functional introducedmore » by Nagy [J. Phys. B 34, 2363 (2001)] (the acronym eDFT proposed in analogy to eHF – ensemble Hartree-Fock method). Local and semi-local ground-state density functionals are employed in both approaches. Approximate ensemble density functionals contain not only spurious self-interaction but also the so-called ghost-interaction which has no counterpart in the ground-state DFT. We propose how to correct the GOK functional for both kinds of interactions in approximations that go beyond the exact-exchange functional. Numerical applications lead to a conclusion that functionals free of the ghost-interaction by construction, i.e., eDFT, yield much more reliable results than approximate self- and ghost-interaction-corrected GOK functional. Additionally, local density functional corrected for self-interaction employed in the eDFT framework yields excitations energies of the accuracy comparable to that of the uncorrected semi-local eDFT functional.« less

Comparative Study of Exchange-Correlation Functional and Potential for Evaluating Thermoelectric Transport Properties in d0 Perovskite Oxides

NASA Astrophysics Data System (ADS)

Ohkubo, Isao; Mori, Takao

2017-07-01

The influence of two different types of exchange-correlation functional/potential, namely, the generalized gradient approximation Perdew-Burke-Ernzerhof (GGA-PBE) functional and the modified Becke-Johnson (mBJ) potential, on the thermoelectric transport properties of d0 perovskite oxides (SrTiO3 and KTaO3) was investigated. The reduction of band dispersion induced by the mBJ scheme allows the improved prediction of band gap values by thelocal density approximation (LDA) and GGA, which increases the resolution of the increases in the density of states (DOS), carrier concentration, and effective mass near the conduction band edge. A comparison of the experimental effective mass values of d0 perovskite oxides shows that the effective mass values provided by the mBJ potential are similar to those provided by the GGA-PBE functional. Comparative analysis of the data obtained from Boltzmann theory calculations using the electronic structures determined with the GGA-PBE functional and the mBJ potential shows a difference in the transport coefficients owing to the increases in the DOS, carrier concentration, and effective mass induced by the mBJ scheme.

Patching the Exchange-Correlation Potential in Density Functional Theory.

PubMed

Huang, Chen

2016-05-10

A method for directly patching exchange-correlation (XC) potentials in materials is derived. The electron density of a system is partitioned into subsystem densities by dividing its Kohn-Sham (KS) potential among the subsystems. Inside each subsystem, its projected KS potential is required to become the total system's KS potential. This requirement, together with the nearsightedness principle of electronic matters, ensures that the electronic structures inside subsystems can be good approximations to the total system's electronic structure. The nearsightedness principle also ensures that subsystem densities could be well localized in their regions, making it possible to use high-level methods to invert the XC potentials for subsystem densities. Two XC patching methods are developed. In the local XC patching method, the total system's XC potential is improved in the cluster region. We show that the coupling between a cluster and its environment is important for achieving a fast convergence of the electronic structure in the cluster region. In the global XC patching method, we discuss how to patch the subsystem XC potentials to construct the XC potential in the total system, aiming to scale up high-level quantum mechanics simulations of materials. Proof-of-principle examples are given.

Fingerprint Ridge Density as a Potential Forensic Anthropological Tool for Sex Identification.

PubMed

Dhall, Jasmine Kaur; Kapoor, Anup Kumar

2016-03-01

In cases of partial or poor print recovery and lack of database/suspect print, fingerprint evidence is generally neglected. In light of such constraints, this study was designed to examine whether ridge density can aid in narrowing down the investigation for sex identification. The study was conducted on the right-hand index digit of 245 males and 246 females belonging to the Punjabis of Delhi region. Five ridge density count areas, namely upper radial, radial, ulnar, upper ulnar, and proximal, were selected and designated. Probability of sex origin was calculated, and stepwise discriminant function analysis was performed to determine the discriminating ability of the selected areas. Females were observed with a significantly higher ridge density than males in all the five areas. Discriminant function analysis and logistic regression exhibited 96.8% and 97.4% accuracy, respectively, in sex identification. Hence, fingerprint ridge density is a potential tool for sex identification, even from partial prints. © 2015 American Academy of Forensic Sciences.

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?

Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2014-05-14

This paper's objective is to create a "consistent" mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization potentials (VIPs) of the molecule, as the latter condition attests to the viability of the exchange-correlation potential (VXC). None of the prominently used DFT approaches show these properties: the optimized effective potential VXC based ab initio dft does. A local, range-separated hybrid potential cam-QTP-00 is introduced as the basis for a "consistent" KS DFT approach. The computed VIPs as the negative of KS eigenvalue have a mean absolute error of 0.8 eV for an extensive set of molecule's electron ionizations, including the core. Barrier heights, equilibrium geometries, and magnetic properties obtained from the potential are in good agreement with experiment. A similar accuracy with less computational efforts can be achieved by using a non-variational global hybrid variant of the QTP-00 approach.

Potential barrier classification by short-time measurement

NASA Astrophysics Data System (ADS)

Granot, Er'El; Marchewka, Avi

2006-03-01

We investigate the short-time dynamics of a delta-function potential barrier on an initially confined wave packet. There are mainly two conclusions: (A) At short times the probability density of the first particles that passed through the barrier is unaffected by it. (B) When the barrier is absorptive (i.e., its potential is imaginary) it affects the transmitted wave function at shorter times than a real potential barrier. Therefore, it is possible to distinguish between an imaginary and a real potential barrier by measuring its effect at short times only on the transmitting wave function.

DFT-BASED AB INITIO STUDY OF THE ELECTRONIC AND OPTICAL PROPERTIES OF CESIUM BASED FLUORO-PEROVSKITE CsMF3 (M = Ca AND Sr)

NASA Astrophysics Data System (ADS)

Harmel, M.; Khachai, H.; Ameri, M.; Khenata, R.; Baki, N.; Haddou, A.; Abbar, B.; UǦUR, Ş.; Omran, S. Bin; Soyalp, F.

2012-12-01

Density functional theory (DFT) is performed to study the structural, electronic and optical properties of cubic fluoroperovskite AMF3 (A = Cs; M = Ca and Sr) compounds. The calculations are based on the total-energy calculations within the full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential is treated by local density approximation (LDA) and generalized gradient approximation (GGA). The structural properties, including lattice constants, bulk modulus and their pressure derivatives are in very good agreement with the available experimental and theoretical data. The calculations of the electronic band structure, density of states and charge density reveal that compounds are both ionic insulators. The optical properties (namely: the real and the imaginary parts of the dielectric function ɛ(ω), the refractive index n(ω) and the extinction coefficient k(ω)) were calculated for radiation up to 40.0 eV.

The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory

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

Jin, Yifan; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu

This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other propertiesmore » such as geometries, reaction barrier heights, and atomization energies.« less

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.

Thermal density functional theory, ensemble density functional theory, and potential functional theory for warm dense matter

NASA Astrophysics Data System (ADS)

Pribram-Jones, Aurora

Warm dense matter (WDM) is a high energy phase between solids and plasmas, with characteristics of both. It is present in the centers of giant planets, within the earth's core, and on the path to ignition of inertial confinement fusion. The high temperatures and pressures of warm dense matter lead to complications in its simulation, as both classical and quantum effects must be included. One of the most successful simulation methods is density functional theory-molecular dynamics (DFT-MD). Despite great success in a diverse array of applications, DFT-MD remains computationally expensive and it neglects the explicit temperature dependence of electron-electron interactions known to exist within exact DFT. Finite-temperature density functional theory (FT DFT) is an extension of the wildly successful ground-state DFT formalism via thermal ensembles, broadening its quantum mechanical treatment of electrons to include systems at non-zero temperatures. Exact mathematical conditions have been used to predict the behavior of approximations in limiting conditions and to connect FT DFT to the ground-state theory. An introduction to FT DFT is given within the context of ensemble DFT and the larger field of DFT is discussed for context. Ensemble DFT is used to describe ensembles of ground-state and excited systems. Exact conditions in ensemble DFT and the performance of approximations depend on ensemble weights. Using an inversion method, exact Kohn-Sham ensemble potentials are found and compared to approximations. The symmetry eigenstate Hartree-exchange approximation is in good agreement with exact calculations because of its inclusion of an ensemble derivative discontinuity. Since ensemble weights in FT DFT are temperature-dependent Fermi weights, this insight may help develop approximations well-suited to both ground-state and FT DFT. A novel, highly efficient approach to free energy calculations, finite-temperature potential functional theory, is derived, which has the potential to transform the simulation of warm dense matter. As a semiclassical method, it connects the normally disparate regimes of cold condensed matter physics and hot plasma physics. This orbital-free approach captures the smooth classical density envelope and quantum density oscillations that are both crucial to accurate modeling of materials where temperature and pressure effects are influential.

Site-occupation embedding theory using Bethe ansatz local density approximations

NASA Astrophysics Data System (ADS)

Senjean, Bruno; Nakatani, Naoki; Tsuchiizu, Masahisa; Fromager, Emmanuel

2018-06-01

Site-occupation embedding theory (SOET) is an alternative formulation of density functional theory (DFT) for model Hamiltonians where the fully interacting Hubbard problem is mapped, in principle exactly, onto an impurity-interacting (rather than a noninteracting) one. It provides a rigorous framework for combining wave-function (or Green function)-based methods with DFT. In this work, exact expressions for the per-site energy and double occupation of the uniform Hubbard model are derived in the context of SOET. As readily seen from these derivations, the so-called bath contribution to the per-site correlation energy is, in addition to the latter, the key density functional quantity to model in SOET. Various approximations based on Bethe ansatz and perturbative solutions to the Hubbard and single-impurity Anderson models are constructed and tested on a one-dimensional ring. The self-consistent calculation of the embedded impurity wave function has been performed with the density-matrix renormalization group method. It has been shown that promising results are obtained in specific regimes of correlation and density. Possible further developments have been proposed in order to provide reliable embedding functionals and potentials.

An extended hybrid density functional (X3LYP) with improved descriptions of nonbond interactions and thermodynamic properties of molecular systems

NASA Astrophysics Data System (ADS)

Xu, Xin; Zhang, Qingsong; Muller, Richard P.; Goddard, William A.

2005-01-01

We derive here the form for the exact exchange energy density for a density that decays with Gaussian-type behavior at long range. This functional is intermediate between the B88 and the PW91 exchange functionals. Using this modified functional to match the form expected for Gaussian densities, we propose the X3LYP extended functional. We find that X3LYP significantly outperforms Becke three parameter Lee-Yang-Parr (B3LYP) for describing van der Waals and hydrogen bond interactions, while performing slightly better than B3LYP for predicting heats of formation, ionization potentials, electron affinities, proton affinities, and total atomic energies as validated with the extended G2 set of atoms and molecules. Thus X3LYP greatly enlarges the field of applications for density functional theory. In particular the success of X3LYP in describing the water dimer (with Re and De within the error bars of the most accurate determinations) makes it an excellent candidate for predicting accurate ligand-protein and ligand-DNA interactions.

Density functional theory of freezing of a system of highly elongated ellipsoidal oligomer solutions

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Mishra, Pankaj

2017-05-01

We have used the density functional theory of freezing to study the liquid crystalline phase behavior of a system of highly elongated ellipsoidal conjugated oligomers dispersed in three different solvents namely chloroform, toluene and their equimolar mixture. The molecules are assumed to interact via solvent-implicit coarse-grained Gay-Berne potential. Pair correlation functions needed as input in the density functional theory have been calculated using the Percus-Yevick (PY) integral equation theory. Considering the isotropic and nematic phases, we have calculated the isotropic-nematic phase transition parameters and presented the temperature-density and pressure-temperature phase diagrams. Different solvent conditions are found not only to affect the transition parameters but also determine the capability of oligomers to form nematic phase in various thermodynamic conditions. In principle, our results are verifiable through computer simulations.

Orbital-dependent density functionals: Theory and applications

NASA Astrophysics Data System (ADS)

Kümmel, Stephan; Kronik, Leeor

2008-01-01

This review provides a perspective on the use of orbital-dependent functionals, which is currently considered one of the most promising avenues in modern density-functional theory. The focus here is on four major themes: the motivation for orbital-dependent functionals in terms of limitations of semilocal functionals; the optimized effective potential as a rigorous approach to incorporating orbital-dependent functionals within the Kohn-Sham framework; the rationale behind and advantages and limitations of four popular classes of orbital-dependent functionals; and the use of orbital-dependent functionals for predicting excited-state properties. For each of these issues, both formal and practical aspects are assessed.

Effective homogeneity of the exchange-correlation and non-interacting kinetic energy functionals under density scaling.

PubMed

Borgoo, Alex; Teale, Andrew M; Tozer, David J

2012-01-21

Correlated electron densities, experimental ionisation potentials, and experimental electron affinities are used to investigate the homogeneity of the exchange-correlation and non-interacting kinetic energy functionals of Kohn-Sham density functional theory under density scaling. Results are presented for atoms and small molecules, paying attention to the influence of the integer discontinuity and the choice of the electron affinity. For the exchange-correlation functional, effective homogeneities are highly system-dependent on either side of the integer discontinuity. By contrast, the average homogeneity-associated with the potential that averages over the discontinuity-is generally close to 4/3 when the discontinuity is computed using positive affinities for systems that do bind an excess electron and negative affinities for those that do not. The proximity to 4/3 becomes increasingly pronounced with increasing atomic number. Evaluating the discontinuity using a zero affinity in systems that do not bind an excess electron instead leads to effective homogeneities on the electron abundant side that are close to 4/3. For the non-interacting kinetic energy functional, the effective homogeneities are less system-dependent and the effect of the integer discontinuity is less pronounced. Average values are uniformly below 5/3. The study provides information that may aid the development of improved exchange-correlation and non-interacting kinetic energy functionals. © 2012 American Institute of Physics

Molecular Model for HNBR with Tunable Cross-Link Density.

PubMed

Molinari, N; Khawaja, M; Sutton, A P; Mostofi, A A

2016-12-15

We introduce a chemically inspired, all-atom model of hydrogenated nitrile butadiene rubber (HNBR) and assess its performance by computing the mass density and glass-transition temperature as a function of cross-link density in the structure. Our HNBR structures are created by a procedure that mimics the real process used to produce HNBR, that is, saturation of the carbon-carbon double bonds in NBR, either by hydrogenation or by cross-linking. The atomic interactions are described by the all-atom "Optimized Potentials for Liquid Simulations" (OPLS-AA). In this paper, first, we assess the use of OPLS-AA in our models, especially using NBR bulk properties, and second, we evaluate the validity of the proposed model for HNBR by investigating mass density and glass transition as a function of the tunable cross-link density. Experimental densities are reproduced within 3% for both elastomers, and qualitatively correct trends in the glass-transition temperature as a function of monomer composition and cross-link density are obtained.

Massively parallel GPU-accelerated minimization of classical density functional theory

NASA Astrophysics Data System (ADS)

Stopper, Daniel; Roth, Roland

2017-08-01

In this paper, we discuss the ability to numerically minimize the grand potential of hard disks in two-dimensional and of hard spheres in three-dimensional space within the framework of classical density functional and fundamental measure theory on modern graphics cards. Our main finding is that a massively parallel minimization leads to an enormous performance gain in comparison to standard sequential minimization schemes. Furthermore, the results indicate that in complex multi-dimensional situations, a heavy parallel minimization of the grand potential seems to be mandatory in order to reach a reasonable balance between accuracy and computational cost.

Nanofilter platform based on functionalized carbon nanotubes for adsorption and elimination of Acrolein, a toxicant in cigarette smoke

NASA Astrophysics Data System (ADS)

Yoosefian, Mehdi; Pakpour, Atef; Etminan, Nazanin

2018-06-01

This paper discusses the use of carboxylated single-walled carbon nanotube as a general nanofilter platform for the removal of acrolein carcinogen from cigarette smoke. The analyses carried out in the detailed study of the electronic and structural effects of the adsorption of acrolein onto COOH loaded on single-walled carbon nanotube under the density functional theory framework. The results of Bader theory of atoms in molecules, natural bond orbital, molecular potential electron surface and density of state confirm the potential application of the suggested nanofilter platform.

On-the-Fly Machine Learning of Atomic Potential in Density Functional Theory Structure Optimization

NASA Astrophysics Data System (ADS)

Jacobsen, T. L.; Jørgensen, M. S.; Hammer, B.

2018-01-01

Machine learning (ML) is used to derive local stability information for density functional theory calculations of systems in relation to the recently discovered SnO2 (110 )-(4 ×1 ) reconstruction. The ML model is trained on (structure, total energy) relations collected during global minimum energy search runs with an evolutionary algorithm (EA). While being built, the ML model is used to guide the EA, thereby speeding up the overall rate by which the EA succeeds. Inspection of the local atomic potentials emerging from the model further shows chemically intuitive patterns.

Investigation of thermoelectricity in KScSn half-Heusler compound

NASA Astrophysics Data System (ADS)

Shrivastava, Deepika; Acharya, Nikita; Sanyal, Sankar P.

2018-05-01

The electronic and transport properties of KScSn half-Heusler (HH) compound have been investigated using first-principles density functional theory and semi classical Boltzmann transport theory. The electronic band structure and density of states (total and partial) show semiconducting nature of KScSn with band gap 0.48 eV which agree well with previously reported results. The transport coefficient such as electrical conductivity, Seebeck coefficient, electronic thermal conductivity and power factor as a function of chemical potential are evaluated. KScSn has high power factor for p-type doping and is a potential candidate for thermoelectric applications.

Phase transition in conjugated oligomers suspended in chloroform

NASA Astrophysics Data System (ADS)

Dwivedi, Shikha; Kumar, Anupam; Yadav, S. N. S.; Mishra, Pankaj

2015-08-01

Density functional theory (DFT) has been used to investigate the isotropic-nematic (I-N) phase transition in a system of high aspect ratio conjugated oligomers suspended in chloroform. The interaction between the oligomers is modeled using Gay-Berne potential in which effect of solvent is implicit. Percus-Yevick integral equation theory has been used to evaluate the pair correlation functions of the fluid phase at several temperatures and densities. These pair correlation function has been used in the DFT to evaluate the I-N freezing parameters. Highly oriented nematic is found to stabilize at low density. The results obtained are in qualitative agreement with the simulation and are verifiable.

Reconstruction of Cell Surface Densities of Ion Pumps, Exchangers, and Channels from mRNA Expression, Conductance Kinetics, Whole-Cell Calcium, and Current-Clamp Voltage Recordings, with an Application to Human Uterine Smooth Muscle Cells

PubMed Central

Atia, Jolene; McCloskey, Conor; Shmygol, Anatoly S.; Rand, David A.; van den Berg, Hugo A.; Blanks, Andrew M.

2016-01-01

Uterine smooth muscle cells remain quiescent throughout most of gestation, only generating spontaneous action potentials immediately prior to, and during, labor. This study presents a method that combines transcriptomics with biophysical recordings to characterise the conductance repertoire of these cells, the ‘conductance repertoire’ being the total complement of ion channels and transporters expressed by an electrically active cell. Transcriptomic analysis provides a set of potential electrogenic entities, of which the conductance repertoire is a subset. Each entity within the conductance repertoire was modeled independently and its gating parameter values were fixed using the available biophysical data. The only remaining free parameters were the surface densities for each entity. We characterise the space of combinations of surface densities (density vectors) consistent with experimentally observed membrane potential and calcium waveforms. This yields insights on the functional redundancy of the system as well as its behavioral versatility. Our approach couples high-throughput transcriptomic data with physiological behaviors in health and disease, and provides a formal method to link genotype to phenotype in excitable systems. We accurately predict current densities and chart functional redundancy. For example, we find that to evoke the observed voltage waveform, the BK channel is functionally redundant whereas hERG is essential. Furthermore, our analysis suggests that activation of calcium-activated chloride conductances by intracellular calcium release is the key factor underlying spontaneous depolarisations. PMID:27105427

Handling times and saturating transmission functions in a snail-worm symbiosis.

PubMed

Hopkins, Skylar R; McGregor, Cari M; Belden, Lisa K; Wojdak, Jeremy M

2018-06-16

All dynamic species interaction models contain an assumption that describes how contact rates scale with population density. Choosing an appropriate contact-density function is important, because different functions have different implications for population dynamics and stability. However, this choice can be challenging, because there are many possible functions, and most are phenomenological and thus difficult to relate to underlying ecological processes. Using one such phenomenological function, we described a nonlinear relationship between field transmission rates and host density in a common snail-oligochaete symbiosis. We then used a well-known contact function from predator-prey models, the Holling Type II functional response, to describe and predict host snail contact rates in the laboratory. The Holling Type II functional response accurately described both the nonlinear contact-density relationship and the average contact duration that we observed. Therefore, we suggest that contact rates saturate with host density in this system because each snail contact requires a non-instantaneous handling time, and additional possible contacts do not occur during that handling time. Handling times and nonlinear contact rates might also explain the nonlinear relationship between symbiont transmission and snail density that we observed in the field, which could be confirmed by future work that controls for other potential sources of seasonal variation in transmission rates. Because most animal contacts are not instantaneous, the Holling Type II functional response might be broadly relevant to diverse host-symbiont systems.

Hartree-Fock theory of the inhomogeneous electron gas at a jellium metal surface: Rigorous upper bounds to the surface energy and accurate work functions

NASA Astrophysics Data System (ADS)

Sahni, V.; Ma, C. Q.

1980-12-01

The inhomogeneous electron gas at a jellium metal surface is studied in the Hartree-Fock approximation by Kohn-Sham density functional theory. Rigorous upper bounds to the surface energy are derived by application of the Rayleigh-Ritz variational principle for the energy, the surface kinetic, electrostatic, and nonlocal exchange energy functionals being determined exactly for the accurate linear-potential model electronic wave functions. The densities obtained by the energy minimization constraint are then employed to determine work-function results via the variationally accurate "displaced-profile change-in-self-consistent-field" expression. The theoretical basis of this non-self-consistent procedure and its demonstrated accuracy for the fully correlated system (as treated within the local-density approximation for exchange and correlation) leads us to conclude these results for the surface energies and work functions to be essentially exact. Work-function values are also determined by the Koopmans'-theorem expression, both for these densities as well as for those obtained by satisfaction of the constraint set on the electrostatic potential by the Budd-Vannimenus theorem. The use of the Hartree-Fock results in the accurate estimation of correlation-effect contributions to these surface properties of the nonuniform electron gas is also indicated. In addition, the original work and approximations made by Bardeen in this attempt at a solution of the Hartree-Fock problem are briefly reviewed in order to contrast with the present work.

Orthogonality of embedded wave functions for different states in frozen-density embedding theory

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

Zech, Alexander; Wesolowski, Tomasz A.; Aquilante, Francesco

2015-10-28

Other than lowest-energy stationary embedded wave functions obtained in Frozen-Density Embedding Theory (FDET) [T. A. Wesolowski, Phys. Rev. A 77, 012504 (2008)] can be associated with electronic excited states but they can be mutually non-orthogonal. Although this does not violate any physical principles — embedded wave functions are only auxiliary objects used to obtain stationary densities — working with orthogonal functions has many practical advantages. In the present work, we show numerically that excitation energies obtained using conventional FDET calculations (allowing for non-orthogonality) can be obtained using embedded wave functions which are strictly orthogonal. The used method preserves the mathematicalmore » structure of FDET and self-consistency between energy, embedded wave function, and the embedding potential (they are connected through the Euler-Lagrange equations). The orthogonality is built-in through the linearization in the embedded density of the relevant components of the total energy functional. Moreover, we show formally that the differences between the expectation values of the embedded Hamiltonian are equal to the excitation energies, which is the exact result within linearized FDET. Linearized FDET is shown to be a robust approximation for a large class of reference densities.« less

A reference-modified density functional theory: An application to solvation free-energy calculations for a Lennard-Jones solution.

PubMed

Sumi, Tomonari; Maruyama, Yutaka; Mitsutake, Ayori; Koga, Kenichiro

2016-06-14

In the conventional classical density functional theory (DFT) for simple fluids, an ideal gas is usually chosen as the reference system because there is a one-to-one correspondence between the external field and the density distribution function, and the exact intrinsic free-energy functional is available for the ideal gas. In this case, the second-order density functional Taylor series expansion of the excess intrinsic free-energy functional provides the hypernetted-chain (HNC) approximation. Recently, it has been shown that the HNC approximation significantly overestimates the solvation free energy (SFE) for an infinitely dilute Lennard-Jones (LJ) solution, especially when the solute particles are several times larger than the solvent particles [T. Miyata and J. Thapa, Chem. Phys. Lett. 604, 122 (2014)]. In the present study, we propose a reference-modified density functional theory as a systematic approach to improve the SFE functional as well as the pair distribution functions. The second-order density functional Taylor series expansion for the excess part of the intrinsic free-energy functional in which a hard-sphere fluid is introduced as the reference system instead of an ideal gas is applied to the LJ pure and infinitely dilute solution systems and is proved to remarkably improve the drawbacks of the HNC approximation. Furthermore, the third-order density functional expansion approximation in which a factorization approximation is applied to the triplet direct correlation function is examined for the LJ systems. We also show that the third-order contribution can yield further refinements for both the pair distribution function and the excess chemical potential for the pure LJ liquids.

Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity.

PubMed

Domingo, Luis R; Ríos-Gutiérrez, Mar; Pérez, Patricia

2016-06-09

Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices like the electrophilic P k + and nucleophilic P k - Parr functions, as the most relevant indices for the study of organic reactivity, are discussed.

Extension of many-body theory and approximate density functionals to fractional charges and fractional spins.

PubMed

Yang, Weitao; Mori-Sánchez, Paula; Cohen, Aron J

2013-09-14

The exact conditions for density functionals and density matrix functionals in terms of fractional charges and fractional spins are known, and their violation in commonly used functionals has been shown to be the root of many major failures in practical applications. However, approximate functionals are designed for physical systems with integer charges and spins, not in terms of the fractional variables. Here we develop a general framework for extending approximate density functionals and many-electron theory to fractional-charge and fractional-spin systems. Our development allows for the fractional extension of any approximate theory that is a functional of G(0), the one-electron Green's function of the non-interacting reference system. The extension to fractional charge and fractional spin systems is based on the ensemble average of the basic variable, G(0). We demonstrate the fractional extension for the following theories: (1) any explicit functional of the one-electron density, such as the local density approximation and generalized gradient approximations; (2) any explicit functional of the one-electron density matrix of the non-interacting reference system, such as the exact exchange functional (or Hartree-Fock theory) and hybrid functionals; (3) many-body perturbation theory; and (4) random-phase approximations. A general rule for such an extension has also been derived through scaling the orbitals and should be useful for functionals where the link to the Green's function is not obvious. The development thus enables the examination of approximate theories against known exact conditions on the fractional variables and the analysis of their failures in chemical and physical applications in terms of violations of exact conditions of the energy functionals. The present work should facilitate the calculation of chemical potentials and fundamental bandgaps with approximate functionals and many-electron theories through the energy derivatives with respect to the fractional charge. It should play an important role in developing accurate approximate density functionals and many-body theory.

Linear-response time-dependent density-functional theory with pairing fields.

PubMed

Peng, Degao; van Aggelen, Helen; Yang, Yang; Yang, Weitao

2014-05-14

Recent development in particle-particle random phase approximation (pp-RPA) broadens the perspective on ground state correlation energies [H. van Aggelen, Y. Yang, and W. Yang, Phys. Rev. A 88, 030501 (2013), Y. Yang, H. van Aggelen, S. N. Steinmann, D. Peng, and W. Yang, J. Chem. Phys. 139, 174110 (2013); D. Peng, S. N. Steinmann, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 104112 (2013)] and N ± 2 excitation energies [Y. Yang, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 224105 (2013)]. So far Hartree-Fock and approximated density-functional orbitals have been utilized to evaluate the pp-RPA equation. In this paper, to further explore the fundamentals and the potential use of pairing matrix dependent functionals, we present the linear-response time-dependent density-functional theory with pairing fields with both adiabatic and frequency-dependent kernels. This theory is related to the density-functional theory and time-dependent density-functional theory for superconductors, but is applied to normal non-superconducting systems for our purpose. Due to the lack of the proof of the one-to-one mapping between the pairing matrix and the pairing field for time-dependent systems, the linear-response theory is established based on the representability assumption of the pairing matrix. The linear response theory justifies the use of approximated density-functionals in the pp-RPA equation. This work sets the fundamentals for future density-functional development to enhance the description of ground state correlation energies and N ± 2 excitation energies.

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

Lindgren, Ingvar; Salomonson, Sten

The locality theorem in density-functional theory (DFT) states that the functional derivative of the Hohenberg-Kohn universal functional can be expressed as a local multiplicative potential function, and this is the basis of DFT and of the successful Kohn-Sham model. Nesbet has in several papers [Phys. Rev. A 58, R12 (1998); ibid.65, 010502 (2001); Adv. Quant. Chem, 43, 1 (2003)] claimed that this theorem is in conflict with fundamental quantum physics, and as a consequence that the Hohenberg-Kohn theory cannot be generally valid. We have commented upon these works [Comment, Phys. Rev. A 67, 056501 (2003)] and recently extended the argumentsmore » [Adv. Quantum Chem. 43, 95 (2003)]. We have shown that there is no such conflict and that the locality theorem is inherently exact. In the present work we have furthermore verified this numerically by constructing a local Kohn-Sham potential for the 1s2s{sup 3}S state of helium that generates the many-body electron density and shown that the corresponding 2s Kohn-Sham orbital eigenvalue agrees with the ionization energy to nine digits. Similar result is obtained with the Hartree-Fock density. Therefore, in addition to verifying the locality theorem, this result also confirms the so-called ionization-potential theorem.« less

The optimized effective potential and the self-interaction correction in density functional theory: Application to molecules

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

Garza, Jorge; Nichols, Jeffrey A.; Dixon, David A.

2000-05-08

The Krieger, Li, and Iafrate approximation to the optimized effective potential including the self-interaction correction for density functional theory has been implemented in a molecular code, NWChem, that uses Gaussian functions to represent the Kohn and Sham spin-orbitals. The differences between the implementation of the self-interaction correction in codes where planewaves are used with an optimized effective potential are discussed. The importance of the localization of the spin-orbitals to maximize the exchange-correlation of the self-interaction correction is discussed. We carried out exchange-only calculations to compare the results obtained with these approximations, and those obtained with the local spin density approximation,more » the generalized gradient approximation and Hartree-Fock theory. Interesting results for the energy difference (GAP) between the highest occupied molecular orbital, HOMO, and the lowest unoccupied molecular orbital, LUMO, (spin-orbital energies of closed shell atoms and molecules) using the optimized effective potential and the self-interaction correction have been obtained. The effect of the diffuse character of the basis set on the HOMO and LUMO eigenvalues at the various levels is discussed. Total energies obtained with the optimized effective potential and the self-interaction correction show that the exchange energy with these approximations is overestimated and this will be an important topic for future work. (c) 2000 American Institute of Physics.« less

High density lipoproteins: Measurement techniques and potential biomarkers of cardiovascular risk

PubMed Central

Hafiane, Anouar; Genest, Jacques

2015-01-01

Plasma high density lipoprotein cholesterol (HDL) comprises a heterogeneous family of lipoprotein species, differing in surface charge, size and lipid and protein compositions. While HDL cholesterol (C) mass is a strong, graded and coherent biomarker of cardiovascular risk, genetic and clinical trial data suggest that the simple measurement of HDL-C may not be causal in preventing atherosclerosis nor reflect HDL functionality. Indeed, the measurement of HDL-C may be a biomarker of cardiovascular health. To assess the issue of HDL function as a potential therapeutic target, robust and simple analytical methods are required. The complex pleiotropic effects of HDL make the development of a single measurement challenging. Development of laboratory assays that accurately HDL function must be developed validated and brought to high-throughput for clinical purposes. This review discusses the limitations of current laboratory technologies for methods that separate and quantify HDL and potential application to predict CVD, with an emphasis on emergent approaches as potential biomarkers in clinical practice. PMID:26674734

Glass Formation of n-Butanol: Coarse-grained Molecular Dynamics Simulations Using Gay-Berne Potential Model

NASA Astrophysics Data System (ADS)

Xie, Gui-long; Zhang, Yong-hong; Huang, Shi-ping

2012-04-01

Using coarse-grained molecular dynamics simulations based on Gay-Berne potential model, we have simulated the cooling process of liquid n-butanol. A new set of GB parameters are obtained by fitting the results of density functional theory calculations. The simulations are carried out in the range of 290-50 K with temperature decrements of 10 K. The cooling characteristics are determined on the basis of the variations of the density, the potential energy and orientational order parameter with temperature, whose slopes all show discontinuity. Both the radial distribution function curves and the second-rank orientational correlation function curves exhibit splitting in the second peak. Using the discontinuous change of these thermodynamic and structure properties, we obtain the glass transition at an estimate of temperature Tg=120±10 K, which is in good agreement with experimental results 110±1 K.

Functionally graded biomimetic energy absorption concept development for transportation systems.

DOT National Transportation Integrated Search

2014-02-01

Mechanics of a functionally graded cylinder subject to static or dynamic axial loading is considered, including a potential application as energy absorber. The mass density and stiffness are power functions of the radial coordinate as may be the case...

Employing general fit-bases for construction of potential energy surfaces with an adaptive density-guided approach

NASA Astrophysics Data System (ADS)

Klinting, Emil Lund; Thomsen, Bo; Godtliebsen, Ian Heide; Christiansen, Ove

2018-02-01

We present an approach to treat sets of general fit-basis functions in a single uniform framework, where the functional form is supplied on input, i.e., the use of different functions does not require new code to be written. The fit-basis functions can be used to carry out linear fits to the grid of single points, which are generated with an adaptive density-guided approach (ADGA). A non-linear conjugate gradient method is used to optimize non-linear parameters if such are present in the fit-basis functions. This means that a set of fit-basis functions with the same inherent shape as the potential cuts can be requested and no other choices with regards to the fit-basis functions need to be taken. The general fit-basis framework is explored in relation to anharmonic potentials for model systems, diatomic molecules, water, and imidazole. The behaviour and performance of Morse and double-well fit-basis functions are compared to that of polynomial fit-basis functions for unsymmetrical single-minimum and symmetrical double-well potentials. Furthermore, calculations for water and imidazole were carried out using both normal coordinates and hybrid optimized and localized coordinates (HOLCs). Our results suggest that choosing a suitable set of fit-basis functions can improve the stability of the fitting routine and the overall efficiency of potential construction by lowering the number of single point calculations required for the ADGA. It is possible to reduce the number of terms in the potential by choosing the Morse and double-well fit-basis functions. These effects are substantial for normal coordinates but become even more pronounced if HOLCs are used.

Scanning tunneling microscopy current from localized basis orbital density functional theory

NASA Astrophysics Data System (ADS)

Gustafsson, Alexander; Paulsson, Magnus

2016-03-01

We present a method capable of calculating elastic scanning tunneling microscopy (STM) currents from localized atomic orbital density functional theory (DFT). To overcome the poor accuracy of the localized orbital description of the wave functions far away from the atoms, we propagate the wave functions, using the total DFT potential. From the propagated wave functions, the Bardeen's perturbative approach provides the tunneling current. To illustrate the method we investigate carbon monoxide adsorbed on a Cu(111) surface and recover the depression/protrusion observed experimentally with normal/CO-functionalized STM tips. The theory furthermore allows us to discuss the significance of s - and p -wave tips.

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

NASA Astrophysics Data System (ADS)

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

2011-01-01

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

Tunneling of coupled methyl quantum rotors in 4-methylpyridine: Single rotor potential versus coupling interaction

NASA Astrophysics Data System (ADS)

Khazaei, Somayeh; Sebastiani, Daniel

2017-11-01

We study the influence of rotational coupling between a pair of methyl rotators on the tunneling spectrum in condensed phase. Two interacting adjacent methyl groups are simulated within a coupled-pair model composed of static rotational potential created by the chemical environment and the interaction potential between two methyl groups. We solve the two-dimensional time-independent Schrödinger equation analytically by expanding the wave functions on the basis set of two independent free-rotor functions. We investigate three scenarios which differ with respect to the relative strength of single-rotor and coupling potential. For each scenario, we illustrate the dependence of the energy level scheme on the coupling strength. It is found that the main determinant of splitting energy levels tends to be a function of the ratio of strengths of coupling and single-rotor potential. The tunnel splitting caused by coupling is maximized for the coupled rotors in which their total hindering potential is relatively shallow. Such a weakly hindered methyl rotational potential is predicted for 4-methylpyridine at low temperature. The experimental observation of multiple tunneling peaks arising from a single type of methyl group in 4-methylpyridine in the inelastic neutron scattering spectrum is widely attributed to the rotor-rotor coupling. In this regard, using a set of first-principles calculations combined with the nudged elastic band method, we investigate the rotational potential energy surface (PES) of the coaxial pairs of rotors in 4-methylpyridine. A Numerov-type method is used to numerically solve the two-dimensional time-independent Schrödinger equation for the calculated 2D-density functional theory profile. Our computed energy levels reproduce the observed tunneling transitions well. Moreover, the calculated density distribution of the three methyl protons resembles the experimental nuclear densities obtained from the Fourier difference method. By mapping the calculated first-principles PES on the model, it is confirmed that the hindering potential in 4-methylpyridine consists of proportionally shallow single-rotor potential to coupling interaction.

Tunneling of coupled methyl quantum rotors in 4-methylpyridine: Single rotor potential versus coupling interaction.

PubMed

Khazaei, Somayeh; Sebastiani, Daniel

2017-11-21

We study the influence of rotational coupling between a pair of methyl rotators on the tunneling spectrum in condensed phase. Two interacting adjacent methyl groups are simulated within a coupled-pair model composed of static rotational potential created by the chemical environment and the interaction potential between two methyl groups. We solve the two-dimensional time-independent Schrödinger equation analytically by expanding the wave functions on the basis set of two independent free-rotor functions. We investigate three scenarios which differ with respect to the relative strength of single-rotor and coupling potential. For each scenario, we illustrate the dependence of the energy level scheme on the coupling strength. It is found that the main determinant of splitting energy levels tends to be a function of the ratio of strengths of coupling and single-rotor potential. The tunnel splitting caused by coupling is maximized for the coupled rotors in which their total hindering potential is relatively shallow. Such a weakly hindered methyl rotational potential is predicted for 4-methylpyridine at low temperature. The experimental observation of multiple tunneling peaks arising from a single type of methyl group in 4-methylpyridine in the inelastic neutron scattering spectrum is widely attributed to the rotor-rotor coupling. In this regard, using a set of first-principles calculations combined with the nudged elastic band method, we investigate the rotational potential energy surface (PES) of the coaxial pairs of rotors in 4-methylpyridine. A Numerov-type method is used to numerically solve the two-dimensional time-independent Schrödinger equation for the calculated 2D-density functional theory profile. Our computed energy levels reproduce the observed tunneling transitions well. Moreover, the calculated density distribution of the three methyl protons resembles the experimental nuclear densities obtained from the Fourier difference method. By mapping the calculated first-principles PES on the model, it is confirmed that the hindering potential in 4-methylpyridine consists of proportionally shallow single-rotor potential to coupling interaction.

Electrokinetic flow in a capillary with a charge-regulating surface polymer layer.

PubMed

Keh, Huan J; Ding, Jau M

2003-07-15

An analytical study of the steady electrokinetic flow in a long uniform capillary tube or slit is presented. The inside wall of the capillary is covered by a layer of adsorbed or covalently bound charge-regulating polymer in equilibrium with the ambient electrolyte solution. In this solvent-permeable and ion-penetrable surface polyelectrolyte layer, ionogenic functional groups and frictional segments are assumed to distribute at uniform densities. The electrical potential and space charge density distributions in the cross section of the capillary are obtained by solving the linearized Poisson-Boltzmann equation. The fluid velocity profile due to the application of an electric field and a pressure gradient through the capillary is obtained from the analytical solution of a modified Navier-Stokes/Brinkman equation. Explicit formulas for the electroosmotic velocity, the average fluid velocity and electric current density on the cross section, and the streaming potential in the capillary are also derived. The results demonstrate that the direction of the electroosmotic flow and the magnitudes of the fluid velocity and electric current density are dominated by the fixed charge density inside the surface polymer layer, which is determined by the regulation characteristics such as the dissociation equilibrium constants of the ionogenic functional groups in the surface layer and the concentration of the potential-determining ions in the bulk solution.

Air density dependence of the response of the PTW SourceCheck 4pi ionization chamber for 125I brachytherapy seeds.

PubMed

Torres Del Río, J; Tornero-López, A M; Guirado, D; Pérez-Calatayud, J; Lallena, A M

2017-06-01

To analyze the air density dependence of the response of the new SourceCheck 4pi ionization chamber, manufactured by PTW. The air density dependence of three different SourceCheck 4pi chambers was studied by measuring 125 I sources. Measurements were taken by varying the pressure from 746.6 to 986.6hPa in a pressure chamber. Three different HDR 1000 Plus ionization chambers were also analyzed under similar conditions. A linear and a potential-like function of the air density were fitted to experimental data and their achievement in describing them was analyzed. SourceCheck 4pi chamber response showed a residual dependence on the air density once the standard pressure and temperature factor was applied. The chamber response was overestimated when the air density was below that under normal atmospheric conditions. A similar dependence was found for the HDR 1000 Plus chambers analyzed. A linear function of the air density permitted a very good description of this residual dependence, better than with a potential function. No significant variability between the different specimens of the same chamber model studied was found. The effect of overestimation observed in the chamber responses once they are corrected for the standard pressure and temperature may represent a non-negligible ∼4% overestimation in high altitude cities as ours (700m AMSL). This overestimation behaves linearly with the air density in all cases analyzed. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Conceptual DFT Descriptors of Amino Acids with Potential Corrosion Inhibition Properties Calculated with the Latest Minnesota Density Functionals.

PubMed

Frau, Juan; Glossman-Mitnik, Daniel

2017-01-01

Amino acids and peptides have the potential to perform as corrosion inhibitors. The chemical reactivity descriptors that arise from Conceptual DFT for the twenty natural amino acids have been calculated by using the latest Minnesota family of density functionals. In order to verify the validity of the calculation of the descriptors directly from the HOMO and LUMO, a comparison has been performed with those obtained through ΔSCF results. Moreover, the active sites for nucleophilic and electrophilic attacks have been identified through Fukui function indices, the dual descriptor Δf( r ) and the electrophilic and nucleophilic Parr functions. The results could be of interest as a starting point for the study of large peptides where the calculation of the radical cation and anion of each system may be computationally harder and costly.

Subsystem functional and the missing ingredient of confinement physics in density functionals.

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

Armiento, Rickard Roberto; Mattsson, Ann Elisabet; Hao, Feng

2010-08-01

The subsystem functional scheme is a promising approach recently proposed for constructing exchange-correlation density functionals. In this scheme, the physics in each part of real materials is described by mapping to a characteristic model system. The 'confinement physics,' an essential physical ingredient that has been left out in present functionals, is studied by employing the harmonic-oscillator (HO) gas model. By performing the potential {yields} density and the density {yields} exchange energy per particle mappings based on two model systems characterizing the physics in the interior (uniform electron-gas model) and surface regions (Airy gas model) of materials for the HO gases,more » we show that the confinement physics emerges when only the lowest subband of the HO gas is occupied by electrons. We examine the approximations of the exchange energy by several state-of-the-art functionals for the HO gas, and none of them produces adequate accuracy in the confinement dominated cases. A generic functional that incorporates the description of the confinement physics is needed.« less

Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

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

Kuwahara, Riichi; Accelrys K. K., Kasumigaseki Tokyu Building 17F, 3-7-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-0013; Tadokoro, Yoichi

In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree–Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is inmore » excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.« less

A Study of Terrain Reductions, Density Anomalies and Geophysical Inversion Methods in Gravity Field Modelling

DTIC Science & Technology

1984-04-01

5.15) where a is a positive constant and 11 IIH the Hilbert space norm associated with the chosen covariance function K. The constant a is arbitrary...Density Anomalies 14 5. Unknown Densities - Geophysical Inversion 16 6. Density Modelling Using Rectangular Prisms 24 6.1 Space Domain 24 6.2 Frequency...theory: to calculate the gravity potential and its derivatives in space due to 6 • given density distributions. When the prime interest is in "external

Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods

NASA Astrophysics Data System (ADS)

Kaupp, Martin; Arbuznikov, Alexei V.; Heßelmann, Andreas; Görling, Andreas

2010-05-01

The isotropic hyperfine coupling constants of the free N(S4) and P(S4) atoms have been evaluated with high-level post-Hartree-Fock and density-functional methods. The phosphorus hyperfine coupling presents a significant challenge to both types of methods. With large basis sets, MP2 and coupled-cluster singles and doubles calculations give much too small values for the phosphorus atom. Triple excitations are needed in coupled-cluster calculations to achieve reasonable agreement with experiment. None of the standard density functionals reproduce even the correct sign of this hyperfine coupling. Similarly, the computed hyperfine couplings depend crucially on the self-consistent treatment in exact-exchange density-functional theory within the optimized effective potential (OEP) method. Well-balanced auxiliary and orbital basis sets are needed for basis-expansion exact-exchange-only OEP approaches to come close to Hartree-Fock or numerical OEP data. Results from the localized Hartree-Fock and Krieger-Li-Iafrate approximations deviate notably from exact OEP data in spite of very similar total energies. Of the functionals tested, only full exact-exchange methods augmented by a correlation functional gave at least the correct sign of the P(S4) hyperfine coupling but with too low absolute values. The subtle interplay between the spin-polarization contributions of the different core shells has been analyzed, and the influence of even very small changes in the exchange-correlation potential could be identified.

A supercritical density of fast Na+ channels ensures rapid propagation of action potentials in GABAergic interneuron axons

PubMed Central

Hu, Hua; Jonas, Peter

2014-01-01

Fast-spiking, parvalbumin-expressing GABAergic interneurons/basket cells (BCs) play a key role in feedforward and feedback inhibition, gamma oscillations, and complex information processing. For these functions, fast propagation of action potentials (APs) from the soma to the presynaptic terminals is important. However, the functional properties of interneuron axons remain elusive. Here, we examined interneuron axons by confocally targeted subcellular patch-clamp recording in rat hippocampal slices. APs were initiated in the proximal axon ~20 μm from the soma, and propagated to the distal axon with high reliability and speed. Subcellular mapping revealed a stepwise increase of Na+ conductance density from the soma to the proximal axon, followed by a further gradual increase in the distal axon. Active cable modeling and experiments with partial channel block indicated that low axonal Na+ conductance density was sufficient for reliability, but high Na+ density was necessary for both speed of propagation and fast-spiking AP phenotype. Our results suggest that a supercritical density of Na+ channels compensates for the morphological properties of interneuron axons (small segmental diameter, extensive branching, and high bouton density), ensuring fast AP propagation and high-frequency repetitive firing. PMID:24657965

An extended hybrid density functional (X3LYP) with improved descriptions of nonbond interactions and thermodynamic properties of molecular systems.

PubMed

Xu, Xin; Zhang, Qingsong; Muller, Richard P; Goddard, William A

2005-01-01

We derive here the form for the exact exchange energy density for a density that decays with Gaussian-type behavior at long range. This functional is intermediate between the B88 and the PW91 exchange functionals. Using this modified functional to match the form expected for Gaussian densities, we propose the X3LYP extended functional. We find that X3LYP significantly outperforms Becke three parameter Lee-Yang-Parr (B3LYP) for describing van der Waals and hydrogen bond interactions, while performing slightly better than B3LYP for predicting heats of formation, ionization potentials, electron affinities, proton affinities, and total atomic energies as validated with the extended G2 set of atoms and molecules. Thus X3LYP greatly enlarges the field of applications for density functional theory. In particular the success of X3LYP in describing the water dimer (with R(e) and D(e) within the error bars of the most accurate determinations) makes it an excellent candidate for predicting accurate ligand-protein and ligand-DNA interactions. (c) 2005 American Institute of Physics.

Universal calculational recipe for solvent-mediated potential: based on a combination of integral equation theory and density functional theory

NASA Astrophysics Data System (ADS)

Zhou, Shiqi

2004-07-01

A universal formalism, which enables calculation of solvent-mediated potential (SMP) between two equal or non-equal solute particles with any shape immersed in solvent reservior consisting of atomic particle and/or polymer chain or their mixture, is proposed by importing a density functional theory externally into OZ equation systems. Only if size asymmetry of the solvent bath components is moderate, the present formalism can calculate the SMP in any complex fluids at the present development stage of statistical mechanics, and therefore avoids all of limitations of previous approaches for SMP. Preliminary calculation indicates the reliability of the present formalism.

Time-dependent spin-density-functional-theory description of He+-He collisions

NASA Astrophysics Data System (ADS)

Baxter, Matthew; Kirchner, Tom; Engel, Eberhard

2017-09-01

Theoretical total cross-section results for all ionization and capture processes in the He+-He collision system are presented in the approximate impact energy range of 10-1000 keV/amu. Calculations were performed within the framework of time-dependent spin-density functional theory. The Krieger-Li-Iafrate approximation was used to determine an accurate exchange-correlation potential in the exchange-only limit. The results of two models, one where electron translation factors in the orbitals used to calculate the potential are ignored and another where partial electron translation factors are included, are compared with available experimental data as well as a selection of previous theoretical calculations.

Computational predictions of zinc oxide hollow structures

NASA Astrophysics Data System (ADS)

Tuoc, Vu Ngoc; Huan, Tran Doan; Thao, Nguyen Thi

2018-03-01

Nanoporous materials are emerging as potential candidates for a wide range of technological applications in environment, electronic, and optoelectronics, to name just a few. Within this active research area, experimental works are predominant while theoretical/computational prediction and study of these materials face some intrinsic challenges, one of them is how to predict porous structures. We propose a computationally and technically feasible approach for predicting zinc oxide structures with hollows at the nano scale. The designed zinc oxide hollow structures are studied with computations using the density functional tight binding and conventional density functional theory methods, revealing a variety of promising mechanical and electronic properties, which can potentially find future realistic applications.

Simplicity of condensed matter at its core: generic definition of a Roskilde-simple system.

PubMed

Schrøder, Thomas B; Dyre, Jeppe C

2014-11-28

The isomorph theory is reformulated by defining Roskilde-simple systems by the property that the order of the potential energies of configurations at one density is maintained when these are scaled uniformly to a different density. If the potential energy as a function of all particle coordinates is denoted by U(R), this requirement translates into U(Ra) < U(Rb) ⇒ U(λRa) < U(λRb). Isomorphs remain curves in the thermodynamic phase diagram along which structure, dynamics, and excess entropy are invariant, implying that the phase diagram is effectively one-dimensional with respect to many reduced-unit properties. In contrast to the original formulation of the isomorph theory, however, the density-scaling exponent is not exclusively a function of density and the isochoric heat capacity is not an exact isomorph invariant. A prediction is given for the latter quantity's variation along the isomorphs. Molecular dynamics simulations of the Lennard-Jones and Lennard-Jones Gaussian systems validate the new approach.

Pair Potential That Reproduces the Shape of Isochrones in Molecular Liquids.

PubMed

Veldhorst, Arno A; Schrøder, Thomas B; Dyre, Jeppe C

2016-08-18

Many liquids have curves (isomorphs) in their phase diagrams along which structure, dynamics, and some thermodynamic quantities are invariant in reduced units. A substantial part of their phase diagrams is thus effectively one dimensional. The shapes of these isomorphs are described by a material-dependent function of density, h(ρ), which for real liquids is well approximated by a power law, ρ(γ). However, in simulations, a power law is not adequate when density changes are large; typical models, such as Lennard-Jones liquids, show that γ(ρ) ≡ d ln h(ρ)/d ln ρ is a decreasing function of density. This article presents results from computer simulations using a new pair potential that diverges at a nonzero distance and can be tuned to give a more realistic shape of γ(ρ). Our results indicate that the finite size of molecules is an important factor to take into account when modeling liquids over a large density range.

Coupling of ab initio density functional theory and molecular dynamics for the multiscale modeling of carbon nanotubes

NASA Astrophysics Data System (ADS)

Ng, T. Y.; Yeak, S. H.; Liew, K. M.

2008-02-01

A multiscale technique is developed that couples empirical molecular dynamics (MD) and ab initio density functional theory (DFT). An overlap handshaking region between the empirical MD and ab initio DFT regions is formulated and the interaction forces between the carbon atoms are calculated based on the second-generation reactive empirical bond order potential, the long-range Lennard-Jones potential as well as the quantum-mechanical DFT derived forces. A density of point algorithm is also developed to track all interatomic distances in the system, and to activate and establish the DFT and handshaking regions. Through parallel computing, this multiscale method is used here to study the dynamic behavior of single-walled carbon nanotubes (SWCNTs) under asymmetrical axial compression. The detection of sideways buckling due to the asymmetrical axial compression is reported and discussed. It is noted from this study on SWCNTs that the MD results may be stiffer compared to those with electron density considerations, i.e. first-principle ab initio methods.

High density event-related potential data acquisition in cognitive neuroscience.

PubMed

Slotnick, Scott D

2010-04-16

Functional magnetic resonance imaging (fMRI) is currently the standard method of evaluating brain function in the field of Cognitive Neuroscience, in part because fMRI data acquisition and analysis techniques are readily available. Because fMRI has excellent spatial resolution but poor temporal resolution, this method can only be used to identify the spatial location of brain activity associated with a given cognitive process (and reveals virtually nothing about the time course of brain activity). By contrast, event-related potential (ERP) recording, a method that is used much less frequently than fMRI, has excellent temporal resolution and thus can track rapid temporal modulations in neural activity. Unfortunately, ERPs are under utilized in Cognitive Neuroscience because data acquisition techniques are not readily available and low density ERP recording has poor spatial resolution. In an effort to foster the increased use of ERPs in Cognitive Neuroscience, the present article details key techniques involved in high density ERP data acquisition. Critically, high density ERPs offer the promise of excellent temporal resolution and good spatial resolution (or excellent spatial resolution if coupled with fMRI), which is necessary to capture the spatial-temporal dynamics of human brain function.

Comparison of Molecular Dynamics with Classical Density Functional and Poisson–Boltzmann Theories of the Electric Double Layer in Nanochannels

PubMed Central

2012-01-01

Comparisons are made among Molecular Dynamics (MD), Classical Density Functional Theory (c-DFT), and Poisson–Boltzmann (PB) modeling of the electric double layer (EDL) for the nonprimitive three component model (3CM) in which the two ion species and solvent molecules are all of finite size. Unlike previous comparisons between c-DFT and Monte Carlo (MC), the present 3CM incorporates Lennard-Jones interactions rather than hard-sphere and hard-wall repulsions. c-DFT and MD results are compared over normalized surface charges ranging from 0.2 to 1.75 and bulk ion concentrations from 10 mM to 1 M. Agreement between the two, assessed by electric surface potential and ion density profiles, is found to be quite good. Wall potentials predicted by PB begin to depart significantly from c-DFT and MD for charge densities exceeding 0.3. Successive layers are observed to charge in a sequential manner such that the solvent becomes fully excluded from each layer before the onset of the next layer. Ultimately, this layer filling phenomenon results in fluid structures, Debye lengths, and electric surface potentials vastly different from the classical PB predictions. PMID:23316120

Solvation and Spectral Line Shifts of Chromium Atoms in Helium Droplets Based on a Density Functional Theory Approach

PubMed Central

2014-01-01

The interaction of an electronically excited, single chromium (Cr) atom with superfluid helium nanodroplets of various size (10 to 2000 helium (He) atoms) is studied with helium density functional theory. Solvation energies and pseudo-diatomic potential energy surfaces are determined for Cr in its ground state as well as in the y7P, a5S, and y5P excited states. The necessary Cr–He pair potentials are calculated by standard methods of molecular orbital-based electronic structure theory. In its electronic ground state the Cr atom is found to be fully submerged in the droplet. A solvation shell structure is derived from fluctuations in the radial helium density. Electronic excitations of an embedded Cr atom are simulated by confronting the relaxed helium density (ρHe), obtained for Cr in the ground state, with interaction pair potentials of excited states. The resulting energy shifts for the transitions z7P ← a7S, y7P ← a7S, z5P ← a5S, and y5P ← a5S are compared to recent fluorescence and photoionization experiments. PMID:24906160

Solvation and spectral line shifts of chromium atoms in helium droplets based on a density functional theory approach.

PubMed

Ratschek, Martin; Pototschnig, Johann V; Hauser, Andreas W; Ernst, Wolfgang E

2014-08-21

The interaction of an electronically excited, single chromium (Cr) atom with superfluid helium nanodroplets of various size (10 to 2000 helium (He) atoms) is studied with helium density functional theory. Solvation energies and pseudo-diatomic potential energy surfaces are determined for Cr in its ground state as well as in the y(7)P, a(5)S, and y(5)P excited states. The necessary Cr-He pair potentials are calculated by standard methods of molecular orbital-based electronic structure theory. In its electronic ground state the Cr atom is found to be fully submerged in the droplet. A solvation shell structure is derived from fluctuations in the radial helium density. Electronic excitations of an embedded Cr atom are simulated by confronting the relaxed helium density (ρHe), obtained for Cr in the ground state, with interaction pair potentials of excited states. The resulting energy shifts for the transitions z(7)P ← a(7)S, y(7)P ← a(7)S, z(5)P ← a(5)S, and y(5)P ← a(5)S are compared to recent fluorescence and photoionization experiments.

Density functional theory study of defects in unalloyed δ-Pu

DOE PAGES

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

2017-03-19

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

Layered interfaces between immiscible liquids studied by density-functional theory and molecular-dynamics simulations.

PubMed

Geysermans, P; Elyeznasni, N; Russier, V

2005-11-22

We present a study of the structure in the interface between two immiscible liquids by density-functional theory and molecular-dynamics calculations. The liquids are modeled by Lennard-Jones potentials, which achieve immiscibility by suppressing the attractive interaction between unlike particles. The density profiles of the liquids display oscillations only in a limited part of the simple liquid-phase diagram (rho,T). When approaching the liquid-vapor coexistence, a significant depletion appears while the layering behavior of the density profile vanishes. By analogy with the liquid-vapor interface and the analysis of the adsorption this behavior is suggested to be strongly related to the drying transition.

Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

PubMed

Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

2013-02-01

The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk.

Linear stability analysis of the Vlasov-Poisson equations in high density plasmas in the presence of crossed fields and density gradients

NASA Technical Reports Server (NTRS)

Kaup, D. J.; Hansen, P. J.; Choudhury, S. Roy; Thomas, Gary E.

1986-01-01

The equations for the single-particle orbits in a nonneutral high density plasma in the presence of inhomogeneous crossed fields are obtained. Using these orbits, the linearized Vlasov equation is solved as an expansion in the orbital radii in the presence of inhomogeneities and density gradients. A model distribution function is introduced whose cold-fluid limit is exactly the same as that used in many previous studies of the cold-fluid equations. This model function is used to reduce the linearized Vlasov-Poisson equations to a second-order ordinary differential equation for the linearized electrostatic potential whose eigenvalue is the perturbation frequency.

Density functional theory study of defects in unalloyed δ-Pu

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

Hernandez, S. C.; Freibert, F. J.; Wills, J. M.

Using density functional theory, we explore in this paper various classical point and complex defects within the face-centered cubic unalloyed δ-plutonium matrix that are potentially induced from self-irradiation. For plutonium only defects, the most energetically stable defect is a distorted split-interstitial. Gallium, the δ-phase stabilizer, is thermodynamically stable as a substitutional defect, but becomes unstable when participating in a complex defect configuration. Finally, complex uranium defects may thermodynamically exist as uranium substitutional with neighboring plutonium interstitial and stabilization of uranium within the lattice is shown via partial density of states and charge density difference plots to be 5f hybridization betweenmore » uranium and plutonium.« less

Structures, phase stabilities, and electrical potentials of Li-Si battery anode materials

NASA Astrophysics Data System (ADS)

Tipton, William W.; Bealing, Clive R.; Mathew, Kiran; Hennig, Richard G.

2013-05-01

The Li-Si materials system holds promise for use as an anode in Li-ion battery applications. For this system, we determine the charge capacity, voltage profiles, and energy storage density solely by ab initio methods without any experimental input. We determine the energetics of the stable and metastable Li-Si phases likely to form during the charging and discharging of a battery. Ab initio molecular dynamics simulations are used to model the structure of amorphous Li-Si as a function of composition, and a genetic algorithm coupled to density-functional theory searches the Li-Si binary phase diagram for small-cell, metastable crystal structures. Calculations of the phonon densities of states using density-functional perturbation theory for selected structures determine the importance of vibrational, including zero-point, contributions to the free energies. The energetics and local structural motifs of these metastable Li-Si phases closely resemble those of the amorphous phases, making these small unit cell crystal phases good approximants of the amorphous phase for use in further studies. The charge capacity is estimated, and the electrical potential profiles and the energy density of Li-Si anodes are predicted. We find, in good agreement with experimental measurements, that the formation of amorphous Li-Si only slightly increases the anode potential. Additionally, the genetic algorithm identifies a previously unreported member of the Li-Si binary phase diagram with composition Li5Si2 which is stable at 0 K with respect to previously known phases. We discuss its relationship to the partially occupied Li7Si3 phase.

Mott Transition in GdMnO3: an Ab Initio Study

NASA Astrophysics Data System (ADS)

Ferreira, W. S.; Moreira, E.; Frazão, N. F.

2018-04-01

Orthorhombic GdMnO3 is studied using density functional theory considering the pseudo-potential plane-wave method within local-spin-density approximation, LSDA. The electronic band structure and density of states, for several hydrostatic pressures, are studied. The Mott transition was observed at 60 GPa. Calculated lattice parameters are close to the experimental measurements, and some indirect band gaps (S→Γ) were obtained within the LSDA level of calculation, between the occupied O-2 p and unoccupied Gd-4 f states. The variation of the gap reduces with increasing pressure, being well fitted to a quadratic function.

v-representability and density functional theory. [for nonrelativistic electrons in nondegenerate ground state

NASA Technical Reports Server (NTRS)

Kohn, W.

1983-01-01

It is shown that if n(r) is the discrete density on a lattice (enclosed in a finite box) associated with a nondegenerate ground state in an external potential v(r) (i.e., is 'v-representable'), then the density n(r) + mu(r), with m(r) arbitrary (apart from trivial constraints) and mu small enough, is also associated with a nondegenerate ground state in an external potential v'(r) near v(r); i.e., n(r) + m(r) is also v-representable. Implications for the Hohenberg-Kohn variational principle and the Kohn-Sham equations are discussed.

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

Motevaselian, M. H.; Mashayak, S. Y.; Aluru, N. R., E-mail: aluru@illinois.edu

Empirical potential-based quasi-continuum theory (EQT) provides a route to incorporate atomistic detail into continuum framework such as the Nernst-Planck equation. EQT can also be used to construct a grand potential functional for classical density functional theory (cDFT). The combination of EQT and cDFT provides a simple and fast approach to predict the inhomogeneous density, potential profiles, and thermodynamic properties of confined fluids. We extend the EQT-cDFT approach to confined fluid mixtures and demonstrate it by simulating a mixture of methane and hydrogen inside slit-like channels of graphene. We show that the EQT-cDFT predictions for the structure of the confined fluidmore » mixture compare well with the molecular dynamics simulation results. In addition, our results show that graphene slit nanopores exhibit a selective adsorption of methane over hydrogen.« less

First-row diatomics: Calculation of the geometry and energetics using self-consistent gradient-functional approximations

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

Kutzler, F.W.; Painter, G.S.

1992-02-15

A fully self-consistent series of nonlocal (gradient) density-functional calculations has been carried out using the augmented-Gaussian-orbital method to determine the magnitude of gradient corrections to the potential-energy curves of the first-row diatomics, Li{sub 2} through F{sub 2}. Both the Langreth-Mehl-Hu and the Perdew-Wang gradient-density functionals were used in calculations of the binding energy, bond length, and vibrational frequency for each dimer. Comparison with results obtained in the local-spin-density approximation (LSDA) using the Vosko-Wilk-Nusair functional, and with experiment, reveals that bond lengths and vibrational frequencies are rather insensitive to details of the gradient functionals, including self-consistency effects, but the gradient correctionsmore » reduce the overbinding commonly observed in the LSDA calculations of first-row diatomics (with the exception of Li{sub 2}, the gradient-functional binding-energy error is only 50--12 % of the LSDA error). The improved binding energies result from a large differential energy lowering, which occurs in open-shell atoms relative to the diatomics. The stabilization of the atom arises from the use of nonspherical charge and spin densities in the gradient-functional calculations. This stabilization is negligibly small in LSDA calculations performed with nonspherical densities.« less

Statistical correlations in an ideal gas of particles obeying fractional exclusion statistics.

PubMed

Pellegrino, F M D; Angilella, G G N; March, N H; Pucci, R

2007-12-01

After a brief discussion of the concepts of fractional exchange and fractional exclusion statistics, we report partly analytical and partly numerical results on thermodynamic properties of assemblies of particles obeying fractional exclusion statistics. The effect of dimensionality is one focal point, the ratio mu/k_(B)T of chemical potential to thermal energy being obtained numerically as a function of a scaled particle density. Pair correlation functions are also presented as a function of the statistical parameter, with Friedel oscillations developing close to the fermion limit, for sufficiently large density.

Exploring the surface reactivity of 3d metal endofullerenes: a density-functional theory study.

PubMed

Estrada-Salas, Rubén E; Valladares, Ariel A

2009-09-24

Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

Conceptual DFT Descriptors of Amino Acids with Potential Corrosion Inhibition Properties Calculated with the Latest Minnesota Density Functionals

PubMed Central

Frau, Juan; Glossman-Mitnik, Daniel

2017-01-01

Amino acids and peptides have the potential to perform as corrosion inhibitors. The chemical reactivity descriptors that arise from Conceptual DFT for the twenty natural amino acids have been calculated by using the latest Minnesota family of density functionals. In order to verify the validity of the calculation of the descriptors directly from the HOMO and LUMO, a comparison has been performed with those obtained through ΔSCF results. Moreover, the active sites for nucleophilic and electrophilic attacks have been identified through Fukui function indices, the dual descriptor Δf(r) and the electrophilic and nucleophilic Parr functions. The results could be of interest as a starting point for the study of large peptides where the calculation of the radical cation and anion of each system may be computationally harder and costly. PMID:28361050

Fission barriers from multidimensionally-constrained covariant density functional theories

NASA Astrophysics Data System (ADS)

Lu, Bing-Nan; Zhao, Jie; Zhao, En-Guang; Zhou, Shan-Gui

2017-11-01

In recent years, we have developed the multidimensionally-constrained covariant density functional theories (MDC-CDFTs) in which both axial and spatial reflection symmetries are broken and all shape degrees of freedom described by βλμ with even μ, such as β20, β22, β30, β32, β40, etc., are included self-consistently. The MDC-CDFTs have been applied to the investigation of potential energy surfaces and fission barriers of actinide nuclei, third minima in potential energy surfaces of light actinides, shapes and potential energy surfaces of superheavy nuclei, octupole correlations between multiple chiral doublet bands in 78Br, octupole correlations in Ba isotopes, the Y32 correlations in N = 150 isotones and Zr isotopes, the spontaneous fission of Fm isotopes, and shapes of hypernuclei. In this contribution we present the formalism of MDC-CDFTs and the application of these theories to the study of fission barriers and potential energy surfaces of actinide nuclei.

Theory of Friedel oscillations in monolayer graphene and group-VI dichalcogenides in a magnetic field

NASA Astrophysics Data System (ADS)

Rusin, Tomasz M.; Zawadzki, Wlodek

2018-05-01

Friedel oscillations (FO) of electron density caused by a deltalike neutral impurity in two-dimensional (2D) systems in a magnetic field are calculated. Three 2D cases are considered: free electron gas, monolayer graphene, and group-VI dichalcogenides. An exact form of the renormalized Green's function is used in the calculations, as obtained by a summation of the infinite Dyson series and regularization procedure. Final results are valid for large ranges of potential strengths V0, electron densities ne, magnetic fields B , and distances from the impurity r . Realistic models for the impurities are used. The first FO of induced density in WS2 are described by the relation Δ n (r ) ∝sin(2 π r /TFO) /r2 , where TFO∝1 /√{EF} . For weak impurity potentials, the amplitudes of FO are proportional to V0. For attractive potentials and high fields, the total electron density remains positive for all r . On the other hand, for low fields, repulsive potentials and small r , the total electron density may become negative, so that many-body effects should be taken into account.

Local-spin-density calculations for iron: Effect of spin interpolation on ground-state properties

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

MacLaren, J.M.; Clougherty, D.P.; Albers, R.C.

1990-08-15

Scalar-relativistic self-consistent linear muffin-tin orbital (LMTO) calculations for bcc and fcc Fe have been performed with several different local approximations to the exchange and correlation energy density and potential. Overall, in contrast to the conclusions of previous studies, we find that the local-spin-density approximation to exchange and correlation can provide an adequate description of bulk Fe {ital provided} that a proper parametrization of the correlation energy density and potential of the homogeneous electron gas over both spin and density is used. Lattice constants, found from the position of the minimum of the total energy as a function of Wigner-Seitz radius,more » agree to within 1% (for {ital s},{ital p},{ital d} LMTO's only) and within 1--2% (for {ital s},{ital p},{ital d},{ital f} LMTO's) of the experimental lattice constants for all forms used for the local correlation. The best agreement, however, was obtained using a local correlation potential derived from the Vosko-Wilk-Nusair form for the spin dependence of the correlation energy density. The calculation performed with this correlation potential was also the only calculation to correctly predict a bcc ferromagnetic ground state.« 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

Interaction between colloidal particles on an oil-water interface in dilute and dense phases.

PubMed

Parolini, Lucia; Law, Adam D; Maestro, Armando; Buzza, D Martin A; Cicuta, Pietro

2015-05-20

The interaction between micron-sized charged colloidal particles at polar/non-polar liquid interfaces remains surprisingly poorly understood for a relatively simple physical chemistry system. By measuring the pair correlation function g(r) for different densities of polystyrene particles at the decane-water interface, and using a powerful predictor-corrector inversion scheme, effective pair-interaction potentials can be obtained up to fairly high densities, and these reproduce the experimental g(r) in forward simulations, so are self consistent. While at low densities these potentials agree with published dipole-dipole repulsion, measured by various methods, an apparent density dependence and long range attraction are obtained when the density is higher. This condition is thus explored in an alternative fashion, measuring the local mobility of colloids when confined by their neighbors. This method of extracting interaction potentials gives results that are consistent with dipolar repulsion throughout the concentration range, with the same magnitude as in the dilute limit. We are unable to rule out the density dependence based on the experimental accuracy of our data, but we show that incomplete equilibration of the experimental system, which would be possible despite long waiting times due to the very strong repulsions, is a possible cause of artefacts in the inverted potentials. We conclude that to within the precision of these measurements, the dilute pair potential remains valid at high density in this system.

Generalized Pauli constraints in reduced density matrix functional theory.

PubMed

Theophilou, Iris; Lathiotakis, Nektarios N; Marques, Miguel A L; Helbig, Nicole

2015-04-21

Functionals of the one-body reduced density matrix (1-RDM) are routinely minimized under Coleman's ensemble N-representability conditions. Recently, the topic of pure-state N-representability conditions, also known as generalized Pauli constraints, received increased attention following the discovery of a systematic way to derive them for any number of electrons and any finite dimensionality of the Hilbert space. The target of this work is to assess the potential impact of the enforcement of the pure-state conditions on the results of reduced density-matrix functional theory calculations. In particular, we examine whether the standard minimization of typical 1-RDM functionals under the ensemble N-representability conditions violates the pure-state conditions for prototype 3-electron systems. We also enforce the pure-state conditions, in addition to the ensemble ones, for the same systems and functionals and compare the correlation energies and optimal occupation numbers with those obtained by the enforcement of the ensemble conditions alone.

Density functional study on the structural and thermodynamic properties of aqueous DNA-electrolyte solution in the framework of cell model.

PubMed

Wang, Ke; Yu, Yang-Xin; Gao, Guang-Hua

2008-05-14

A density functional theory (DFT) in the framework of cell model is proposed to calculate the structural and thermodynamic properties of aqueous DNA-electrolyte solution with finite DNA concentrations. The hard-sphere contribution to the excess Helmholtz energy functional is derived from the modified fundamental measure theory, and the electrostatic interaction is evaluated through a quadratic functional Taylor expansion around a uniform fluid. The electroneutrality in the cell leads to a variational equation with a constraint. Since the reference fluid is selected to be a bulk phase, the Lagrange multiplier proves to be the potential drop across the cell boundary (Donnan potential). The ion profiles and electrostatic potential profiles in the cell are calculated from the present DFT-cell model. Our DFT-cell model gives better prediction of ion profiles than the Poisson-Boltzmann (PB)- or modified PB-cell models when compared to the molecular simulation data. The effects of polyelectrolyte concentration, ion size, and added-salt concentration on the electrostatic potential difference between the DNA surface and the cell boundary are investigated. The expression of osmotic coefficient is derived from the general formula of grand potential. The osmotic coefficients predicted by the DFT are lower than the PB results and are closer to the simulation results and experimental data.

Density functional theory (DFT) study of a new novel bionanosensor hybrid; tryptophan/Pd doped single walled carbon nanotube

NASA Astrophysics Data System (ADS)

Yoosefian, Mehdi; Etminan, Nazanin

2016-07-01

In order to explore a new novel L-amino acid/transition metal doped single walled carbon nanotube based biosensor, density functional theory calculations were studied. These hybrid structures of organic-inorganic nanobiosensors are able to detect the smallest amino acid building block of proteins. The configurations of amine and carbonyl group coordination of tryptophan aromatic amino acid adsorbed on Pd/doped single walled carbon nanotube were compared. The frontier molecular orbital theory, quantum theory atom in molecule and natural bond orbital analysis were performed. The molecular electrostatic potential and the electron density surfaces were constructed. The calculations indicated that the Pd/SWCNT was sensitive to tryptophan suggesting the importance of interaction with biological molecule and potential detecting application. The proposed nanobiosensor represents a highly sensitive detection of protein at ultra-low concentration in diagnosis applications.

Endocochlear potential generation is associated with intercellular communication in the stria vascularis: structural analysis in the viable dominant spotting mouse mutant.

PubMed

Carlisle, L; Steel, K; Forge, A

1990-11-01

Deafness in the viable dominant spotting mouse mutant is due to a primary defect of the stria vascularis which results in absence of the positive endocochlear potential in scala media. Endocochlear potentials were measured and the structure of stria vascularis of mutants with potentials close to zero was compared with that in normal littermate controls by use of morphometric methods. The stria vascularis was significantly thinner in mutants. Marginal cells were not significantly different from controls in terms of volume density or intramembrane particle density but the network density of tight junctions was significantly reduced in the mutants. A virtual absence of gap junctions between basal cells and marginal or intermediate cells was observed, but intramembrane particle density and junctional complexes between adjacent basal cells were not different from controls. The volume density of basal cells was significantly greater in mutants. Intermediate cells accounted for a significantly smaller volume density of the stria vascularis in mutants and had a lower density of intramembrane particles than controls. Melanocytes were not identified in the stria vascularis of mutants. These results suggest that communication between marginal, intermediate and basal cells might be important to the normal function of the stria vascularis.

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions.

PubMed

Karasiev, Valentin V; Dufty, James W; Trickey, S B

2018-02-16

Realizing the potential for predictive density functional calculations of matter under extreme conditions depends crucially upon having an exchange-correlation (XC) free-energy functional accurate over a wide range of state conditions. Unlike the ground-state case, no such functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free-energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Its accuracy in the warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated T. Pressure shifts for hot electrons in compressed static fcc Al and for low-density Al demonstrate the combined magnitude of thermal and gradient effects handled well by this functional over a wide T range.

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

NASA Astrophysics Data System (ADS)

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

2018-02-01

Realizing the potential for predictive density functional calculations of matter under extreme conditions depends crucially upon having an exchange-correlation (X C ) free-energy functional accurate over a wide range of state conditions. Unlike the ground-state case, no such functional exists. We remedy that with systematic construction of a generalized gradient approximation X C free-energy functional based on rigorous constraints, including the free-energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T , high-T , and homogeneous electron gas limits. Its accuracy in the warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated T . Pressure shifts for hot electrons in compressed static fcc Al and for low-density Al demonstrate the combined magnitude of thermal and gradient effects handled well by this functional over a wide T range.

Structure of spherical electric double layers with fully asymmetric electrolytes: a systematic study by Monte Carlo simulations and density functional theory.

PubMed

Patra, Chandra N

2014-11-14

A systematic investigation of the spherical electric double layers with the electrolytes having size as well as charge asymmetry is carried out using density functional theory and Monte Carlo simulations. The system is considered within the primitive model, where the macroion is a structureless hard spherical colloid, the small ions as charged hard spheres of different size, and the solvent is represented as a dielectric continuum. The present theory approximates the hard sphere part of the one particle correlation function using a weighted density approach whereas a perturbation expansion around the uniform fluid is applied to evaluate the ionic contribution. The theory is in quantitative agreement with Monte Carlo simulation for the density and the mean electrostatic potential profiles over a wide range of electrolyte concentrations, surface charge densities, valence of small ions, and macroion sizes. The theory provides distinctive evidence of charge and size correlations within the electrode-electrolyte interface in spherical geometry.

Effects of molecular elongation on liquid crystalline phase behaviour: isotropic-nematic transition

NASA Astrophysics Data System (ADS)

Singh, Ram Chandra; Ram, Jokhan

2003-08-01

We present the density-functional approach to study the isotropic-nematic transitions and calculate the values of freezing parameters of the Gay-Berne liquid crystal model, concentrating on the effects of varying the molecular elongation, x0. For this, we have solved the Percus-Yevick integral equation theory to calculate the pair-correlation functions of a fluid the molecules of which interact via a Gay-Berne pair potential. These results have been used in the density-functional theory as an input to locate the isotropic-nematic transition and calculate freezing parameters for a range of length-to-width parameters 3.0⩽ x0⩽4.0 at reduced temperatures 0.95 and 1.25. We observed that as x0 is increased, the isotropic-nematic transition is seen to move to lower density at a given temperature. We find that the density-functional theory is good to study the freezing transitions in such fluids. We have also compared our results with computer simulation results wherever they are available.

Magnetic exchange couplings from constrained density functional theory: an efficient approach utilizing analytic derivatives.

PubMed

Phillips, Jordan J; Peralta, Juan E

2011-11-14

We introduce a method for evaluating magnetic exchange couplings based on the constrained density functional theory (C-DFT) approach of Rudra, Wu, and Van Voorhis [J. Chem. Phys. 124, 024103 (2006)]. Our method shares the same physical principles as C-DFT but makes use of the fact that the electronic energy changes quadratically and bilinearly with respect to the constraints in the range of interest. This allows us to use coupled perturbed Kohn-Sham spin density functional theory to determine approximately the corrections to the energy of the different spin configurations and construct a priori the relevant energy-landscapes obtained by constrained spin density functional theory. We assess this methodology in a set of binuclear transition-metal complexes and show that it reproduces very closely the results of C-DFT. This demonstrates a proof-of-concept for this method as a potential tool for studying a number of other molecular phenomena. Additionally, routes to improving upon the limitations of this method are discussed. © 2011 American Institute of Physics

Exact density-potential pairs from complex-shifted axisymmetric systems

NASA Astrophysics Data System (ADS)

Ciotti, Luca; Marinacci, Federico

2008-07-01

In a previous paper, the complex-shift method has been applied to self-gravitating spherical systems, producing new analytical axisymmetric density-potential pairs. We now extend the treatment to the Miyamoto-Nagai disc and the Binney logarithmic halo, and we study the resulting axisymmetric and triaxial analytical density-potential pairs; we also show how to obtain the surface density of shifted systems from the complex shift of the surface density of the parent model. In particular, the systems obtained from Miyamoto-Nagai discs can be used to describe disc galaxies with a peanut-shaped bulge or with a central triaxial bar, depending on the direction of the shift vector. By using a constructive method that can be applied to generic axisymmetric systems, we finally show that the Miyamoto-Nagai and the Satoh discs, and the Binney logarithmic halo cannot be obtained from the complex shift of any spherical parent distribution. As a by-product of this study, we also found two new generating functions in closed form for even and odd Legendre polynomials, respectively.

The effect of a periodic absorptive strip arrangement on an interior sound field in a room.

PubMed

Park, Joo-Bae; Grosh, Karl; Kim, Yang-Hann

2005-02-01

In this paper we study the effect of periodically arranged sound absorptive strips on the mean acoustic potential energy density distribution of a room. The strips are assumed to be attached on the room's surface of interest. In order to determine their effect, the mean acoustic potential energy density variation is evaluated as the function of a ratio of the strip's arrangement period to wavelength. The evaluation demonstrates that the mean acoustic potential energy density tends to converge. In addition, a comparison with a case in which absorptive materials completely cover the selected absorptive plane shows that a periodic arrangement that uses only half of the absorptive material can be more efficient than a total covering, unless the frequency of interest does not coincide with the room's resonant frequencies. Consequently, the results prove that the ratio of the arrangement period to the wavelength plays an important role in the effectiveness of a periodic absorptive strip arrangement to minimize a room's mean acoustic potential energy density.

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.

Discontinuity of the exchange-correlation potential and the functional derivative of the noninteracting kinetic energy as the number of electrons crosses integer boundaries in Li, Be, and B.

PubMed

Morrison, Robert C

2015-01-07

Accurate densities were determined from configuration interaction wave functions for atoms and ions of Li, Be, and B with up to four electrons. Exchange-correlation potentials, Vxc(r), and functional derivatives of the noninteracting kinetic energy, δK[ρ]/δρ(r), obtained from these densities were used to examine their discontinuities as the number of electrons N increases across integer boundaries for N = 1, N = 2, and N = 3. These numerical results are consistent with conclusions that the discontinuities are characterized by a jump in the chemical potential while the shape of Vxc(r) varies continuously as an integer boundary is crossed. The discontinuity of the Vxc(r) is positive, depends on the ionization potential, electron affinity, and orbital energy differences, and the discontinuity in δK[ρ]/δρ(r) depends on the difference between the energies of the highest occupied and lowest unoccupied orbitals. The noninteracting kinetic energy and the exchange correlation energy have been computed for integer and noninteger values of N between 1 and 4.

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

Fromm, Andrea; Bonitz, Michael; Dufty, James

The idea of treating quantum systems by semiclassical representations using effective quantum potentials (forces) has been successfully applied in equilibrium by many authors, see e.g. [D. Bohm, Phys. Rev. 85 (1986) 166 and 180; D.K. Ferry, J.R. Zhou, Phys. Rev. B 48 (1993) 7944; A.V. Filinov, M. Bonitz, W. Ebeling, J. Phys. A 36 (2003) 5957 and references cited therein]. Here, this idea is extended to nonequilibrium quantum systems in an external field. A gauge-invariant quantum kinetic theory for weakly inhomogeneous charged particle systems in a strong electromagnetic field is developed within the framework of nonequilibrium Green's functions. The equationmore » for the spectral density is simplified by introducing a classical (local) form for the kinetics. Nonlocal quantum effects are accounted for in this way by replacing the bare external confinement potential with an effective quantum potential. The equation for this effective potential is identified and solved for weak inhomogeneity in the collisionless limit. The resulting nonequilibrium spectral function is used to determine the density of states and the modification of the Born collision operator in the kinetic equation for the Wigner function due to quantum confinement effects.« less

Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials.

PubMed

Verma, Prakash; Bartlett, Rodney J

2016-07-21

Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.

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

Yu, Kuang; Libisch, Florian; Carter, Emily A., E-mail: eac@princeton.edu

We report a new implementation of the density functional embedding theory (DFET) in the VASP code, using the projector-augmented-wave (PAW) formalism. Newly developed algorithms allow us to efficiently perform optimized effective potential optimizations within PAW. The new algorithm generates robust and physically correct embedding potentials, as we verified using several test systems including a covalently bound molecule, a metal surface, and bulk semiconductors. We show that with the resulting embedding potential, embedded cluster models can reproduce the electronic structure of point defects in bulk semiconductors, thereby demonstrating the validity of DFET in semiconductors for the first time. Compared to ourmore » previous version, the new implementation of DFET within VASP affords use of all features of VASP (e.g., a systematic PAW library, a wide selection of functionals, a more flexible choice of U correction formalisms, and faster computational speed) with DFET. Furthermore, our results are fairly robust with respect to both plane-wave and Gaussian type orbital basis sets in the embedded cluster calculations. This suggests that the density functional embedding method is potentially an accurate and efficient way to study properties of isolated defects in semiconductors.« less

A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorptions on the (0001) Surface of Double Hexagonal Close Packed Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Atta-Fynn, Raymond; Ray, Asok

2008-03-01

Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorptions on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals (FLAPW+lo) method. The three-fold hollow hcp site was found to be the most stable site for H adsorption, while the two-fold bridge adsorption site was found to be the most stable site for O adsorption. Chemisorption energies and adsorption geometries for different adsorption sites will be discussed. The change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the adatom will be discussed. The implications of chemisorption on Am 5f electron localization-delocalization will also be discussed.

Validating density-functional theory simulations at high energy-density conditions with liquid krypton shock experiments to 850 GPa on Sandia's Z machine

DOE PAGES

Mattsson, Thomas R.; Root, Seth; Mattsson, Ann E.; ...

2014-11-11

We use Sandia's Z machine and magnetically accelerated flyer plates to shock compress liquid krypton to 850 GPa and compare with results from density-functional theory (DFT) based simulations using the AM05 functional. We also employ quantum Monte Carlo calculations to motivate the choice of AM05. We conclude that the DFT results are sensitive to the quality of the pseudopotential in terms of scattering properties at high energy/temperature. A new Kr projector augmented wave potential was constructed with improved scattering properties which resulted in excellent agreement with the experimental results to 850 GPa and temperatures above 10 eV (110 kK). Inmore » conclusion, we present comparisons of our data from the Z experiments and DFT calculations to current equation of state models of krypton to determine the best model for high energy-density applications.« less

π-π stacking tackled with density functional theory

PubMed Central

Swart, Marcel; van der Wijst, Tushar; Fonseca Guerra, Célia

2007-01-01

Through comparison with ab initio reference data, we have evaluated the performance of various density functionals for describing π-π interactions as a function of the geometry between two stacked benzenes or benzene analogs, between two stacked DNA bases, and between two stacked Watson–Crick pairs. Our main purpose is to find a robust and computationally efficient density functional to be used specifically and only for describing π-π stacking interactions in DNA and other biological molecules in the framework of our recently developed QM/QM approach "QUILD". In line with previous studies, most standard density functionals recover, at best, only part of the favorable stacking interactions. An exception is the new KT1 functional, which correctly yields bound π-stacked structures. Surprisingly, a similarly good performance is achieved with the computationally very robust and efficient local density approximation (LDA). Furthermore, we show that classical electrostatic interactions determine the shape and depth of the π-π stacking potential energy surface. Figure Additivity approximation for the π-π interaction between two stacked Watson–Crick base pairs in terms of pairwise interactions between individual bases Electronic supplementary material The online version of this article (doi:10.1007/s00894-007-0239-y) contains supplementary material, which is available to authorized users. PMID:17874150

A density matrix-based method for the linear-scaling calculation of dynamic second- and third-order properties at the Hartree-Fock and Kohn-Sham density functional theory levels.

PubMed

Kussmann, Jörg; Ochsenfeld, Christian

2007-11-28

A density matrix-based time-dependent self-consistent field (D-TDSCF) method for the calculation of dynamic polarizabilities and first hyperpolarizabilities using the Hartree-Fock and Kohn-Sham density functional theory approaches is presented. The D-TDSCF method allows us to reduce the asymptotic scaling behavior of the computational effort from cubic to linear for systems with a nonvanishing band gap. The linear scaling is achieved by combining a density matrix-based reformulation of the TDSCF equations with linear-scaling schemes for the formation of Fock- or Kohn-Sham-type matrices. In our reformulation only potentially linear-scaling matrices enter the formulation and efficient sparse algebra routines can be employed. Furthermore, the corresponding formulas for the first hyperpolarizabilities are given in terms of zeroth- and first-order one-particle reduced density matrices according to Wigner's (2n+1) rule. The scaling behavior of our method is illustrated for first exemplary calculations with systems of up to 1011 atoms and 8899 basis functions.

Effect of altered reproductive function and lowered testosterone levels on bone density in male endurance athletes.

PubMed

Bennell, K L; Brukner, P D; Malcolm, S A

1996-09-01

It is apparent that bone density in male athletes can be reduced without a concomitant decrease in testosterone, suggesting that bone density and testosterone concentrations in the normal range are not closely related in male athletes. Further research is necessary to monitor concurrent changes in bone density and testosterone over a period of time in exercising males. In any case, the effect of exercise on the male reproductive system does not appear as extreme as that which can occur in female athletes, and any impact on bone density is not nearly as evident. These results imply that factors apart from testosterone concentrations must be responsible for the observed osteopenia in some male athletes. Many factors have the potential to adversely affect bone density, independently of alterations in reproductive function. These include low calcium intake, energy deficit, weight loss, psychological stress, and low body fat, all of which may be associated with intense endurance training. Future research investigating skeletal health in male athletes should include a thorough assessment of reproductive function in addition to these other factors.

Density functional theoretical modeling, electrostatic surface potential and surface enhanced Raman spectroscopic studies on biosynthesized silver nanoparticles: observation of 400 PM sensitivity to explosives.

PubMed

Sil, Sanchita; Chaturvedi, Deepika; Krishnappa, Keerthi B; Kumar, Srividya; Asthana, S N; Umapathy, Siva

2014-04-24

Interaction of adsorbate on charged surfaces, orientation of the analyte on the surface, and surface enhancement aspects have been studied. These aspects have been explored in details to explain the surface-enhanced Raman spectroscopic (SERS) spectra of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW or CL-20), a well-known explosive, and 2,4,6-trinitrotoluene (TNT) using one-pot synthesis of silver nanoparticles via biosynthetic route using natural precursor extracts of clove and pepper. The biosynthesized silver nanoparticles (bio Ag Nps) have been characterized using UV-vis spectroscopy, scanning electron microscopy and atomic force microscopy. SERS studies conducted using bio Ag Nps on different water insoluble analytes, such as CL-20 and TNT, lead to SERS signals at concentration levels of 400 pM. The experimental findings have been corroborated with density functional computational results, electrostatic surface potential calculations, Fukui functions and ζ potential measurements.

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

Exchange potential from the common energy denominator approximation for the Kohn-Sham Green's function: Application to (hyper)polarizabilities of molecular chains

NASA Astrophysics Data System (ADS)

Grüning, M.; Gritsenko, O. V.; Baerends, E. J.

2002-04-01

An approximate Kohn-Sham (KS) exchange potential vxσCEDA is developed, based on the common energy denominator approximation (CEDA) for the static orbital Green's function, which preserves the essential structure of the density response function. vxσCEDA is an explicit functional of the occupied KS orbitals, which has the Slater vSσ and response vrespσCEDA potentials as its components. The latter exhibits the characteristic step structure with "diagonal" contributions from the orbital densities |ψiσ|2, as well as "off-diagonal" ones from the occupied-occupied orbital products ψiσψj(≠1)σ*. Comparison of the results of atomic and molecular ground-state CEDA calculations with those of the Krieger-Li-Iafrate (KLI), exact exchange (EXX), and Hartree-Fock (HF) methods show, that both KLI and CEDA potentials can be considered as very good analytical "closure approximations" to the exact KS exchange potential. The total CEDA and KLI energies nearly coincide with the EXX ones and the corresponding orbital energies ɛiσ are rather close to each other for the light atoms and small molecules considered. The CEDA, KLI, EXX-ɛiσ values provide the qualitatively correct order of ionizations and they give an estimate of VIPs comparable to that of the HF Koopmans' theorem. However, the additional off-diagonal orbital structure of vxσCEDA appears to be essential for the calculated response properties of molecular chains. KLI already considerably improves the calculated (hyper)polarizabilities of the prototype hydrogen chains Hn over local density approximation (LDA) and standard generalized gradient approximations (GGAs), while the CEDA results are definitely an improvement over the KLI ones. The reasons of this success are the specific orbital structures of the CEDA and KLI response potentials, which produce in an external field an ultranonlocal field-counteracting exchange potential.

The numerical and functional responses of a granivorous rodent and the fate of Neotropical tree seeds

USGS Publications Warehouse

Klinger, R.; Rejmanek, M.

2009-01-01

Despite their potential to provide mechanistic explanations of rates of seed dispersal and seed fate, the functional and numerical responses of seed predators have never been explicitly examined within this context. Therefore, we investigated the numerical response of a small-mammal seed predator, Heteromys desmarestianus, to disturbance-induced changes in food availability and evaluated the degree to which removal and fate of seeds of eight tree species in a lowland tropical forest in Belize were related to the functional response of H. desmarestianus to varying seed densities. Mark-recapture trapping was used to estimate abundance of H. desmarestianus in six 0.5-ha grids from July 2000 to September 2002. Fruit availability and seed fate were estimated in each grid, and two experiments nested within the grids were used to determine (1) the form of the functional response for nine levels of fruit density (2-32 fruits/m 2), (2) the removal rate and handling times, and (3) the total proportion of fruits removed. The total proportion of fruits removed was determined primarily by the numerical response of H. desmarestianus to fruit availability, while removal rates and the proportion of seeds eaten or cached were related primarily to the form of the functional response. However, the numerical and functional responses interacted; H. desmarestianus showed strong spatial and temporal numerical responses to total fruit availability, and their density relative to fruit availability resulted in variation in the form of the functional response. Types I, II, and III functional responses were observed, as were density-independent responses, and these responses varied both among and within fruit species. The highest proportions of fruits were eaten when the Type III functional response was detected, which was when fruit availability was high relative to H. desmarestianus population density. Numerous idiosyncratic influences on seed fate have been documented, but our results indicate that shifts in the numerical and functional responses of seed predators to seasonal and interannual variation in seed availability potentially provide a general mechanistic explanation for patterns of removal and fate for vertebrate-dispersed seeds. ?? 2009 by the Ecological Society of America.

On the GIBBS thermodynamic potential of seawater

NASA Astrophysics Data System (ADS)

Feistel, Rainer; Hagen, Eberhard

Free Enthalpy, the GIBBS thermodynamic potential G(S,t,p) of seawater, has been recomputed including the sound speed equation of DEL GROSSO (1974), temperatures of maximum density (TMD) of CALDWELL (1978), freezing point depression measurements of DOHERTY and KESTER (1974), rederived limiting laws and ice properties, and an extended set of dilution heat data of BROMLEY (1968) and MILLERO, HANSEN and HOFF (1973). As a new reference state, the standard ocean state has been chosen. The resulting average deviations are 0.0006 kg m -3 for pure water density at 1 atm, 0.002 kg m -3 for seawater density at 1 atm, 0.02 m/s for sound speed, 0.01 J kgK -1 for heat capacity at 1 atm, 0.4 kJ kg -1 for dilution heats, 0.002°C for freezing points, and 0.04°C for TMDs. Resulting pressure-dependent freezing points are in good agreement with experiments and UNESCO (1978) formulas. Enthalpy as thermodynamic potential has been explicitly determined for easy computation of potential temperature, potential density, and sound speed. All functions are expressed in the new International Temperature Scale ITS-90.

Synthesis, crystal structure, vibrational spectra and theoretical calculations of quantum chemistry of a potential antimicrobial Meldrum's acid derivative

NASA Astrophysics Data System (ADS)

Campelo, M. J. M.; Freire, P. T. C.; Mendes Filho, J.; de Toledo, T. A.; Teixeira, A. M. R.; da Silva, L. E.; Bento, R. R. F.; Faria, J. L. B.; Pizani, P. S.; Gusmão, G. O. M.; Coutinho, H. D. M.; Oliveira, M. T. A.

2017-10-01

A new derivative of Meldrum's acid 5-((5-chloropyridin-2-ylamino)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (CYMM) of molecular formula C12H11ClN2O4 was synthesized and structurally characterized using single crystal X-ray diffraction technique. The vibrational properties of the crystal were studied by Fourier Transform infrared (FT-IR), Fourier Transform Raman (FT-Raman) techniques and theoretical calculations of quantum chemistry using Density functional theory (DFT) and Density functional perturbation theory (DFPT). A comparison with experimental spectra allowed the assignment of all the normal modes. The descriptions of the normal modes were carried by means of potential energy distribution (PED). Additionally, analysis of the antimicrobial activity and antibiotic resistance modulatory activity was carried out to evaluate the antibacterial potential of the CYMM.

QCD equation of state at nonzero chemical potential: continuum results with physical quark masses at order μ 2

NASA Astrophysics Data System (ADS)

Borsányi, Sz.; Endrődi, G.; Fodor, Z.; Katz, S. D.; Krieg, S.; Ratti, C.; Szabó, K. K.

2012-08-01

We determine the equation of state of QCD for nonzero chemical potentials via a Taylor expansion of the pressure. The results are obtained for N f = 2 + 1 flavors of quarks with physical masses, on various lattice spacings. We present results for the pressure, interaction measure, energy density, entropy density, and the speed of sound for small chemical potentials. At low temperatures we compare our results with the Hadron Resonance Gas model. We also express our observables along trajectories of constant entropy over particle number. A simple parameterization is given (the Matlab/Octave script parameterization.m, submitted to the arXiv along with the paper), which can be used to reconstruct the observables as functions of T and μ, or as functions of T and S/N.

Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory

PubMed Central

Fowler, Nicholas J.; Blanford, Christopher F.

2017-01-01

Abstract Blue copper proteins, such as azurin, show dramatic changes in Cu2+/Cu+ reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high‐level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long‐range electrostatic changes and hence can be modeled accurately with continuum electrostatics. PMID:28815759

Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

2018-01-01

The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

Interfacially Optimized, High Energy Density Nanoparticle-Polymer Composites for Capacitive Energy Storage

NASA Astrophysics Data System (ADS)

Shipman, Joshua; Riggs, Brian; Luo, Sijun; Adireddy, Shiva; Chrisey, Douglas

Energy storage is a green energy technology, however it must be cost effective and scalable to meet future energy demands. Polymer-nanoparticle composites are low cost and potentially offer high energy storage. This is based on the high breakdown strength of polymers and the high dielectric constant of ceramic nanoparticles, but the incoherent nature of the interface between the two components prevents the realization of their combined full potential. We have created inkjet printable nanoparticle-polymer composites that have mitigated many of these interface effects, guided by first principle modelling of the interface. We detail density functional theory modelling of the interface and how it has guided our use in in specific surface functionalizations and other inorganic layers. We have validated our approach by using finite element analysis of the interface. By choosing the correct surface functionalization we are able to create dipole traps which further increase the breakdown strength of our composites. Our nano-scale understanding has allowed us to create the highest energy density composites currently available (>40 J/cm3).

Spatial Distribution of Oxygen Chemical Potential under Potential Gradients and Theoretical Maximum Power Density with 8YSZ Electrolyte

NASA Astrophysics Data System (ADS)

Lim, Dae-Kwang; Im, Ha-Ni; Song, Sun-Ju

2016-01-01

The maximum power density of SOFC with 8YSZ electrolyte as the function of thickness was calculated by integrating partial conductivities of charge carriers under various DC bias conditions at a fixed oxygen chemical potential gradient at both sides of the electrolyte. The partial conductivities were successfully taken using the Hebb-Wagner polarization method as a function of temperature and oxygen partial pressure, and the spatial distribution of oxygen partial pressure across the electrolyte was calculated based on Choudhury and Patterson’s model by considering zero electrode polarization. At positive voltage conditions corresponding to SOFC and SOEC, the high conductivity region was expanded, but at negative cell voltage condition, the low conductivity region near n-type to p-type transition was expanded. In addition, the maximum power density calculated from the current-voltage characteristic showed approximately 5.76 W/cm2 at 700 oC with 10 μm thick-8YSZ, while the oxygen partial pressure of the cathode and anode sides maintained ≈0.21 and 10-22 atm.

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.

Grid-free density functional calculations on periodic systems.

PubMed

Varga, Stefan

2007-09-21

Density fitting scheme is applied to the exchange part of the Kohn-Sham potential matrix in a grid-free local density approximation for infinite systems with translational periodicity. It is shown that within this approach the computational demands for the exchange part scale in the same way as for the Coulomb part. The efficiency of the scheme is demonstrated on a model infinite polymer chain. For simplicity, the implementation with Dirac-Slater Xalpha exchange functional is presented only. Several choices of auxiliary basis set expansion coefficients were tested with both Coulomb and overlap metric. Their effectiveness is discussed also in terms of robustness and norm preservation.

Grid-free density functional calculations on periodic systems

NASA Astrophysics Data System (ADS)

Varga, Štefan

2007-09-01

Density fitting scheme is applied to the exchange part of the Kohn-Sham potential matrix in a grid-free local density approximation for infinite systems with translational periodicity. It is shown that within this approach the computational demands for the exchange part scale in the same way as for the Coulomb part. The efficiency of the scheme is demonstrated on a model infinite polymer chain. For simplicity, the implementation with Dirac-Slater Xα exchange functional is presented only. Several choices of auxiliary basis set expansion coefficients were tested with both Coulomb and overlap metric. Their effectiveness is discussed also in terms of robustness and norm preservation.

Equilibrium finite-frequency noise of an interacting mesoscopic capacitor studied in time-dependent density functional theory

NASA Astrophysics Data System (ADS)

Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

2018-03-01

We calculate the frequency-dependent equilibrium noise of a mesoscopic capacitor in time-dependent density functional theory (TDDFT). The capacitor is modeled as a single-level quantum dot with on-site Coulomb interaction and tunnel coupling to a nearby reservoir. The noise spectra are derived from linear-response conductances via the fluctuation-dissipation theorem. Thereby, we analyze the performance of a recently derived exchange-correlation potential with time-nonlocal density dependence in the finite-frequency linear-response regime. We compare our TDDFT noise spectra with real-time perturbation theory and find excellent agreement for noise frequencies below the reservoir temperature.

Challenges for semilocal density functionals with asymptotically nonvanishing potentials

NASA Astrophysics Data System (ADS)

Aschebrock, Thilo; Armiento, Rickard; Kümmel, Stephan

2017-08-01

The Becke-Johnson model potential [A. D. Becke and E. R. Johnson, J. Chem. Phys. 124, 221101 (2006), 10.1063/1.2213970] and the potential of the AK13 functional [R. Armiento and S. Kümmel, Phys. Rev. Lett. 111, 036402 (2013), 10.1103/PhysRevLett.111.036402] have been shown to mimic features of the exact Kohn-Sham exchange potential, such as step structures that are associated with shell closings and particle-number changes. A key element in the construction of these functionals is that the potential has a limiting value far outside a finite system that is a system-dependent constant rather than zero. We discuss a set of anomalous features in these functionals that are closely connected to the nonvanishing asymptotic potential. The findings constitute a formidable challenge for the future development of semilocal functionals based on the concept of a nonvanishing asymptotic constant.

X-ray absorption in insulators with non-Hermitian real-time time-dependent density functional theory.

PubMed

Fernando, Ranelka G; Balhoff, Mary C; Lopata, Kenneth

2015-02-10

Non-Hermitian real-time time-dependent density functional theory was used to compute the Si L-edge X-ray absorption spectrum of α-quartz using an embedded finite cluster model and atom-centered basis sets. Using tuned range-separated functionals and molecular orbital-based imaginary absorbing potentials, the excited states spanning the pre-edge to ∼20 eV above the ionization edge were obtained in good agreement with experimental data. This approach is generalizable to TDDFT studies of core-level spectroscopy and dynamics in a wide range of materials.

Serenity: A subsystem quantum chemistry program.

PubMed

Unsleber, Jan P; Dresselhaus, Thomas; Klahr, Kevin; Schnieders, David; Böckers, Michael; Barton, Dennis; Neugebauer, Johannes

2018-05-15

We present the new quantum chemistry program Serenity. It implements a wide variety of functionalities with a focus on subsystem methodology. The modular code structure in combination with publicly available external tools and particular design concepts ensures extensibility and robustness with a focus on the needs of a subsystem program. Several important features of the program are exemplified with sample calculations with subsystem density-functional theory, potential reconstruction techniques, a projection-based embedding approach and combinations thereof with geometry optimization, semi-numerical frequency calculations and linear-response time-dependent density-functional theory. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

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

Pribram-Jones, A.; Burke, K.

We show that the adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upward from the system's physical temperature. We also show how to relate different correlation components to each other, either in terms of temperature or coupling-constant integrations. Lastly, we illustrate our results on the uniform electron gas.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation.

PubMed

Escaño, Mary Clare Sison; Arevalo, Ryan Lacdao; Gyenge, Elod; Kasai, Hideaki

2014-09-03

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4(-) on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation

NASA Astrophysics Data System (ADS)

Sison Escaño, Mary Clare; Lacdao Arevalo, Ryan; Gyenge, Elod; Kasai, Hideaki

2014-09-01

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4- on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

Microbial structural diversity estimated by dilution-extinction of phenotypic traits and T-RFLP analysis along a land-use intensification gradient

NASA Technical Reports Server (NTRS)

Gomez, Elena del V.; Garland, Jay L.; Roberts, Michael S.

2004-01-01

The present work tested whether the relationship between functional traits and inoculum density reflected structural diversity in bacterial communities from a land-use intensification gradient applying a mathematical model. Terminal restriction fragment length polymorphism (T-RFLP) analysis was also performed to provide an independent assessment of species richness. Successive 10-fold dilutions of a soil suspension were inoculated onto Biolog GN(R) microplates. Soil bacterial density was determined by total cell and plate counts. The relationship between phenotypic traits and inoculum density fit the model, allowing the estimation of maximal phenotypic potential (Rmax) and inoculum density (KI) at which Rmax will be half-reduced. Though Rmax decreased with time elapsed since clearing of native vegetation, KI remained high in two of the disturbed sites. The genetic pool of bacterial community did not experience a significant reduction, but the active fraction responding in the Biolog assay was adversely affected, suggesting a reduction in the functional potential. c2004 Federation of European Microbiological Societies. Published by Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory.

PubMed

Inkaya, Ersin; Dinçer, Muharrem; Sahan, Emine; Yıldırım, Ismail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, (1)H NMR, (13)C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z=2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and structural characterization of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine with theoretical calculations using density functional theory

NASA Astrophysics Data System (ADS)

İnkaya, Ersin; Dinçer, Muharrem; Şahan, Emine; Yıldırım, İsmail

2013-10-01

In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameters (FT-IR, 1H NMR, 13C NMR) of 5-benzoyl-4-phenyl-2-methylthio-1H-pyrimidine. The compound crystallizes in the triclinic space group P-1 with Z = 2. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) and 6-311++G(d,p) basis sets in ground state and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecules has been obtained by mapping electron density isosurface with electrostatic potential (ESP). Also, non-linear optical properties of the title compound were performed at B3LYP/6-311++G(d,p) level. The theoretical results showed an excellent agreement with the experimental values.

Galaxy halo expansions: a new biorthogonal family of potential-density pairs

NASA Astrophysics Data System (ADS)

Lilley, Edward J.; Sanders, Jason L.; Evans, N. Wyn; Erkal, Denis

2018-05-01

Efficient expansions of the gravitational field of (dark) haloes have two main uses in the modelling of galaxies: first, they provide a compact representation of numerically constructed (or real) cosmological haloes, incorporating the effects of triaxiality, lopsidedness or other distortion. Secondly, they provide the basis functions for self-consistent field expansion algorithms used in the evolution of N-body systems. We present a new family of biorthogonal potential-density pairs constructed using the Hankel transform of the Laguerre polynomials. The lowest order density basis functions are double-power-law profiles cusped like ρ ˜ r-2+1/α at small radii with asymptotic density fall-off like ρ ˜ r-3-1/(2α). Here, α is a parameter satisfying α ≥ 1/2. The family therefore spans the range of inner density cusps found in numerical simulations, but has much shallower - and hence more realistic - outer slopes than the corresponding members of the only previously known family deduced by Zhao and exemplified by Hernquist & Ostriker. When α = 1, the lowest order density profile has an inner density cusp of ρ ˜ r-1 and an outer density slope of ρ ˜ r-3.5, similar to the famous Navarro, Frenk & White (NFW) model. For this reason, we demonstrate that our new expansion provides a more accurate representation of flattened NFW haloes than the competing Hernquist-Ostriker expansion. We utilize our new expansion by analysing a suite of numerically constructed haloes and providing the distributions of the expansion coefficients.

Wedge-shaped potential and Airy-function electron localization in oxide superlattices.

PubMed

Popovic, Z S; Satpathy, S

2005-05-06

Oxide superlattices and microstructures hold the promise for creating a new class of devices with unprecedented functionalities. Density-functional studies of the recently fabricated, lattice-matched perovskite titanates (SrTiO3)n/(LaTiO3)m reveal a classic wedge-shaped potential well for the monolayer (m = 1) structure, originating from the Coulomb potential of a two-dimensional charged La sheet. The potential in turn confines the electrons in the Airy-function-localized states. Magnetism is suppressed for the monolayer structure, while in structures with a thicker LaTiO3 part, bulk antiferromagnetism is recovered, with a narrow transition region separating the magnetic LaTiO3 and the nonmagnetic SrTiO3.

COMPUTATIONAL ELECTROCHEMISTRY: AQUEOUS ONE-ELECTRON OXIDATION POTENTIALS FOR SUBSTITUTED ANILINES

EPA Science Inventory

Semiempirical molecular orbital theory and density functional theory are used to compute one-electron oxidation potentials for aniline and a set of 21 mono- and di-substituted anilines in aqueous solution. Linear relationships between theoretical predictions and experiment are co...

Implementation and benchmark of a long-range corrected functional in the density functional based tight-binding method

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

Lutsker, V.; Niehaus, T. A., E-mail: thomas.niehaus@physik.uni-regensburg.de; Aradi, B.

2015-11-14

Bridging the gap between first principles methods and empirical schemes, the density functional based tight-binding method (DFTB) has become a versatile tool in predictive atomistic simulations over the past years. One of the major restrictions of this method is the limitation to local or gradient corrected exchange-correlation functionals. This excludes the important class of hybrid or long-range corrected functionals, which are advantageous in thermochemistry, as well as in the computation of vibrational, photoelectron, and optical spectra. The present work provides a detailed account of the implementation of DFTB for a long-range corrected functional in generalized Kohn-Sham theory. We apply themore » method to a set of organic molecules and compare ionization potentials and electron affinities with the original DFTB method and higher level theory. The new scheme cures the significant overpolarization in electric fields found for local DFTB, which parallels the functional dependence in first principles density functional theory (DFT). At the same time, the computational savings with respect to full DFT calculations are not compromised as evidenced by numerical benchmark data.« less

Implementation of Two-Component Time-Dependent Density Functional Theory in TURBOMOLE.

PubMed

Kühn, Michael; Weigend, Florian

2013-12-10

We report the efficient implementation of a two-component time-dependent density functional theory proposed by Wang et al. (Wang, F.; Ziegler, T.; van Lenthe, E.; van Gisbergen, S.; Baerends, E. J. J. Chem. Phys. 2005, 122, 204103) that accounts for spin-orbit effects on excitations of closed-shell systems by employing a noncollinear exchange-correlation kernel. In contrast to the aforementioned implementation, our method is based on two-component effective core potentials as well as Gaussian-type basis functions. It is implemented in the TURBOMOLE program suite for functionals of the local density approximation and the generalized gradient approximation. Accuracy is assessed by comparison of two-component vertical excitation energies of heavy atoms and ions (Cd, Hg, Au(+)) and small molecules (I2, TlH) to other two- and four-component approaches. Efficiency is demonstrated by calculating the electronic spectrum of Au20.

Forward and inverse functional variations in rotationally inelastic scattering

NASA Astrophysics Data System (ADS)

Guzman, Robert; Rabitz, Herschel

1986-09-01

This paper considers the response of various rotational energy transfer processes to functional variations about an assumed model intermolecular potential. Attention is focused on the scattering of an atom and a linear rigid rotor. The collision dynamics are approximated by employing both the infinite order sudden (IOS) and exponential distorted wave (EDW) methods to describe Ar-N2 and He-H2, respectively. The following cross sections are considered: state-to-state differential and integral, final state summed differential and integral, and effective diffusion and viscosity cross sections. Attention is first given to the forward sensitivity densities δ0/δV(R,r) where 0 denotes any of the aforementioned cross sections, R is the intermolecular distance, and r is the internal coordinates. These forward sensitivity densities (functional derivatives) offer a quantitative measure of the importance of different regions of the potential surface to a chosen cross section. Via knowledge of the forward sensitivities and a particular variation δV(R,r) the concomitant response δ0 is generated. It was found that locally a variation in the potential can give rise to a large response in the cross sections as measured by these forward densities. In contrast, a unit percent change in the overall potential produced a 1%-10% change in the cross sections studied indicating that the large + and - responses to local variations tend to cancel. In addition, inverse sensitivity densities δV(R,r)/δ0 are obtained. These inverse densities are of interest since they are the exact solution to the infinitesimal inverse scattering problem. Although the inverse sensitivity densities do not in themselves form an inversion algorithm, they do offer a quantitative measure of the importance of performing particular measurements for the ultimate purpose of inversion. Using a set of state-to-state integral cross sections we found that the resultant responses from the infinitesimal inversion were typically small such that ‖δV(R,r)‖≪‖V(R,r)‖. From the viewpoint of an actual inversion, these results indicate that only through an extensive effort will significant knowledge of the potential be gained from the cross sections. All of these calculations serve to illustrate the methodology, and other observables as well as dynamical schemes could be explored as desired.

Survival of the most transferable at the top of Jacob's ladder: Defining and testing the ωB97M(2) double hybrid density functional

NASA Astrophysics Data System (ADS)

Mardirossian, Narbe; Head-Gordon, Martin

2018-06-01

A meta-generalized gradient approximation, range-separated double hybrid (DH) density functional with VV10 non-local correlation is presented. The final 14-parameter functional form is determined by screening trillions of candidate fits through a combination of best subset selection, forward stepwise selection, and random sample consensus (RANSAC) outlier detection. The MGCDB84 database of 4986 data points is employed in this work, containing a training set of 870 data points, a validation set of 2964 data points, and a test set of 1152 data points. Following an xDH approach, orbitals from the ωB97M-V density functional are used to compute the second-order perturbation theory correction. The resulting functional, ωB97M(2), is benchmarked against a variety of leading double hybrid density functionals, including B2PLYP-D3(BJ), B2GPPLYP-D3(BJ), ωB97X-2(TQZ), XYG3, PTPSS-D3(0), XYGJ-OS, DSD-PBEP86-D3(BJ), and DSD-PBEPBE-D3(BJ). Encouragingly, the overall performance of ωB97M(2) on nearly 5000 data points clearly surpasses that of all of the tested density functionals. As a Rung 5 density functional, ωB97M(2) completes our family of combinatorially optimized functionals, complementing B97M-V on Rung 3, and ωB97X-V and ωB97M-V on Rung 4. The results suggest that ωB97M(2) has the potential to serve as a powerful predictive tool for accurate and efficient electronic structure calculations of main-group chemistry.

Combining two-body density functionals with multiconfigurational wavefunctions: diatomic molecules

NASA Astrophysics Data System (ADS)

McDouall, Joseph J. W.

The MCSCF method provides a correct zero-order wavefunction for all regions of molecular potential energy surfaces. To obtain quantitative accuracy a proper treatment of the dynamic correlation problem must be implemented. Traditionally this has been achieved through multireference variants of perturbation theory, configuration interaction and coupled cluster theory. The computational cost of such techniques makes them prohibitive for all but the smallest molecular problems. Reported here is an investigation into the efficacy of two-body density functionals in providing the dynamic correlation energy for MCSCF reference states. Tests were made on the two-body density functionals of Colle and Salvetti (CS), Moscardó and San-Fabián (MSF), and Moscardó and Pérez-Jiménez (MPJ5) in predicting the equilibrium bond lengths, harmonic frequencies and dissociation energies of fifteen diatomic molecules (3B2, 3BN, 2BS, 1C2, 2CN, 1CO, 1F2, 1FCl, 1N2, 3NCl, 3O2, 1PN, 3Si2, 3SiO, 3SO) using full valence-shell CASSCF reference wavefunctions. Also studied were modifications of these functionals recently suggested by Miehlich, Stoll and Savin (MSS) and Gräfenstein and Cremer (GC). The results obtained show accuracy comparable with and typically superior to the popular Kohn-Sham BLYP and B3LYP methods. However, the latter methods are not applicable in all regions of a potential energy surface, and even predict incorrect ground states for some systems. The use of two-body density functionals with MCSCF reference states does not share this shortcoming.

A full-potential approach to the relativistic single-site Green's function

DOE PAGES

Liu, Xianglin; Wang, Yang; Eisenbach, Markus; ...

2016-07-07

One major purpose of studying the single-site scattering problem is to obtain the scattering matrices and differential equation solutions indispensable to multiple scattering theory (MST) calculations. On the other hand, the single-site scattering itself is also appealing because it reveals the physical environment experienced by electrons around the scattering center. In this study, we demonstrate a new formalism to calculate the relativistic full-potential single-site Green's function. We implement this method to calculate the single-site density of states and electron charge densities. Lastly, the code is rigorously tested and with the help of Krein's theorem, the relativistic effects and full potentialmore » effects in group V elements and noble metals are thoroughly investigated.« less

Copper interstitial recombination centers in Cu3N

NASA Astrophysics Data System (ADS)

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; Hanifi, David; Salleo, Alberto; Magyari-Köpe, Blanka; Nishi, Yoshio; Bent, Stacey F.; Clemens, Bruce M.

2018-06-01

We present a comprehensive study of the earth-abundant semiconductor Cu3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies VCu have shallow defect levels while copper interstitials Cui behave as deep potential wells in the conduction band, which mediate Shockley-Read-Hall recombination. The existence of Cui defects has been experimentally verified using photothermal deflection spectroscopy. A Cu3N /ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. The absence of photocurrent can be explained by a large concentration of Cui recombination centers capturing electrons in p -type Cu3N .

Electron energy distribution function in the divertor region of the COMPASS tokamak during neutral beam injection heating

NASA Astrophysics Data System (ADS)

Hasan, E.; Dimitrova, M.; Havlicek, J.; Mitošinková, K.; Stöckel, J.; Varju, J.; Popov, Tsv K.; Komm, M.; Dejarnac, R.; Hacek, P.; Panek, R.; the COMPASS Team

2018-02-01

This paper presents the results from swept probe measurements in the divertor region of the COMPASS tokamak in D-shaped, L-mode discharges, with toroidal magnetic field BT = 1.15 T, plasma current Ip = 180 kA and line-average electron densities varying from 2 to 8×1019 m-3. Using neutral beam injection heating, the electron energy distribution function is studied before and during the application of the beam. The current-voltage characteristics data are processed using the first-derivative probe technique. This technique allows one to evaluate the plasma potential and the real electron energy distribution function (respectively, the electron temperatures and densities). At the low average electron density of 2×1019 m-3, the electron energy distribution function is bi-Maxwellian with a low-energy electron population with temperatures 4-6 eV and a high-energy electron group 12-25 eV. As the line-average electron density is increased, the electron temperatures decrease. At line-average electron densities above 7×1019 m-3, the electron energy distribution function is found to be Maxwellian with a temperature of 6-8.5 eV. The effect of the neutral beam injection heating power in the divertor region is also studied.

Bypassing the malfunction junction in warm dense matter simulations

NASA Astrophysics Data System (ADS)

Cangi, Attila; Pribram-Jones, Aurora

2015-03-01

Simulation of warm dense matter requires computational methods that capture both quantum and classical behavior efficiently under high-temperature and high-density conditions. The state-of-the-art approach to model electrons and ions under those conditions is density functional theory molecular dynamics, but this method's computational cost skyrockets as temperatures and densities increase. We propose finite-temperature potential functional theory as an in-principle-exact alternative that suffers no such drawback. In analogy to the zero-temperature theory developed previously, we derive an orbital-free free energy approximation through a coupling-constant formalism. Our density approximation and its associated free energy approximation demonstrate the method's accuracy and efficiency. A.C. has been partially supported by NSF Grant CHE-1112442. A.P.J. is supported by DOE Grant DE-FG02-97ER25308.

Excitation energies from range-separated time-dependent density and density matrix functional theory.

PubMed

Pernal, Katarzyna

2012-05-14

Time-dependent density functional theory (TD-DFT) in the adiabatic formulation exhibits known failures when applied to predicting excitation energies. One of them is the lack of the doubly excited configurations. On the other hand, the time-dependent theory based on a one-electron reduced density matrix functional (time-dependent density matrix functional theory, TD-DMFT) has proven accurate in determining single and double excitations of H(2) molecule if the exact functional is employed in the adiabatic approximation. We propose a new approach for computing excited state energies that relies on functionals of electron density and one-electron reduced density matrix, where the latter is applied in the long-range region of electron-electron interactions. A similar approach has been recently successfully employed in predicting ground state potential energy curves of diatomic molecules even in the dissociation limit, where static correlation effects are dominating. In the paper, a time-dependent functional theory based on the range-separation of electronic interaction operator is rigorously formulated. To turn the approach into a practical scheme the adiabatic approximation is proposed for the short- and long-range components of the coupling matrix present in the linear response equations. In the end, the problem of finding excitation energies is turned into an eigenproblem for a symmetric matrix. Assignment of obtained excitations is discussed and it is shown how to identify double excitations from the analysis of approximate transition density matrix elements. The proposed method used with the short-range local density approximation (srLDA) and the long-range Buijse-Baerends density matrix functional (lrBB) is applied to H(2) molecule (at equilibrium geometry and in the dissociation limit) and to Be atom. The method accounts for double excitations in the investigated systems but, unfortunately, the accuracy of some of them is poor. The quality of the other excitations is in general much better than that offered by TD-DFT-LDA or TD-DMFT-BB approximations if the range-separation parameter is properly chosen. The latter remains an open problem.

No need for external orthogonality in subsystem density-functional theory.

PubMed

Unsleber, Jan P; Neugebauer, Johannes; Jacob, Christoph R

2016-08-03

Recent reports on the necessity of using externally orthogonal orbitals in subsystem density-functional theory (SDFT) [Annu. Rep. Comput. Chem., 8, 2012, 53; J. Phys. Chem. A, 118, 2014, 9182] are re-investigated. We show that in the basis-set limit, supermolecular Kohn-Sham-DFT (KS-DFT) densities can exactly be represented as a sum of subsystem densities, even if the subsystem orbitals are not externally orthogonal. This is illustrated using both an analytical example and in basis-set free numerical calculations for an atomic test case. We further show that even with finite basis sets, SDFT calculations using accurate reconstructed potentials can closely approach the supermolecular KS-DFT density, and that the deviations between SDFT and KS-DFT decrease as the basis-set limit is approached. Our results demonstrate that formally, there is no need to enforce external orthogonality in SDFT, even though this might be a useful strategy when developing projection-based DFT embedding schemes.

Coarse-grained forms for equations describing the microscopic motion of particles in a fluid.

PubMed

Das, Shankar P; Yoshimori, Akira

2013-10-01

Exact equations of motion for the microscopically defined collective density ρ(x,t) and the momentum density ĝ(x,t) of a fluid have been obtained in the past starting from the corresponding Langevin equations representing the dynamics of the fluid particles. In the present work we average these exact equations of microscopic dynamics over the local equilibrium distribution to obtain stochastic partial differential equations for the coarse-grained densities with smooth spatial and temporal dependence. In particular, we consider Dean's exact balance equation for the microscopic density of a system of interacting Brownian particles to obtain the basic equation of the dynamic density functional theory with noise. Our analysis demonstrates that on thermal averaging the dependence of the exact equations on the bare interaction potential is converted to dependence on the corresponding thermodynamic direct correlation functions in the coarse-grained equations.

Modern Possibilities for Calculating Some Properties of Molecules and Crystals from the Experimental Electron Density

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

Stash, A.I.; Tsirelson, V.G.

2005-03-01

Methods for calculating some properties of molecules and crystals from the electron density reconstructed from a precise X-ray diffraction experiment using the multipole model are considered. These properties include, on the one hand, the characteristics of the electron density and the inner-crystal electrostatic field and, on the other hand, the local electronic energies (kinetic, potential, total), the exchange energy density, the electron-pair localization function, the localized-orbital locator, the effective crystal potential, and others. It is shown that the integration of these characteristics over pseudoatomic volumes bounded by the surfaces of the zero flux of the electron density gradient makes itmore » possible to characterize directly from an experiment the properties of molecules and crystals in terms of the atomic contributions. The computer program WinXPRO2004, realizing these possibilities, is briefly described.« less

On the role of second number-conserving functional derivatives

NASA Astrophysics Data System (ADS)

Gál, Tamás

2006-06-01

It is found that number-conserving second derivatives, of functional differentiation constrained to the domain of functional variables ρ(x) of a given norm ∫ρ(x)dx, are not obtained via two successive number-conserving differentiations, contrary to the case of unrestricted second derivatives. Investigating the role of second number-conserving derivatives, with the density-functional formulation of time-dependent quantum mechanics in focus, it is shown how number-conserving differentiation handles the dual nature of the Kohn Sham potential arising in the practical use of the theory. On the other hand, it is pointed out that number-conserving derivatives cannot resolve the causality paradox connected with the second derivative of the exchange-correlation part of the action density functional.

Bulk and interfacial structures of reline deep eutectic solvent: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Kaur, Supreet; Sharma, Shobha; Kashyap, Hemant K.

2017-11-01

We apply all-atom molecular dynamics simulations to describe the bulk morphology and interfacial structure of reline, a deep eutectic solvent comprising choline chloride and urea in 1:2 molar ratio, near neutral and charged graphene electrodes. For the bulk phase structural investigation, we analyze the simulated real-space radial distribution functions, X-ray/neutron scattering structure functions, and their partial components. Our study shows that both hydrogen-bonding and long-range correlations between different constituents of reline play a crucial role to lay out the bulk structure of reline. Further, we examine the variation of number density profiles, orientational order parameters, and electrostatic potentials near the neutral and charged graphene electrodes with varying electrode charge density. The present study reveals the presence of profound structural layering of not only the ionic components of reline but also urea near the electrodes. In addition, depending on the electrode charge density, the choline ions and urea molecules render different orientations near the electrodes. The simulated number density and electrostatic potential profiles for reline clearly show the presence of multilayer structures up to a distance of 1.2 nm from the respective electrodes. The observation of positive values of the surface potential at zero charge indicates the presence of significant nonelectrostatic attraction between the choline cation and graphene electrode. The computed differential capacitance (Cd) for reline exhibits an asymmetric bell-shaped curve, signifying different variation of Cd with positive and negative surface potentials.

Bulk and interfacial structures of reline deep eutectic solvent: A molecular dynamics study.

PubMed

Kaur, Supreet; Sharma, Shobha; Kashyap, Hemant K

2017-11-21

We apply all-atom molecular dynamics simulations to describe the bulk morphology and interfacial structure of reline, a deep eutectic solvent comprising choline chloride and urea in 1:2 molar ratio, near neutral and charged graphene electrodes. For the bulk phase structural investigation, we analyze the simulated real-space radial distribution functions, X-ray/neutron scattering structure functions, and their partial components. Our study shows that both hydrogen-bonding and long-range correlations between different constituents of reline play a crucial role to lay out the bulk structure of reline. Further, we examine the variation of number density profiles, orientational order parameters, and electrostatic potentials near the neutral and charged graphene electrodes with varying electrode charge density. The present study reveals the presence of profound structural layering of not only the ionic components of reline but also urea near the electrodes. In addition, depending on the electrode charge density, the choline ions and urea molecules render different orientations near the electrodes. The simulated number density and electrostatic potential profiles for reline clearly show the presence of multilayer structures up to a distance of 1.2 nm from the respective electrodes. The observation of positive values of the surface potential at zero charge indicates the presence of significant nonelectrostatic attraction between the choline cation and graphene electrode. The computed differential capacitance (C d ) for reline exhibits an asymmetric bell-shaped curve, signifying different variation of C d with positive and negative surface potentials.

Physical Meaning of Virtual Kohn-Sham Orbitals and Orbital Energies: An Ideal Basis for the Description of Molecular Excitations.

PubMed

van Meer, R; Gritsenko, O V; Baerends, E J

2014-10-14

In recent years, several benchmark studies on the performance of large sets of functionals in time-dependent density functional theory (TDDFT) calculations of excitation energies have been performed. The tested functionals do not approximate exact Kohn-Sham orbitals and orbital energies closely. We highlight the advantages of (close to) exact Kohn-Sham orbitals and orbital energies for a simple description, very often as just a single orbital-to-orbital transition, of molecular excitations. Benchmark calculations are performed for the statistical average of orbital potentials (SAOP) functional for the potential [J. Chem. Phys. 2000, 112, 1344; 2001, 114, 652], which approximates the true Kohn-Sham potential much better than LDA, GGA, mGGA, and hybrid potentials do. An accurate Kohn-Sham potential does not only perform satisfactorily for calculated vertical excitation energies of both valence and Rydberg transitions but also exhibits appealing properties of the KS orbitals including occupied orbital energies close to ionization energies, virtual-occupied orbital energy gaps very close to excitation energies, realistic shapes of virtual orbitals, leading to straightforward interpretation of most excitations as single orbital transitions. We stress that such advantages are completely lost in time-dependent Hartree-Fock and partly in hybrid approaches. Many excitations and excitation energies calculated with local density, generalized gradient, and hybrid functionals are spurious. There is, with an accurate KS, or even the LDA or GGA potentials, nothing problematic about the "band gap" in molecules: the HOMO-LUMO gap is close to the first excitation energy (the optical gap).

In Silico Modeling of Indigo and Tyrian Purple Single-Electron Nano-Transistors Using Density Functional Theory Approach

NASA Astrophysics Data System (ADS)

Shityakov, Sergey; Roewer, Norbert; Förster, Carola; Broscheit, Jens-Albert

2017-07-01

The purpose of this study was to develop and implement an in silico model of indigoid-based single-electron transistor (SET) nanodevices, which consist of indigoid molecules from natural dye weakly coupled to gold electrodes that function in a Coulomb blockade regime. The electronic properties of the indigoid molecules were investigated using the optimized density-functional theory (DFT) with a continuum model. Higher electron transport characteristics were determined for Tyrian purple, consistent with experimentally derived data. Overall, these results can be used to correctly predict and emphasize the electron transport functions of organic SETs, demonstrating their potential for sustainable nanoelectronics comprising the biodegradable and biocompatible materials.

Ground-state energies and highest occupied eigenvalues of atoms in exchange-only density-functional theory

NASA Astrophysics Data System (ADS)

Li, Yan; Harbola, Manoj K.; Krieger, J. B.; Sahni, Viraht

1989-11-01

The exchange-correlation potential of the Kohn-Sham density-functional theory has recently been interpreted as the work required to move an electron against the electric field of its Fermi-Coulomb hole charge distribution. In this paper we present self-consistent results for ground-state total energies and highest occupied eigenvalues of closed subshell atoms as obtained by this formalism in the exchange-only approximation. The total energies, which are an upper bound, lie within 50 ppm of Hartree-Fock theory for atoms heavier than Be. The highest occupied eigenvalues, as a consequence of this interpretation, approximate well the experimental ionization potentials. In addition, the self-consistently calculated exchange potentials are very close to those of Talman and co-workers [J. D. Talman and W. F. Shadwick, Phys. Rev. A 14, 36 (1976); K. Aashamar, T. M. Luke, and J. D. Talman, At. Data Nucl. Data Tables 22, 443 (1978)].

Multifunctional mussel-inspired copolymerized epigallocatechin gallate (EGCG)/arginine coating: the potential as an ad-layer for vascular materials.

PubMed

Luo, Rifang; Tang, Linlin; Xie, Lingxia; Wang, Jin; Huang, Nan; Wang, Yunbing

2016-12-01

Surface properties are considered to be important factors in addressing proper functionalities. In this paper, a multifunctional mussel-inspired coating was prepared via the direct copolymerization of epigallocatechin gallate (EGCG) and arginine. The coating formation was confirmed by X-ray photoelectron spectroscopy and Fourier transform infrared spectra. The EGCG/arginine coating contained diverse functional groups like amines, phenols and carboxyls, whose densities were also tunable. Such mussel-inspired coating could also be applied as an ad-layer for its secondary reactivity, demonstrated by quartz crystal microbalance technique. Moreover, the tunable surface density of phenols showed potential ability in modulating endothelial cell and smooth muscle cell viability. The coatings rich in phenols presented excellent free radical scavenging property. Current results strongly indicated the potential of EGCG/arginine coatings to be applied as an ad-layer for vascular materials.

Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn-Sham Theory.

PubMed

Sharpe, Daniel J; Levy, Mel; Tozer, David J

2018-02-13

Levy and Zahariev [Phys. Rev. Lett. 113 113002 (2014)] have proposed a new approach for performing density functional theory calculations, termed direct energy Kohn-Sham (DEKS) theory. In this approach, the electronic energy equals the sum of orbital energies, obtained from Kohn-Sham-like orbital equations involving a shifted Hartree-exchange-correlation potential, which must be approximated. In the present study, density scaling homogeneity considerations are used to facilitate DEKS calculations on a series of atoms and molecules, leading to three nonlocal approximations to the shifted potential. The first two rely on preliminary Kohn-Sham calculations using a standard generalized gradient approximation (GGA) exchange-correlation functional and the results illustrate the benefit of describing the dominant Hartree component of the shift exactly. A uniform electron gas analysis is used to eliminate the need for these preliminary Kohn-Sham calculations, leading to a potential with an unconventional form that yields encouraging results, providing strong motivation for further research in DEKS theory.

Infection Unit Density as an Index of Infection Potential of Arbuscular Mycorrhizal Fungi.

PubMed

Ohtomo, Ryo; Kobae, Yoshihiro; Morimoto, Sho; Oka, Norikuni

2018-03-29

The effective use of arbuscular mycorrhizal (AM) fungal function to promote host plant phosphate uptake in agricultural practice requires the accurate quantitative evaluation of AM fungal infection potential in field soil or AM fungal inoculation material. The number of infection units (IUs), intraradical fungal structures derived from single root entries formed after a short cultivation period, may reflect the number of propagules in soil when pot soil is completely permeated by the host root. However, the original IU method, in which all AM propagules in a pot are counted, requires the fine tuning of plant growing conditions and is considered to be laborious. The objective of the present study was to test whether IU density, not the total count of IU, but the number of IUs per unit root length, reflects the density of AM fungal propagules in soil. IU density assessed after 12 d of host plant cultivation and 3,3'-diaminobenzidine (DAB) staining showed a stronger linear correlation with propagule density than the mean infection percentage (MIP). In addition, IU density was affected less by the host plant species than MIP. We suggest that IU density provides a more rapid and reliable quantitation of the propagule density of AM fungi than MIP or the original IU method. Thus, IU density may be a more robust index of AM fungal infection potential for research and practical applications.

Density-functional theory applied to d- and f-electron systems

NASA Astrophysics Data System (ADS)

Wu, Xueyuan

Density functional theory (DFT) has been applied to study the electronic and geometric structures of prototype d- and f-electron systems. For the d-electron system, all electron DFT with gradient corrections to the exchange and correlation functionals has been used to investigate the properties of small neutral and cationic vanadium clusters. Results are in good agreement with available experimental and other theoretical data. For the f-electron system, a hybrid DFT, namely, B3LYP (Becke's 3-parameter hybrid functional using the correlation functional of Lee, Yang and Parr) with relativistic effective core potentials and cluster models has been applied to investigate the nature of chemical bonding of both the bulk and the surfaces of plutonium monoxide and dioxide. Using periodic models, the electronic and geometric structures of PuO2 and its (110) surface, as well as water adsorption on this surface have also been investigated using DFT in both local density approximation (LDA) and generalized gradient approximation (GGA) formalisms.

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

DOE PAGES

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

2018-02-14

The potential for density functional calculations to predict the properties of matter under extreme conditions depends crucially upon having a non-empirical approximate free energy functional valid over a wide range of state conditions. Unlike the ground-state case, no such free-energy exchange- correlation (XC) functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Application in Kohn-Sham calculations for hot electrons inmore » a static fcc Aluminum lattice demon- strates the combined magnitude of thermal and gradient effects handled by this functional. Its accuracy in the increasingly important warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated temperatures and by low density Al calculations over a wide T range.« less

Nonempirical Semilocal Free-Energy Density Functional for Matter under Extreme Conditions

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

Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.

The potential for density functional calculations to predict the properties of matter under extreme conditions depends crucially upon having a non-empirical approximate free energy functional valid over a wide range of state conditions. Unlike the ground-state case, no such free-energy exchange- correlation (XC) functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Application in Kohn-Sham calculations for hot electrons inmore » a static fcc Aluminum lattice demon- strates the combined magnitude of thermal and gradient effects handled by this functional. Its accuracy in the increasingly important warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated temperatures and by low density Al calculations over a wide T range.« less

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.

Enhancing Post-Expansion Chondrogenic Potential of Costochondral Cells in Self-Assembled Neocartilage

PubMed Central

Murphy, Meghan K.; Huey, Daniel J.; Reimer, Andrew J.; Hu, Jerry C.; Athanasiou, Kyriacos A.

2013-01-01

The insufficient healing capacity of articular cartilage necessitates mechanically functional biologic tissue replacements. Using cells to form biomimetic cartilage implants is met with the challenges of cell scarcity and donor site morbidity, requiring expanded cells that possess the ability to generate robust neocartilage. To address this, this study assesses the effects of expansion medium supplementation (bFGF, TFP, FBS) and self-assembled construct seeding density (2, 3, 4 million cells/5 mm dia. construct) on the ability of costochondral cells to generate biochemically and biomechanically robust neocartilage. Results show TFP (1 ng/mL TGF-β1, 5 ng/mL bFGF, 10 ng/mL PDGF) supplementation of serum-free chondrogenic expansion medium enhances the post-expansion chondrogenic potential of costochondral cells, evidenced by increased glycosaminoglycan content, decreased type I/II collagen ratio, and enhanced compressive properties. Low density (2 million cells/construct) enhances matrix synthesis and tensile and compressive mechanical properties. Combined, TFP and Low density interact to further enhance construct properties. That is, with TFP, Low density increases type II collagen content by over 100%, tensile stiffness by over 300%, and compressive moduli by over 140%, compared with High density. In conclusion, the interaction of TFP and Low density seeding enhances construct material properties, allowing for a mechanically functional, biomimetic cartilage to be formed using clinically relevant costochondral cells. PMID:23437288

Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory.

PubMed

Fowler, Nicholas J; Blanford, Christopher F; Warwicker, Jim; de Visser, Sam P

2017-11-02

Blue copper proteins, such as azurin, show dramatic changes in Cu 2+ /Cu + reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high-level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long-range electrostatic changes and hence can be modeled accurately with continuum electrostatics. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Density-functional study on the dopant-segregation mechanism: Chemical potential dependence of dopant-defect complex at Si/SiO2 interface

NASA Astrophysics Data System (ADS)

Kawai, Hiroki; Nakasaki, Yasushi; Kanemura, Takahisa; Ishihara, Takamitsu

2018-04-01

Dopant segregation at Si/SiO2 interface has been a serious problem in silicon device technology. This paper reports a comprehensive density-functional study on the segregation mechanisms of boron, phosphorous, and arsenic at the Si/SiO2 interface. We found that three kinds of interfacial defects, namely, interstitial oxygen, oxygen vacancy, and silicon vacancy with two oxygen atoms, are stable in the possible chemical potential range. Thus, we consider these defects as trap sites for the dopants. For these defects, the dopant segregation energies, the electrical activities of the trapped dopants, and the kinetic energy barriers of the trapping/detrapping processes are calculated. As a result, trapping at the interstitial oxygen site is indicated to be the most plausible mechanism of the dopant segregation. The interstitial oxygen works as a major trap site since it has a high areal density at the Si/SiO2 interface due to the low formation energy.

Atomistic and molecular effects in electric double layers at high surface charges

DOE PAGES

Templeton, Jeremy Alan; Lee, Jonathan; Mani, Ali

2015-06-16

Here, the Poisson–Boltzmann theory for electrolytes near a charged surface is known to be invalid due to unaccounted physics associated with high ion concentration regimes. In order to investigate this regime, fluids density functional theory (f-DFT) and molecular dynamics (MD) simulations were used to determine electric surface potential as a function of surface charge. Based on these detailed computations, for electrolytes with nonpolar solvent, the surface potential is shown to depend quadratically on the surface charge in the high charge limit. We demonstrate that modified Poisson–Boltzmann theories can model this limit if they are augmented with atomic packing densities providedmore » by MD. However, when the solvent is a highly polar molecule water an intermediate regime is identified in which a constant capacitance is realized. Simulation results demonstrate the mechanism underlying this regime, and for the salt water system studied here, it persists throughout the range of physically realistic surface charge densities so the potential’s quadratic surface charge dependence is not obtained.« less

First principle investigations of the physical properties of hydrogen-rich MgH2

NASA Astrophysics Data System (ADS)

Zarshenas, Mohammed; Ahmed, R.; Benali Kanoun, Mohammed; Haq, Bakhtiar ul; Radzi Mat Isa, Ahmad; Goumri-Said, Souraya

2013-12-01

Hydrogen being a cleaner energy carrier has increased the importance of hydrogen-containing light metal hydrides, in particular those with large gravimetric hydrogen density like magnesium hydride (MgH2). In this study, density functional and density functional perturbation theories are combined to investigate the structural, elastic, thermodynamic, electronic and optical properties of MgH2. Our structural parameters calculated with those proposed by Perdew, Burke and Ernzerof generalized gradient approximation (PBE-GGA) and Wu-Cohen GGA (WC-GGA) are in agreement with experimental measurements, however the underestimated band gap values calculated using PBE-GGA and WC-GGA were greatly improved with the GGA suggested by Engle and Vosko and the modified Becke-Johnson exchange correlation potential by Trans and Blaha. As for the thermodynamic properties the specific heat values at low temperatures were found to obey the T3 rule and at higher temperatures Dulong and Petit's law. Our analysis of the optical properties of MgH2 also points to its potential application in optoelectronics.

Paws without claws? Ecological effects of large carnivores in anthropogenic landscapes

PubMed Central

Sahlén, E.; Elmhagen, B.; Chamaillé-Jammes, S.; Sand, H.; Lone, K.; Cromsigt, J. P. G. M.

2016-01-01

Large carnivores are frequently presented as saviours of biodiversity and ecosystem functioning through their creation of trophic cascades, an idea largely based on studies coming primarily out of relatively natural landscapes. However, in large parts of the world, particularly in Europe, large carnivores live in and are returning to strongly human-modified ecosystems. At present, we lack a coherent framework to predict the effects of large carnivores in these anthropogenic landscapes. We review how human actions influence the ecological roles of large carnivores by affecting their density or behaviour or those of mesopredators or prey species. We argue that the potential for density-mediated trophic cascades in anthropogenic landscapes is limited to unproductive areas where even low carnivore numbers may impact prey densities or to the limited parts of the landscape where carnivores are allowed to reach ecologically functional densities. The potential for behaviourally mediated trophic cascades may be larger and more widespread, because even low carnivore densities affect prey behaviour. We conclude that predator–prey interactions in anthropogenic landscapes will be highly context-dependent and human actions will often attenuate the ecological effects of large carnivores. We highlight the knowledge gaps and outline a new research avenue to study the role of carnivores in anthropogenic landscapes. PMID:27798302

Description of plasmon-like band in silver clusters: the importance of the long-range Hartree-Fock exchange in time-dependent density-functional theory simulations.

PubMed

Rabilloud, Franck

2014-10-14

Absorption spectra of Ag20 and Ag55(q) (q = +1, -3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.

Dispersion correction derived from first principles for density functional theory and Hartree-Fock theory.

PubMed

Guidez, Emilie B; Gordon, Mark S

2015-03-12

The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Hartree-Fock (HF-D(EFP)) energies. Overall, DFT-D(EFP) performs similarly to the semiempirical DFT-D corrections for the test cases investigated in this work. HF-D(EFP) tends to underestimate binding energies and overestimate intermolecular equilibrium distances, relative to coupled cluster theory, most likely due to incomplete accounting for electron correlation. Overall, this first-principles dispersion correction yields results that are in good agreement with coupled-cluster calculations at a low computational cost.

A Molecular Electron Density Theory Study of the Chemical Reactivity of Cis- and Trans-Resveratrol.

PubMed

Frau, Juan; Muñoz, Francisco; Glossman-Mitnik, Daniel

2016-12-01

The chemical reactivity of resveratrol isomers with the potential to play a role as inhibitors of the nonenzymatic glycation of amino acids and proteins, both acting as antioxidants and as chelating agents for metallic ions such as Cu, Al and Fe, have been studied by resorting to the latest family of Minnesota density functionals. The chemical reactivity descriptors have been calculated through Molecular Electron Density Theory encompassing Conceptual DFT. The active sites for nucleophilic and electrophilic attacks have been chosen by relating them to the Fukui function indices, the dual descriptor f ( 2 ) ( r ) and the electrophilic and nucleophilic Parr functions. The validity of "Koopmans' theorem in DFT" has been assessed by means of a comparison between the descriptors calculated through vertical energy values and those arising from the HOMO and LUMO values.

Criticality of the electron-nucleus cusp condition to local effective potential-energy theories

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

Pan Xiaoyin; Sahni, Viraht; Graduate School of the City University of New York, 360 Fifth Avenue, New York, New York 10016

2003-01-01

Local(multiplicative) effective potential energy-theories of electronic structure comprise the transformation of the Schroedinger equation for interacting Fermi systems to model noninteracting Fermi or Bose systems whereby the equivalent density and energy are obtained. By employing the integrated form of the Kato electron-nucleus cusp condition, we prove that the effective electron-interaction potential energy of these model fermions or bosons is finite at a nucleus. The proof is general and valid for arbitrary system whether it be atomic, molecular, or solid state, and for arbitrary state and symmetry. This then provides justification for all prior work in the literature based on themore » assumption of finiteness of this potential energy at a nucleus. We further demonstrate the criticality of the electron-nucleus cusp condition to such theories by an example of the hydrogen molecule. We show thereby that both model system effective electron-interaction potential energies, as determined from densities derived from accurate wave functions, will be singular at the nucleus unless the wave function satisfies the electron-nucleus cusp condition.« less

Achieving DFT accuracy with a machine-learning interatomic potential: Thermomechanics and defects in bcc ferromagnetic iron

NASA Astrophysics Data System (ADS)

Dragoni, Daniele; Daff, Thomas D.; Csányi, Gábor; Marzari, Nicola

2018-01-01

We show that the Gaussian Approximation Potential (GAP) machine-learning framework can describe complex magnetic potential energy surfaces, taking ferromagnetic iron as a paradigmatic challenging case. The training database includes total energies, forces, and stresses obtained from density-functional theory in the generalized-gradient approximation, and comprises approximately 150,000 local atomic environments, ranging from pristine and defected bulk configurations to surfaces and generalized stacking faults with different crystallographic orientations. We find the structural, vibrational, and thermodynamic properties of the GAP model to be in excellent agreement with those obtained directly from first-principles electronic-structure calculations. There is good transferability to quantities, such as Peierls energy barriers, which are determined to a large extent by atomic configurations that were not part of the training set. We observe the benefit and the need of using highly converged electronic-structure calculations to sample a target potential energy surface. The end result is a systematically improvable potential that can achieve the same accuracy of density-functional theory calculations, but at a fraction of the computational cost.

Large deviation function for a driven underdamped particle in a periodic potential

NASA Astrophysics Data System (ADS)

Fischer, Lukas P.; Pietzonka, Patrick; Seifert, Udo

2018-02-01

Employing large deviation theory, we explore current fluctuations of underdamped Brownian motion for the paradigmatic example of a single particle in a one-dimensional periodic potential. Two different approaches to the large deviation function of the particle current are presented. First, we derive an explicit expression for the large deviation functional of the empirical phase space density, which replaces the level 2.5 functional used for overdamped dynamics. Using this approach, we obtain several bounds on the large deviation function of the particle current. We compare these to bounds for overdamped dynamics that have recently been derived, motivated by the thermodynamic uncertainty relation. Second, we provide a method to calculate the large deviation function via the cumulant generating function. We use this method to assess the tightness of the bounds in a numerical case study for a cosine potential.

DAMQT: A package for the analysis of electron density in molecules

NASA Astrophysics Data System (ADS)

López, Rafael; Rico, Jaime Fernández; Ramírez, Guillermo; Ema, Ignacio; Zorrilla, David

2009-09-01

DAMQT is a package for the analysis of the electron density in molecules and the fast computation of the density, density deformations, electrostatic potential and field, and Hellmann-Feynman forces. The method is based on the partition of the electron density into atomic fragments by means of a least deformation criterion. Each atomic fragment of the density is expanded in regular spherical harmonics times radial factors, which are piecewise represented in terms of analytical functions. This representation is used for the fast evaluation of the electrostatic potential and field generated by the electron density and nuclei, as well as for the computation of the Hellmann-Feynman forces on the nuclei. An analysis of the atomic and molecular deformations of the density can be also carried out, yielding a picture that connects with several concepts of the empirical structural chemistry. Program summaryProgram title: DAMQT1.0 Catalogue identifier: AEDL_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEDL_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GPLv3 No. of lines in distributed program, including test data, etc.: 278 356 No. of bytes in distributed program, including test data, etc.: 31 065 317 Distribution format: tar.gz Programming language: Fortran90 and C++ Computer: Any Operating system: Linux, Windows (Xp, Vista) RAM: 190 Mbytes Classification: 16.1 External routines: Trolltech's Qt (4.3 or higher) ( http://www.qtsoftware.com/products), OpenGL (1.1 or higher) ( http://www.opengl.org/), GLUT 3.7 ( http://www.opengl.org/resources/libraries/glut/). Nature of problem: Analysis of the molecular electron density and density deformations, including fast evaluation of electrostatic potential, electric field and Hellmann-Feynman forces on nuclei. Solution method: The method of Deformed Atoms in Molecules, reported elsewhere [1], is used for partitioning the molecular electron density into atomic fragments, which are further expanded in spherical harmonics times radial factors. The partition is used for defining molecular density deformations and for the fast calculation of several properties associated to density. Restrictions: The current version is limited to 120 atoms, 2000 contracted functions, and l=5 in basis functions. Density must come from a LCAO calculation (any level) with spherical (not Cartesian) Gaussian functions. Unusual features: The program contains an OPEN statement to binary files (stream) in file GOPENMOL.F90. This statement has not a standard syntax in Fortran 90. Two possibilities are considered in conditional compilation: Intel's ifort and Fortran2003 standard. This latter is applied to compilers other than ifort (gfortran uses this one, for instance). Additional comments: The distribution file for this program is over 30 Mbytes and therefore is not delivered directly when download or e-mail is requested. Instead a html file giving details of how the program can be obtained is sent. Running time: Largely dependent on the system size and the module run (from fractions of a second to hours). References: [1] J. Fernández Rico, R. López, I. Ema, G. Ramírez, J. Mol. Struct. (Theochem) 727 (2005) 115.

Some Exact Results for the Schroedinger Wave Equation with a Time Dependent Potential

NASA Technical Reports Server (NTRS)

Campbell, Joel

2009-01-01

The time dependent Schroedinger equation with a time dependent delta function potential is solved exactly for many special cases. In all other cases the problem can be reduced to an integral equation of the Volterra type. It is shown that by knowing the wave function at the origin, one may derive the wave function everywhere. Thus, the problem is reduced from a PDE in two variables to an integral equation in one. These results are used to compare adiabatic versus sudden changes in the potential. It is shown that adiabatic changes in the p otential lead to conservation of the normalization of the probability density.

Quantum mechanical probability current as electromagnetic 4-current from topological EM fields

NASA Astrophysics Data System (ADS)

van der Mark, Martin B.

2015-09-01

Starting from a complex 4-potential A = αdβ we show that the 4-current density in electromagnetism and the probability current density in relativistic quantum mechanics are of identical form. With the Dirac-Clifford algebra Cl1,3 as mathematical basis, the given 4-potential allows topological solutions of the fields, quite similar to Bateman's construction, but with a double field solution that was overlooked previously. A more general nullvector condition is found and wave-functions of charged and neutral particles appear as topological configurations of the electromagnetic fields.

Formally exact integral equation theory of the exchange-only potential in density functional theory: Refined closure approximation

NASA Astrophysics Data System (ADS)

March, N. H.; Nagy, Á.

A fonnally exact integral equation theory for the exchange-only potential Vx(r) in density functional theory was recently set up by Howard and March [I.A. Howard, N.H. March, J. Chem. Phys. 119 (2003) 5789]. It involved a `closure' function P(r) satisfying the exact sum rule ∫ P(r) dr = 0. The simplest choice P(r) = 0 recovers then the approximation proposed by Della Sala and Görling [F. Della Sala, A. Görling, J. Chem. Phys. 115 (2001) 5718] and by Gritsenko and Baerends [O.V. Gritsenko, E.J. Baerends, Phys. Rev. A 64 (2001) 042506]. Here, refined choices of P(r) are proposed, the most direct being based on the KLI (Krieger-Li-Iafrate) approximation. A further choice given some attention is where P(r) involves frontier orbital properties. In particular, the introduction of the LUMO (lowest unoccupied molecular) orbital, along with the energy separation between HOMO (highest occupied molecular orbital) and LUMO levels, should prove a significant step beyond current approximations to the optimized potential method, all of which involve only single-particle occupied orbitals.

Modified Fourth-Order Kinetic Energy Gradient Expansion with Hartree Potential-Dependent Coefficients.

PubMed

Constantin, Lucian A; Fabiano, Eduardo; Della Sala, Fabio

2017-09-12

Using the semiclassical neutral atom theory, we developed a modified fourth-order kinetic energy (KE) gradient expansion (GE4m) that keeps unchanged all the linear-response terms of the uniform electron gas and gives a significant improvement with respect to the known semilocal functionals for both large atoms and jellium surfaces. On the other hand, GE4m is not accurate for light atoms; thus, we modified the GE4m coefficients making them dependent on a novel ingredient, the reduced Hartree potential, recently introduced in the Journal of Chemical Physics 2016, 145, 084110, in the context of exchange functionals. The resulting KE gradient expansion functional, named uGE4m, belongs to the novel class of u-meta-generalized-gradient-approximations (uMGGA) whose members depend on the conventional ingredients (i.e., the reduced gradient and Laplacian of the density) as well as on the reduced Hartree potential. To test uGE4m, we defined an appropriate benchmark (including total KE and KE differences for atoms, molecules and jellium clusters) for gradient expansion functionals, that is, including only those systems which are mainly described by a slowly varying density regime. While most of the GGA and meta-GGA KE functionals (we tested 18 of them) are accurate for some properties and inaccurate for others, uGE4m shows a consistently good performance for all the properties considered. This represents a qualitative boost in the KE functional development and highlights the importance of the reduced Hartree potential for the construction of next-generation KE functionals.

Extended polarization in 3rd order SCC-DFTB from chemical potential equilization

PubMed Central

Kaminski, Steve; Giese, Timothy J.; Gaus, Michael; York, Darrin M.; Elstner, Marcus

2012-01-01

In this work we augment the approximate density functional method SCC-DFTB (DFTB3) with the chemical potential equilization (CPE) approach in order to improve the performance for molecular electronic polarizabilities. The CPE method, originally implemented for NDDO type methods by Giese and York, has been shown to emend minimal basis methods wrt response properties significantly, and has been applied to SCC-DFTB recently. CPE allows to overcome this inherent limitation of minimal basis methods by supplying an additional response density. The systematic underestimation is thereby corrected quantitatively without the need to extend the atomic orbital basis, i.e. without increasing the overall computational cost significantly. Especially the dependency of polarizability as a function of molecular charge state was significantly improved from the CPE extension of DFTB3. The empirical parameters introduced by the CPE approach were optimized for 172 organic molecules in order to match the results from density functional methods (DFT) methods using large basis sets. However, the first order derivatives of molecular polarizabilities, as e.g. required to compute Raman activities, are not improved by the current CPE implementation, i.e. Raman spectra are not improved. PMID:22894819

Structure and capacitance of an electric double layer of an asymmetric valency dimer electrolyte: A comparison of the density functional theory with Monte Carlo simulations

DOE PAGES

Henderson, Douglas; Silvestre-Alcantara, Whasington; Kaja, Monika; ...

2016-08-18

Here, the density functional theory is applied to a study of the structure and differential capacitance of a planar electric double layer formed by a valency asymmetric mixture of charged dimers and monomers. The dimer consists of two tangentially tethered hard spheres of equal diameters of which one is charged and the other is neutral, while the monomer is a charged hard sphere of the same size. The dimer electrolyte is next to a uniformly charged, smooth planar electrode. The electrode-particle singlet distributions, the mean electrostatic potential, and the differential capacitance for the model double layer are evaluated for amore » 2:1/1:2 valency electrolyte at a given concentration. Important consequences of asymmetry in charges and in ion shapes are (i) a finite, non-zero potential of zero charge, and (ii) asymmetric shaped 2:1 and 1:2 capacitance curves which are not mirror images of each other. Comparisons of the density functional results with the corresponding Monte Carlo simulations show the theoretical predictions to be in good agreement with the simulations overall except near zero surface charge.« less

Coupled-cluster, Möller Plesset (MP2), Density Fitted Local MP2, and Density Functional Theory Examination of the Energetic and Structural Features of Hydrophobic Solvation: Water and Pentane

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

Ghadar, Yasaman; Clark, Aurora E.

2012-02-02

The interaction potentials between immiscible polar and non-polar solvents are a major driving force behind the formation of liquid:liquid interfaces. In this work, the interaction energy of water–pentane dimer has been determined using coupled-cluster theory with single double (triple) excitations [CCSD(T)], 2nd order Möller Plesset perturbation theory (MP2), density fitted local MP2 (DF-LMP2), as well as density functional theory using a wide variety of density functionals and several different basis sets. The M05-2X exchange correlation functionals exhibit excellent agreement with CCSD(T) and DF-LMP2 after taking into account basis set superposition error. The gas phase water–pentane interaction energy is found tomore » be quite sensitive to the specific pentane isomer (2,2- dimethylpropane vs. n-pentane) and relative orientation of the monomeric constituents. Subsequent solution phase cluster calculations of 2,2-dimethylpropane and n-pentane solvated by water indicate a positive free energy of solvation that is in good agreement with available experimental data. Structural parameters are quite sensitive to the density functional employed and reflect differences in the two-body interaction energy calculated by each method. In contrast, cluster calculations of pentane solvation of H2O solute are found to be inadequate for describing the organic solvent, likely due to limitations associated with the functionals employed (B3LYP, BHandH, and M05-2X).« less

Pair potentials for liquid sodium near freezing from electron theory and from inversion of the measured structure factor

NASA Astrophysics Data System (ADS)

Perrot, F.; March, N. H.

An effective pair potential for liquid sodium near freezing has been calculated from electron theory using the density-functional method. The main features of the potential extracted by Reatto, Levesque, and Weis [phys. Rev. A 33, 3451 (1986)] by inverting the measured structure factor of Greenfield, Wellendorf, and Wiser [Phys. Rev. A 4, 1607 (1971)] are faithfully reflected by electron theory. To obtain precise agreement between the two methods will evidently require further progress in setting up nonlocal exchange and correlation functionals.

Copper interstitial recombination centers in Cu 3 N

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

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

Copper interstitial recombination centers in Cu 3 N

DOE PAGES

Yee, Ye Sheng; Inoue, Hisashi; Hultqvist, Adam; ...

2018-06-04

We present a comprehensive study of the earth-abundant semiconductor Cu 3N as a potential solar energy conversion material, using density functional theory and experimental methods. Density functional theory indicates that among the dominant intrinsic point defects, copper vacancies V Cu have shallow defect levels while copper interstitials Cu i behave as deep potential wells in the conduction band which mediate Shockley-Read-Hall recombination. The existence of Cu i defects has been experimentally verified using photothermal deflection spectroscopy. A Cu 3N/ZnS heterojunction diode with good current-voltage rectification behavior has been demonstrated experimentally, but no photocurrent is generated under illumination. Finally, the absencemore » of photocurrent can be explained by a large concentration of Cu i recombination centers capturing electrons in p-type Cu 3N.« less

Communication: Simple liquids' high-density viscosity

NASA Astrophysics Data System (ADS)

Costigliola, Lorenzo; Pedersen, Ulf R.; Heyes, David M.; Schrøder, Thomas B.; Dyre, Jeppe C.

2018-02-01

This paper argues that the viscosity of simple fluids at densities above that of the triple point is a specific function of temperature relative to the freezing temperature at the density in question. The proposed viscosity expression, which is arrived at in part by reference to the isomorph theory of systems with hidden scale invariance, describes computer simulations of the Lennard-Jones system as well as argon and methane experimental data and simulation results for an effective-pair-potential model of liquid sodium.

Gravity dual of spin and charge density waves

NASA Astrophysics Data System (ADS)

Jokela, Niko; Järvinen, Matti; Lippert, Matthew

2014-12-01

At high enough charge density, the homogeneous state of the D3-D7' model is unstable to fluctuations at nonzero momentum. We investigate the end point of this instability, finding a spatially modulated ground state, which is a charge and spin density wave. We analyze the phase structure of the model as a function of chemical potential and magnetic field and find the phase transition from the homogeneous state to be first order, with a second-order critical point at zero magnetic field.

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.

Exercise-mediated changes in high-density lipoprotein: impact on form and function.

PubMed

Blazek, Alisa; Rutsky, Jessica; Osei, Kwame; Maiseyeu, Andrei; Rajagopalan, Sanjay

2013-09-01

The goal of this systematic review was to assess the current understanding of the effects of exercise intervention on high-density lipoprotein (HDL) cholesterol (HDL-C) and changes in HDL function as well as modification of these effects by genomic factors. The reviewed studies demonstrate that exercise has modest effects on HDL-C with limited data suggesting an effect on HDL function. Genetic polymorphisms in proteins associated with HDL metabolism play a role in modifying the HDL-C response to exercise and possibly its function. Exercise as an intervention for patients at risk for cardiovascular events can lead to small improvements in HDL-C and potential changes in HDL function. There is an important modifier effect of genetics in determining these changes. Copyright © 2013 Mosby, Inc. All rights reserved.

Vibrational Properties of Hydrogen-Bonded Systems Using the Multireference Generalization to the "On-the-Fly" Electronic Structure within Quantum Wavepacket ab Initio Molecular Dynamics (QWAIMD).

PubMed

Li, Junjie; Li, Xiaohu; Iyengar, Srinivasan S

2014-06-10

We discuss a multiconfigurational treatment of the "on-the-fly" electronic structure within the quantum wavepacket ab initio molecular dynamics (QWAIMD) method for coupled treatment of quantum nuclear effects with electronic structural effects. Here, multiple single-particle electronic density matrices are simultaneously propagated with a quantum nuclear wavepacket and other classical nuclear degrees of freedom. The multiple density matrices are coupled through a nonorthogonal configuration interaction (NOCI) procedure to construct the instantaneous potential surface. An adaptive-mesh-guided set of basis functions composed of Gaussian primitives are used to simplify the electronic structure calculations. Specifically, with the replacement of the atom-centered basis functions positioned on the centers of the quantum-mechanically treated nuclei by a mesh-guided band of basis functions, the two-electron integrals used to compute the electronic structure potential surface become independent of the quantum nuclear variable and hence reusable along the entire Cartesian grid representing the quantum nuclear coordinates. This reduces the computational complexity involved in obtaining a potential surface and facilitates the interpretation of the individual density matrices as representative diabatic states. The parametric nuclear position dependence of the diabatic states is evaluated at the initial time-step using a Shannon-entropy-based sampling function that depends on an approximation to the quantum nuclear wavepacket and the potential surface. This development is meant as a precursor to an on-the-fly fully multireference electronic structure procedure embedded, on-the-fly, within a quantum nuclear dynamics formalism. We benchmark the current development by computing structural, dynamic, and spectroscopic features for a series of bihalide hydrogen-bonded systems: FHF(-), ClHCl(-), BrHBr(-), and BrHCl(-). We find that the donor-acceptor structural features are in good agreement with experiments. Spectroscopic features are computed using a unified velocity/flux autocorrelation function and include vibrational fundamentals and combination bands. These agree well with experiments and other theories.

Critical quench dynamics in confined systems.

PubMed

Collura, Mario; Karevski, Dragi

2010-05-21

We analyze the coherent quantum evolution of a many-particle system after slowly sweeping a power-law confining potential. The amplitude of the confining potential is varied in time along a power-law ramp such that the many-particle system finally reaches or crosses a critical point. Under this protocol we derive general scaling laws for the density of excitations created during the nonadiabatic sweep of the confining potential. It is found that the mean excitation density follows an algebraic law as a function of the sweeping rate with an exponent that depends on the space-time properties of the potential. We confirm our scaling laws by first order adiabatic calculation and exact results on the Ising quantum chain with a varying transverse field.

Applications of Density Functional Theory in Soft Condensed Matter

NASA Astrophysics Data System (ADS)

Löwen, Hartmut

Applications of classical density functional theory (DFT) to soft matter systems like colloids, liquid crystals and polymer solutions are discussed with a focus on the freezing transition and on nonequilibrium Brownian dynamics. First, after a brief reminder of equilibrium density functional theory, DFT is applied to the freezing transition of liquids into crystalline lattices. In particular, spherical particles with radially symmetric pair potentials will be treated (like hard spheres, the classical one-component plasma or Gaussian-core particles). Second, the DFT will be generalized towards Brownian dynamics in order to tackle nonequilibrium problems. After a general introduction to Brownian dynamics using the complementary Smoluchowski and Langevin pictures appropriate for the dynamics of colloidal suspensions, the dynamical density functional theory (DDFT) will be derived from the Smoluchowski equation. This will be done first for spherical particles (e.g. hard spheres or Gaussian-cores) without hydrodynamic interactions. Then we show how to incorporate hydrodynamic interactions between the colloidal particles into the DDFT framework and compare to Brownian dynamics computer simulations. Third orientational degrees of freedom (rod-like particles) will be considered as well. In the latter case, the stability of intermediate liquid crystalline phases (isotropic, nematic, smectic-A, plastic crystals etc) can be predicted. Finally, the corresponding dynamical extension of density functional theory towards orientational degrees of freedom is proposed and the collective behaviour of "active" (self-propelled) Brownian particles is briefly discussed.

The potential role of perivascular lymphatic vessels in preservation of kidney allograft function.

PubMed

Tsuchimoto, Akihiro; Nakano, Toshiaki; Hasegawa, Shoko; Masutani, Kosuke; Matsukuma, Yuta; Eriguchi, Masahiro; Nagata, Masaharu; Nishiki, Takehiro; Kitada, Hidehisa; Tanaka, Masao; Kitazono, Takanari; Tsuruya, Kazuhiko

2017-08-01

Lymphangiogenesis occurs in diseased native kidneys and kidney allografts, and correlates with histological injury; however, the clinical significance of lymphatic vessels in kidney allografts is unclear. This study retrospectively reviewed 63 kidney transplant patients who underwent protocol biopsies. Lymphatic vessels were identified by immunohistochemical staining for podoplanin, and were classified according to their location as perivascular or interstitial lymphatic vessels. The associations between perivascular lymphatic density and kidney allograft function and pathological findings were analyzed. There were no significant differences in perivascular lymphatic densities in kidney allograft biopsy specimens obtained at 0 h, 3 months and 12 months. The groups with higher perivascular lymphatic density showed a lower proportion of progression of interstitial fibrosis/tubular atrophy grade from 3 to 12 months (P for trend = 0.039). Perivascular lymphatic density was significantly associated with annual decline of estimated glomerular filtration rate after 12 months (r = -0.31, P = 0.017), even after adjusting for multiple confounders (standardized β = -0.30, P = 0.019). High perivascular lymphatic density is associated with favourable kidney allograft function. The perivascular lymphatic network may be involved in inhibition of allograft fibrosis and stabilization of graft function.

Reformulated space-charge-limited current model and its application to disordered organic systems

NASA Astrophysics Data System (ADS)

Woellner, Cristiano F.; Freire, José A.

2011-02-01

We have reformulated a traditional model used to describe the current-voltage dependence of low mobility materials sandwiched between planar electrodes by using the quasi-electrochemical potential as the fundamental variable instead of the local electric field or the local charge carrier density. This allows the material density-of-states to enter explicitly in the equations and dispenses with the need to assume a particular type of contact. The diffusion current is included and as a consequence the current-voltage dependence obtained covers, with increasing bias, the diffusion limited current, the space-charge limited current, and the injection limited current regimes. The generalized Einstein relation and the field and density dependent mobility are naturally incorporated into the formalism; these two points being of particular relevance for disordered organic semiconductors. The reformulated model can be applied to any material where the carrier density and the mobility may be written as a function of the quasi-electrochemical potential. We applied it to the textbook example of a nondegenerate, constant mobility material and showed how a single dimensionless parameter determines the form of the I(V) curve. We obtained integral expressions for the carrier density and for the mobility as a function of the quasi-electrochemical potential for a Gaussianly disordered organic material and found the general form of the I(V) curve for such materials over the full range of bias, showing how the energetic disorder alone can give rise, in the space-charge limited current regime, to an I∝Vn dependence with an exponent n larger than 2.

A density functional theory study on the thermodynamic and dynamic properties of anthraquinone analogue cathode materials for rechargeable lithium ion batteries.

PubMed

Yang, Shu-Jing; Qin, Xiao-Ya; He, Rongxing; Shen, Wei; Li, Ming; Zhao, Liu-Bin

2017-05-21

Organic redox compounds have become the emerging electrode materials for rechargeable lithium ion batteries. The high electrochemical performance provides organic electrode materials with great opportunities to be applied in electric energy storage devices. Among the different types of organic materials, conjugated carbonyl compounds are the most promising type at present, because only they can simultaneously achieve, high energy density, high cycling stability, and high power density. In this research, a series of heteroatom substituted anthraquinone (AQ) derivatives were designed theoretically so that the high theoretical capacity of AQ remained. The discharge and charge mechanism as well as the thermodynamic and dynamic properties of AQ and its derivatives were investigated using first-principles density functional theory. Using heteroatom substitution, both the thermodynamic and dynamic properties of AQ as cathode materials could be largely improved. Among these conjugated carboxyl compounds, BDOZD and BDIOZD with a simultaneously high theoretical capacity and high working potential exhibit the largest energy density of about 780 W h kg -1 , which is 41% larger than that of AQ. The PQD with the smallest value of λ gives the largest charge transfer rate constant, which is about four times as large as the prototype molecule, AQ. The most interesting finding is that the lithium ion transfer plays a very important role in influencing both the discharge potential and electrochemical charge transfer rate. The present study illustrates that theoretical calculations provide a highly effective way to discover potential materials for use with rechargeable lithium ion batteries.

Hydrodynamic limit of Wigner-Poisson kinetic theory: Revisited

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

Akbari-Moghanjoughi, M.; International Centre for Advanced Studies in Physical Sciences and Institute for Theoretical Physics, Ruhr University Bochum, D-44780 Bochum

2015-02-15

In this paper, we revisit the hydrodynamic limit of the Langmuir wave dispersion relation based on the Wigner-Poisson model in connection with that obtained directly from the original Lindhard dielectric function based on the random-phase-approximation. It is observed that the (fourth-order) expansion of the exact Lindhard dielectric constant correctly reduces to the hydrodynamic dispersion relation with an additional term of fourth-order, beside that caused by the quantum diffraction effect. It is also revealed that the generalized Lindhard dielectric theory accounts for the recently discovered Shukla-Eliasson attractive potential (SEAP). However, the expansion of the exact Lindhard static dielectric function leads tomore » a k{sup 4} term of different magnitude than that obtained from the linearized quantum hydrodynamics model. It is shown that a correction factor of 1/9 should be included in the term arising from the quantum Bohm potential of the momentum balance equation in fluid model in order for a correct plasma dielectric response treatment. Finally, it is observed that the long-range oscillatory screening potential (Friedel oscillations) of type cos(2k{sub F}r)/r{sup 3}, which is a consequence of the divergence of the dielectric function at point k = 2k{sub F} in a quantum plasma, arises due to the finiteness of the Fermi-wavenumber and is smeared out in the limit of very high electron number-densities, typical of white dwarfs and neutron stars. In the very low electron number-density regime, typical of semiconductors and metals, where the Friedel oscillation wavelength becomes much larger compared to the interparticle distances, the SEAP appears with a much deeper potential valley. It is remarked that the fourth-order approximate Lindhard dielectric constant approaches that of the linearized quantum hydrodynamic in the limit if very high electron number-density. By evaluation of the imaginary part of the Lindhard dielectric function, it is shown that the Landau-damping region in ω-k plane increases dramatically by increase of the electron number-density.« less

Molecular properties via a subsystem density functional theory formulation: a common framework for electronic embedding.

PubMed

Höfener, Sebastian; Gomes, André Severo Pereira; Visscher, Lucas

2012-01-28

In this article, we present a consistent derivation of a density functional theory (DFT) based embedding method which encompasses wave-function theory-in-DFT (WFT-in-DFT) and the DFT-based subsystem formulation of response theory (DFT-in-DFT) by Neugebauer [J. Neugebauer, J. Chem. Phys. 131, 084104 (2009)] as special cases. This formulation, which is based on the time-averaged quasi-energy formalism, makes use of the variation Lagrangian techniques to allow the use of non-variational (in particular: coupled cluster) wave-function-based methods. We show how, in the time-independent limit, we naturally obtain expressions for the ground-state DFT-in-DFT and WFT-in-DFT embedding via a local potential. We furthermore provide working equations for the special case in which coupled cluster theory is used to obtain the density and excitation energies of the active subsystem. A sample application is given to demonstrate the method. © 2012 American Institute of Physics

The adsorption of NO, NH3, N2 on carbon surface: a density functional theory study.

PubMed

Wang, Jiayong; Yang, Mo; Deng, Debing; Qiu, Shuxia

2017-08-11

To explore the adsorption mechanism of NO, NH 3 , N 2 on a carbon surface, and the effect of basic and acidic functional groups, density functional theory was employed to investigate the interactions between these molecules and carbon surfaces. Molecular electrostatic potential, Mulliken population analyses, reduced density gradient, and Mayer bond order analyses were used to clarify the adsorption mechanism. The results indicate that van der Waals interactions are responsible for N 2 physisorption, and N 2 is the least likely to adsorb on a carbon surface. Modification of carbon materials to decorate basic or acidic functional groups could enhance the NH 3 physisorption because of hydrogen bonding or electrostatic interactions, however, NO physisorption on a carbon surface is poor. Zig-zag sites are more reactive than armchair sites when these gas molecules absorb on the edge sites of carbon surface. Graphical abstract NH 3 , N 2 , NO adsortion on carbon surface.

CheckDen, a program to compute quantum molecular properties on spatial grids.

PubMed

Pacios, Luis F; Fernandez, Alberto

2009-09-01

CheckDen, a program to compute quantum molecular properties on a variety of spatial grids is presented. The program reads as unique input wavefunction files written by standard quantum packages and calculates the electron density rho(r), promolecule and density difference function, gradient of rho(r), Laplacian of rho(r), information entropy, electrostatic potential, kinetic energy densities G(r) and K(r), electron localization function (ELF), and localized orbital locator (LOL) function. These properties can be calculated on a wide range of one-, two-, and three-dimensional grids that can be processed by widely used graphics programs to render high-resolution images. CheckDen offers also other options as extracting separate atom contributions to the property computed, converting grid output data into CUBE and OpenDX volumetric data formats, and perform arithmetic combinations with grid files in all the recognized formats.

Vibrational, spectroscopic, molecular docking and density functional theory studies on N-(5-aminopyridin-2-yl)acetamide

NASA Astrophysics Data System (ADS)

Asath, R. Mohamed; Rekha, T. N.; Premkumar, S.; Mathavan, T.; Benial, A. Milton Franklin

2016-12-01

Conformational analysis was carried out for N-(5-aminopyridin-2-yl)acetamide (APA) molecule. The most stable, optimized structure was predicted by the density functional theory calculations using the B3LYP functional with cc-pVQZ basis set. The optimized structural parameters and vibrational frequencies were calculated. The experimental and theoretical vibrational frequencies were assigned and compared. Ultraviolet-visible spectrum was simulated and validated experimentally. The molecular electrostatic potential surface was simulated. Frontier molecular orbitals and related molecular properties were computed, which reveals that the higher molecular reactivity and stability of the APA molecule and further density of states spectrum was simulated. The natural bond orbital analysis was also performed to confirm the bioactivity of the APA molecule. Antidiabetic activity was studied based on the molecular docking analysis and the APA molecule was identified that it can act as a good inhibitor against diabetic nephropathy.

On the phase diagram of water with density functional theory potentials: the melting temperature of Ice I-h with the Perdew-Burke-Ernzerhof and Becke-Lee-Yang-Parr functionals

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

Yoo, Soohaeng; Zeng, Xiao Cheng; Xantheas, Sotiris S.

2009-06-11

The melting temperature (Tm) of ice Ih was determined from constant enthalphy (NPH) Born-Oppenheimer Molecular Dynamics (BOMD) simulations to be 417±3 K for the Perdew-Burke-Ernzerhof (PBE) and 411±4 K for the Becke-Lee-Yang-Parr (BLYP) density functionals using a coexisting ice (Ih)-liquid phase at constant pressures of P = 2,500 and 10,000 bar and a density ρ = 1 g/cm3, respectively. This suggests that ambient condition simulations at ρ = 1 g/cm3 will rather describe a supercooled state that is overstructured when compared to liquid water. This work was supported by the US Department of Energy Office of Basic Energy Sciences' Chemicalmore » Sciences program. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Density function theoretical study on the complex involved in Th atom-activated C-C bond in C2H6

NASA Astrophysics Data System (ADS)

Qing-Qing, Wang; Peng, Li; Tao, Gao; Hong-Yan, Wang; Bing-Yun, Ao

2016-06-01

Density functional theory (DFT) calculations are performed to investigate the reactivity of Th atom toward ethane C-C bond activation. A comprehensive description of the reaction mechanisms leading to two different reaction products is presented. We report a complete exploration of the potential energy surfaces by taking into consideration different spin states. In addition, the intermediate and transition states along the reaction paths are characterized. Total, partial, and overlap population density of state diagrams and analyses are also presented. Furthermore, the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function (ELF) and Mayer bond order. Infrared spectrum (IR) is obtained and further discussed based on the optimized geometries. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160, 21401173, and 11364023).

Random-Phase Approximation Methods

NASA Astrophysics Data System (ADS)

Chen, Guo P.; Voora, Vamsee K.; Agee, Matthew M.; Balasubramani, Sree Ganesh; Furche, Filipp

2017-05-01

Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical picture of screening and simple diagrammatic analysis. A new decomposition of the RPA correlation energy into plasmonic modes leads to an appealing visualization of electron correlation in terms of charge density fluctuations. Recent developments in the areas of beyond-RPA methods, RPA correlation potentials, and efficient algorithms for RPA energy and property calculations are reviewed. The ability of RPA to approximately capture static correlation in molecules is quantified by an analysis of RPA natural occupation numbers. We illustrate the use of RPA methods in applications to small-gap systems such as open-shell d- and f-element compounds, radicals, and weakly bound complexes, where semilocal density functional results exhibit strong functional dependence.

Monte Carlo method for computing density of states and quench probability of potential energy and enthalpy landscapes.

PubMed

Mauro, John C; Loucks, Roger J; Balakrishnan, Jitendra; Raghavan, Srikanth

2007-05-21

The thermodynamics and kinetics of a many-body system can be described in terms of a potential energy landscape in multidimensional configuration space. The partition function of such a landscape can be written in terms of a density of states, which can be computed using a variety of Monte Carlo techniques. In this paper, a new self-consistent Monte Carlo method for computing density of states is described that uses importance sampling and a multiplicative update factor to achieve rapid convergence. The technique is then applied to compute the equilibrium quench probability of the various inherent structures (minima) in the landscape. The quench probability depends on both the potential energy of the inherent structure and the volume of its corresponding basin in configuration space. Finally, the methodology is extended to the isothermal-isobaric ensemble in order to compute inherent structure quench probabilities in an enthalpy landscape.

Redox potential distribution of an organic-rich contaminated site obtained by the inversion of self-potential data

NASA Astrophysics Data System (ADS)

Abbas, M.; Jardani, A.; Soueid Ahmed, A.; Revil, A.; Brigaud, L.; Bégassat, Ph.; Dupont, J. P.

2017-11-01

Mapping the redox potential of shallow aquifers impacted by hydrocarbon contaminant plumes is important for the characterization and remediation of such contaminated sites. The redox potential of groundwater is indicative of the biodegradation of hydrocarbons and is important in delineating the shapes of contaminant plumes. The self-potential method was used to reconstruct the redox potential of groundwater associated with an organic-rich contaminant plume in northern France. The self-potential technique is a passive technique consisting in recording the electrical potential distribution at the surface of the Earth. A self-potential map is essentially the sum of two contributions, one associated with groundwater flow referred to as the electrokinetic component, and one associated with redox potential anomalies referred to as the electroredox component (thermoelectric and diffusion potentials are generally negligible). A groundwater flow model was first used to remove the electrokinetic component from the observed self-potential data. Then, a residual self-potential map was obtained. The source current density generating the residual self-potential signals is assumed to be associated with the position of the water table, an interface characterized by a change in both the electrical conductivity and the redox potential. The source current density was obtained through an inverse problem by minimizing a cost function including a data misfit contribution and a regularizer. This inversion algorithm allows the determination of the vertical and horizontal components of the source current density taking into account the electrical conductivity distribution of the saturated and non-saturated zones obtained independently by electrical resistivity tomography. The redox potential distribution was finally determined from the inverted residual source current density. A redox map was successfully built and the estimated redox potential values correlated well with in-situ measurements.

Parallel implementation of Hartree-Fock and density functional theory analytical second derivatives

NASA Astrophysics Data System (ADS)

Baker, Jon; Wolinski, Krzysztof; Malagoli, Massimo; Pulay, Peter

2004-01-01

We present an efficient, parallel implementation for the calculation of Hartree-Fock and density functional theory analytical Hessian (force constant, nuclear second derivative) matrices. These are important for the determination of harmonic vibrational frequencies, and to classify stationary points on potential energy surfaces. Our program is designed for modest parallelism (4-16 CPUs) as exemplified by our standard eight-processor QuantumCube™. We can routinely handle systems with up to 100+ atoms and 1000+ basis functions using under 0.5 GB of RAM memory per CPU. Timings are presented for several systems, ranging in size from aspirin (C9H8O4) to nickel octaethylporphyrin (C36H44N4Ni).

Phonon dispersion and local density of states in NiPd alloy using modified embedded atom method potential

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

Joshi, Subodh, E-mail: subodhssgk@gmail.com; Chand, Manesh, E-mail: maneshchand@gmail.com; Dabral, Krishna, E-mail: kmkrishna.dabral@gmail.com

2016-05-06

A modified embedded atom method (MEAM) potential model up to second neighbours has been used to calculate the phonon dispersions for Ni{sub 0.55}Pd{sub 0.45} alloy in which Pd is introduced as substitutional impurity. Using the force-constants obtained from MEAM potential, the local vibrational density of states in host Ni and substitutional Pd atoms using Green’s function method has been calculated. The calculation of phonon dispersions of NiPd alloy shows a good agreement with the experimental results. Condition of resonance mode has also been investigated and resonance mode in the frequency spectrum of impurity atom at low frequency is observed.

Sum rules for the uniform-background model of an atomic-sharp metal corner

NASA Astrophysics Data System (ADS)

Streitenberger, P.

1994-04-01

Analytical results are derived for the electrostatic potential of an atomic-sharp 90° metal corner in the uniform-background model. The electrostatic potential at a free jellium edge and the jellium corner, respectively, is determined exactly in terms of the energy per electron of the uniform electron gas integrated over the background density. The surface energy, the edge formation energy and the derivative of the corner formation energy with respect to the background density are given as integrals over the electrostatic potential. The present approach represents a novel approach to such sum rules, inclusive of the Budd-Vannimenus sum rules for a free jellium surface, based on general properties of linear response functions.

Periodicity in the autocorrelation function as a mechanism for regularly occurring zero crossings or extreme values of a Gaussian process.

PubMed

Wilson, Lorna R M; Hopcraft, Keith I

2017-12-01

The problem of zero crossings is of great historical prevalence and promises extensive application. The challenge is to establish precisely how the autocorrelation function or power spectrum of a one-dimensional continuous random process determines the density function of the intervals between the zero crossings of that process. This paper investigates the case where periodicities are incorporated into the autocorrelation function of a smooth process. Numerical simulations, and statistics about the number of crossings in a fixed interval, reveal that in this case the zero crossings segue between a random and deterministic point process depending on the relative time scales of the periodic and nonperiodic components of the autocorrelation function. By considering the Laplace transform of the density function, we show that incorporating correlation between successive intervals is essential to obtaining accurate results for the interval variance. The same method enables prediction of the density function tail in some regions, and we suggest approaches for extending this to cover all regions. In an ever-more complex world, the potential applications for this scale of regularity in a random process are far reaching and powerful.

Periodicity in the autocorrelation function as a mechanism for regularly occurring zero crossings or extreme values of a Gaussian process

NASA Astrophysics Data System (ADS)

Wilson, Lorna R. M.; Hopcraft, Keith I.

2017-12-01

The problem of zero crossings is of great historical prevalence and promises extensive application. The challenge is to establish precisely how the autocorrelation function or power spectrum of a one-dimensional continuous random process determines the density function of the intervals between the zero crossings of that process. This paper investigates the case where periodicities are incorporated into the autocorrelation function of a smooth process. Numerical simulations, and statistics about the number of crossings in a fixed interval, reveal that in this case the zero crossings segue between a random and deterministic point process depending on the relative time scales of the periodic and nonperiodic components of the autocorrelation function. By considering the Laplace transform of the density function, we show that incorporating correlation between successive intervals is essential to obtaining accurate results for the interval variance. The same method enables prediction of the density function tail in some regions, and we suggest approaches for extending this to cover all regions. In an ever-more complex world, the potential applications for this scale of regularity in a random process are far reaching and powerful.

DFT and TD-DFT calculations of metallotetraphenylporphyrin and metallotetraphenylporphyrin fullerene complexes as potential dye sensitizers for solar cells

NASA Astrophysics Data System (ADS)

El Mahdy, A. M.; Halim, Shimaa Abdel; Taha, H. O.

2018-05-01

Density functional theory (DFT) and time-dependent DFT calculations have been employed to model metallotetraphenylporphyrin dyes and metallotetraphenylporphyrin -fullerene complexes in order to investigate the geometries, electronic structures, the density of states, non-linear optical properties (NLO), IR-vis spectra, molecular electrostatic potential contours, and electrophilicity. To calculate the excited states of the tetraphenyl porphyrin analogs, time-dependent density functional theory (TD-DFT) are used. Their UV-vis spectra were also obtained and a comparison with available experimental and theoretical results is included. The results reveal that the metal and the tertiary butyl groups of the dyes are electron donors, and the tetraphenylporphyrin rings are electron acceptors. The HOMOs of the dyes fall within the (TiO2)60 and Ti38O76 band gaps and support the issue of typical interfacial electron transfer reaction. The resulting potential drop of Mn-TPP-C60 increased by ca. 3.50% under the effect of the tertiary butyl groups. The increase in the potential drop indicates that the tertiary butyl complexes could be a better choice for the strong operation of the molecular rectifiers. The introduction of metal atom and tertiary butyl groups to the tetraphenyl porphyrin moiety leads to a stronger response to the external electric field and induces higher photo-to-current conversion efficiency. This also shifts the absorption in the dyes and makes them potential candidates for harvesting light in the entire visible and near IR region for photovoltaic applications.

First-principle study of structural, electronic and magnetic properties of (FeC)n (n = 1-8) and (FeC)8TM (TM = V, Cr, Mn and Co) clusters.

PubMed

Li, Cheng-Gang; Zhang, Jie; Zhang, Wu-Qin; Tang, Ya-Nan; Ren, Bao-Zeng; Hu, Yan-Fei

2017-12-13

The structural, electronic and magnetic properties of the (FeC) n (n = 1-8) clusters are studied using the unbiased CALYPSO structure search method and density functional theory. A combination of the PBE functional and 6-311 + G* basis set is used for determining global minima on potential energy surfaces of (FeC) n clusters. Relatively stabilities are analyzed via computing their binding energies, second order difference and HOMO-LUMO gaps. In addition, the origin of magnetic properties, spin density and density of states are discussed in detail, respectively. At last, based on the same computational method, the structures, magnetic properties and density of states are systemically investigated for the 3d (V, Cr, Mn and Co) atom doped (FeC) 8 cluster.

Low-memory iterative density fitting.

PubMed

Grajciar, Lukáš

2015-07-30

A new low-memory modification of the density fitting approximation based on a combination of a continuous fast multipole method (CFMM) and a preconditioned conjugate gradient solver is presented. Iterative conjugate gradient solver uses preconditioners formed from blocks of the Coulomb metric matrix that decrease the number of iterations needed for convergence by up to one order of magnitude. The matrix-vector products needed within the iterative algorithm are calculated using CFMM, which evaluates them with the linear scaling memory requirements only. Compared with the standard density fitting implementation, up to 15-fold reduction of the memory requirements is achieved for the most efficient preconditioner at a cost of only 25% increase in computational time. The potential of the method is demonstrated by performing density functional theory calculations for zeolite fragment with 2592 atoms and 121,248 auxiliary basis functions on a single 12-core CPU workstation. © 2015 Wiley Periodicals, Inc.

Possible metabolic impact of Ramadan fasting in healthy men.

PubMed

Vardarli, Mustafa Cumhur; Hammes, Hans-Peter; Vardarli, İrfan

2014-01-01

Insulin sensitivity and β-cell function during Ramadan fasting in healthy male subjects have not been investigated so far. We assessed the changes of these and other metabolic parameters to judge the potential metabolic benefits of Ramadan fasting. Twenty-four healthy males of Turkish origin living in Germany, with normal glucose tolerance, participated in this study during Ramadan of 2009; 19 who completed fasting were analyzed. Blood was drawn at sunset after a period of fasting lasting approximately 15 h on days 0, 16, and 30 of Ramadan, as well as 7 and 28 days later. Insulin sensitivity (Homeostasis Model Assessment, HOMA), β-cell function, and other parameters were assessed. Ramadan fasting was associated with a significant reduction (-) or increment (+) for the following variables: insulin sensitivity (-20%; P = 0.04), β-cell function (+10%; P = 0.049), high-density lipoprotein cholesterol (-23%; P = 0.0003), low-density lipoprotein cholesterol (+14%; P = 0.007), nonesterified fatty acids (-62%; P < 0.0001), resistin (-20%; P = 0.01), adiponectin (+16%; P = 0.003), and glucagon (-21%; P = 0.01). C-peptide, insulin, leptin, triglyceride, and very low-density lipoprotein cholesterol concentrations were not significantly changed. Ramadan fasting is associated with transiently impaired insulin sensitivity, compensated for by an increased β-cell function. However, the pattern of insulin resistance-mediating adipocytokines suggests a potentially beneficial metabolic effect of Ramadan fasting.

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

The local work function: Concept and implications

NASA Astrophysics Data System (ADS)

Wandelt, K.

1997-02-01

The term 'local work function' is now widely applied. The present work discusses the common physical basis of 'photoemission of adsorbed xenon (PAX)' and 'two-photon photonemissionspectroscopy of image potential states' as local work function probes. New examples with bimetallic and defective surfaces are presented which demonstrate the capability of PAX measurements for the characterization of heterogeneous surfaces on an atomic scale. Finally, implications of the existence of short-range variations of the surface potential at surface steps are addressed. In particular, dynamical work function change measurements are a sensitive probe for the step-density at surfaces and, as such, a powerful in-situ method to monitor film growth.

Coupled structural, thermal, phase-change and electromagnetic analysis for superconductors, volume 2

NASA Technical Reports Server (NTRS)

Felippa, Carlos A.; Farhat, Charbel; Park, K. C.; Militello, Carmelo; Schuler, James J.

1993-01-01

Two families of parametrized mixed variational principles for linear electromagnetodynamics are constructed. The first family is applicable when the current density distribution is known a priori. Its six independent fields are magnetic intensity and flux density, magnetic potential, electric intensity and flux density and electric potential. Through appropriate specialization of parameters the first principle reduces to more conventional principles proposed in the literature. The second family is appropriate when the current density distribution and a conjugate Lagrange multiplier field are adjoined, giving a total of eight independently varied fields. In this case it is shown that a conventional variational principle exists only in the time-independent (static) case. Several static functionals with reduced number of varied fields are presented. The application of one of these principles to construct finite elements with current prediction capabilities is illustrated with a numerical example.

Coulomb Impurity Problem of Graphene in Strong Coupling Regime in Magnetic Fields.

PubMed

Kim, S C; Yang, S-R Eric

2015-10-01

We investigate the Coulomb impurity problem of graphene in strong coupling limit in the presence of magnetic fields. When the strength of the Coulomb potential is sufficiently strong the electron of the lowest energy boundstate of the n = 0 Landau level may fall to the center of the potential. To prevent this spurious effect the Coulomb potential must be regularized. The scaling function for the inverse probability density of this state at the center of the impurity potential is computed in the strong coupling regime. The dependence of the computed scaling function on the regularization parameter changes significantly as the strong coupling regime is approached.

Molecular design and property prediction of high density polynitro[3.3.3]-propellane-derivatized frameworks as potential high explosives.

PubMed

Zhang, Qinghua; Zhang, Jiaheng; Qi, Xiujuan; Shreeve, Jean'ne M

2014-11-13

Research in energetic materials is now heavily focused on the design and synthesis of novel insensitive high explosives (IHEs) for specialized applications. As an effective and time-saving tool for screening potential explosive structures, computer simulation has been widely used for the prediction of detonation properties of energetic molecules with relatively high precision. In this work, a series of new polynitrotetraoxopentaaza[3.3.3]-propellane molecules with tricyclic structures were designed. Their properties as potential high explosives including density, heats of formation, detonation properties, impact sensitivity, etc., have been extensively evaluated using volume-based thermodynamic calculations and density functional theory (DFT).These new energetic molecules exhibit high densities of >1.82 g cm(-3), in which 1 gives the highest density of 2.04 g cm(-3). Moreover, most new materials show good detonation properties and acceptable impact sensitivities, in which 5 displays much higher detonation velocity (9482 m s(-1)) and pressure (43.9 GPa) than HMX and has a h50 value of 11 cm. These results are expected to facilitate the experimental synthesis of new-generation nitramine-based high explosives.

Electronic Zero-Point Oscillations in the Strong-Interaction Limit of Density Functional Theory.

PubMed

Gori-Giorgi, Paola; Vignale, Giovanni; Seidl, Michael

2009-04-14

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron Hamiltonian, this same operator is multiplied by a real parameter λ varying between 0 (Kohn-Sham system) and 1 (physical system). In this process, usually called adiabatic connection, the one-electron density is kept fixed by a suitable local one-body potential. The strong-interaction limit of density functional theory, defined as the limit λ→∞, turns out to be like the opposite noninteracting Kohn-Sham limit (λ→0) mathematically simpler than the physical (λ = 1) case and can be used to build an approximate interpolation formula between λ→0 and λ→∞ for the exchange-correlation energy. Here we extend the systematic treatment of the λ→∞ limit [Phys. Rev. A 2007, 75, 042511] to the next leading term, describing zero-point oscillations of strictly correlated electrons, with numerical examples for small spherical atoms. We also propose an improved approximate functional for the zero-point term and a revised interpolation formula for the exchange-correlation energy satisfying more exact constraints.

Self-Consistent Optimization of Excited States within Density-Functional Tight-Binding.

PubMed

Kowalczyk, Tim; Le, Khoa; Irle, Stephan

2016-01-12

We present an implementation of energies and gradients for the ΔDFTB method, an analogue of Δ-self-consistent-field density functional theory (ΔSCF) within density-functional tight-binding, for the lowest singlet excited state of closed-shell molecules. Benchmarks of ΔDFTB excitation energies, optimized geometries, Stokes shifts, and vibrational frequencies reveal that ΔDFTB provides a qualitatively correct description of changes in molecular geometries and vibrational frequencies due to excited-state relaxation. The accuracy of ΔDFTB Stokes shifts is comparable to that of ΔSCF-DFT, and ΔDFTB performs similarly to ΔSCF with the PBE functional for vertical excitation energies of larger chromophores where the need for efficient excited-state methods is most urgent. We provide some justification for the use of an excited-state reference density in the DFTB expansion of the electronic energy and demonstrate that ΔDFTB preserves many of the properties of its parent ΔSCF approach. This implementation fills an important gap in the extended framework of DFTB, where access to excited states has been limited to the time-dependent linear-response approach, and affords access to rapid exploration of a valuable class of excited-state potential energy surfaces.

Methemoglobinemia hemotoxicity of some antimalarial 8-aminoquinoline analogues and their hydroxylated derivatives: density functional theory computation of ionization potentials

USDA-ARS?s Scientific Manuscript database

The administration of primaquine (PQ), an essential drug for treatment and radical cure of malaria, can lead to methemoglobin formation and life-threatening hemolysis for glucose-6-phosphate dehydrogenase deficient patients. The ionization potential (IP, a quantitative measure of the ability to lose...

Rapidly calculated density functional theory (DFT) relaxed Iso-potential Phi Si Maps: Beta-cellobiose

USDA-ARS?s Scientific Manuscript database

New cellobiose Phi-H/Si-H maps are rapidly generated using a mixed basis set DFT method, found to achieve a high level of confidence while reducing computer resources dramatically. Relaxed iso-potential maps are made for different conformational states of cellobiose, showing how glycosidic bond dihe...

Novel density functional methodology for the computation of accurate electronic and thermodynamic properties of molecular systems and improved long-range behavior

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

Kafafi, S.A.

1998-12-10

A novel general purpose density functional methodology for the computation of accurate electronic and thermodynamic properties of molecules and improved long-range behavior is reported. Assuming the separability of the exchange (E{sub x}) and correlation (E{sub c}) contributions to the total exchange-correlation energy functional (E{sub xc}), the E{sub x} term consists of a hybrid mixture of 37.5% Hartree-Fock exchange and the appropriate local spin density exchange using the adiabatic connection formula. He demonstrated that E{sub x} and its corresponding potential V{sub x} [=dE{sub x}/d{rho}(r)] have the proper asymptotic limits at r = 0 and r {r_arrow} {infinity}, E{sub c} consists ofmore » the Vosko, Wilk, and Nusair formula for the free-electron gas correlation energy and a generalized gradient approximation term with one adjustable parameter. V{sub c} [=dE{sub c}/d{rho}(r)] was shown to obey the r {r_arrow} {infinity} limit of the corresponding potential derived from exact atomic exchange-correlation computations; namely, V{sub c} is proportional to r{sup {minus}4}. Most importantly, he demonstrated that, at r values where dispersion forces are operating, V{sub c} is proportional to 1/r{sup n} (n = 4, 6, 8, {hor_ellipsis}). The reported method was denoted by K2-BVWN because it used two adjustable parameters in its formulation. The K2-BVWN scheme scales as N{sup 3}, where N is the number of basis functions, compared to {approximately}N{sup 7} for Gaussian-2 (G2) ab initio theory and related methods, {approximately}N{sup 5} for Barone`s mPW1,3PW, and {approximately}N{sup 4} for Becke`s three-parameter density functional approaches. The G2 data set complemented by the reported molecular systems investigated in this work was recommended as a critical test for evaluating novel ab initio and density functional methodologies. The K2-BVWN method has been implemented in the Gaussian series of programs.« less

Density-to-Potential Inversions to Guide Development of Exchange-Correlation Approximations at Finite Temperature

NASA Astrophysics Data System (ADS)

Jensen, Daniel; Wasserman, Adam; Baczewski, Andrew

The construction of approximations to the exchange-correlation potential for warm dense matter (WDM) is a topic of significant recent interest. In this work, we study the inverse problem of Kohn-Sham (KS) DFT as a means of guiding functional design at zero temperature and in WDM. Whereas the forward problem solves the KS equations to produce a density from a specified exchange-correlation potential, the inverse problem seeks to construct the exchange-correlation potential from specified densities. These two problems require different computational methods and convergence criteria despite sharing the same mathematical equations. We present two new inversion methods based on constrained variational and PDE-constrained optimization methods. We adapt these methods to finite temperature calculations to reveal the exchange-correlation potential's temperature dependence in WDM-relevant conditions. The different inversion methods presented are applied to both non-interacting and interacting model systems for comparison. 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 Security Administration under contract DE-AC04-94.

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Virial Coefficients for the Liquid Argon

NASA Astrophysics Data System (ADS)

Korth, Micheal; Kim, Saesun

2014-03-01

We begin with a geometric model of hard colliding spheres and calculate probability densities in an iterative sequence of calculations that lead to the pair correlation function. The model is based on a kinetic theory approach developed by Shinomoto, to which we added an interatomic potential for argon based on the model from Aziz. From values of the pair correlation function at various values of density, we were able to find viral coefficients of liquid argon. The low order coefficients are in good agreement with theoretical hard sphere coefficients, but appropriate data for argon to which these results might be compared is difficult to find.

Mean-field density functional theory of a nanoconfined classical, three-dimensional Heisenberg fluid. I. The role of molecular anchoring

NASA Astrophysics Data System (ADS)

Cattes, Stefanie M.; Gubbins, Keith E.; Schoen, Martin

2016-05-01

In this work, we employ classical density functional theory (DFT) to investigate for the first time equilibrium properties of a Heisenberg fluid confined to nanoscopic slit pores of variable width. Within DFT pair correlations are treated at modified mean-field level. We consider three types of walls: hard ones, where the fluid-wall potential becomes infinite upon molecular contact but vanishes otherwise, and hard walls with superimposed short-range attraction with and without explicit orientation dependence. To model the distance dependence of the attractions, we employ a Yukawa potential. The orientation dependence is realized through anchoring of molecules at the substrates, i.e., an energetic discrimination of specific molecular orientations. If the walls are hard or attractive without specific anchoring, the results are "quasi-bulk"-like in that they can be linked to a confinement-induced reduction of the bulk mean field. In these cases, the precise nature of the walls is completely irrelevant at coexistence. Only for specific anchoring nontrivial features arise, because then the fluid-wall interaction potential affects the orientation distribution function in a nontrivial way and thus appears explicitly in the Euler-Lagrange equations to be solved for minima of the grand potential of coexisting phases.

Empirical temperature-dependent intermolecular potentials determined by data mining from crystal data

NASA Astrophysics Data System (ADS)

Hofmann, D. W. M.; Kuleshova, L. N.

2018-05-01

Modern force fields are accurate enough to describe thermal effects in molecular crystals. Here, we have extended our earlier approach to discrete force fields for various temperatures to a force field with a continuous function. For the parametrisation of the force field, we used data mining on experimental structures with the temperature as an additional descriptor. The obtained force field can be used to minimise energy at a finite temperature and for molecular dynamics with zero-K potentials. The applicability of the method has been demonstrated for the prediction of crystal density, temperature density gradients and transition temperature.

Modeling solvation effects in real-space and real-time within density functional approaches

NASA Astrophysics Data System (ADS)

Delgado, Alain; Corni, Stefano; Pittalis, Stefano; Rozzi, Carlo Andrea

2015-10-01

The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the Octopus code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.

Modeling solvation effects in real-space and real-time within density functional approaches

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

Delgado, Alain; Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana; Corni, Stefano

2015-10-14

The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that aremore » close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.« less

Modified Holographic Ricci Dark Energy in Chameleon Brans-Dicke Cosmology and Its Thermodynamic Consequence

NASA Astrophysics Data System (ADS)

Jawad, A.; Chattopadhyay, S.; Bhattacharya, S.; Pasqua, A.

2015-04-01

The objective of this paper is to discuss the Chameleon Brans-Dicke gravity with non-minimally matter coupling of scalar field. We take modified Holographic Ricci dark energy model in this gravity with its energy density in interaction with energy density of cold dark matter. We assume power-law ansatz for scale factor and scalar field to discuss potential as well as coupling functions in the evolving universe. These reconstructed functions are plotted versus scalar field and time for different values of power component of scale factor n. We observe that potential and coupling functions represent increasing behavior, in particular, consistent results for a specific value of n. Finally, we have examined validity of the generalized second law of thermodynamics and we have observed its validity for all values of n. The financial Supported from Department of Science and Technology, Govt. of India under Project Grant No. SR/FTP/PS-167/2011 is thankfully acknowledged by SC

Efficient Adsorption Characteristics of Pristine and Silver-Doped Graphene Oxide Towards Contaminants: A Potential Membrane Material for Water Purification?

PubMed

Panigrahi, Puspamitra; Dhinakaran, Ashok Kumar; Sekar, Yuvaraj; Ahuja, Rajeev; Hussain, Tanveer

2018-05-16

In this work, we have investigated the potential of pristine and silver (Ag)-functionalized graphene oxide monolayers GO (GO-Ag) as efficient membranes for water filtration. Our first principles calculations based on density functional theory (DFT) reveal the hydrophilic nature of GO surfaces. The phonon frequency calculations within density functional perturbation theory (DFPT) confirmed the stability of GO sheets in aqueous media. Van der Waals-corrected binding energies of GO sheet towards heavy metals suggest that even pristine GO sheets are completely impermeable to various heavy metals like arsenic (As) and lead (Pb). However, compared to GO, the GO-Ag sheets have a much higher affinity towards the three amino acids histidine, phenyl-alanine and tyrosine, which are the main component of a bacteria cell wall. The GO-Ag sheet is found to be extremely efficient for bacteria inactivation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density functional theory calculations of continuum lowering in strongly coupled plasmas.

PubMed

Vinko, S M; Ciricosta, O; Wark, J S

2014-03-24

An accurate description of the ionization potential depression of ions in plasmas due to their interaction with the environment is a fundamental problem in plasma physics, playing a key role in determining the ionization balance, charge state distribution, opacity and plasma equation of state. Here we present a method to study the structure and position of the continuum of highly ionized dense plasmas using finite-temperature density functional theory in combination with excited-state projector augmented-wave potentials. The method is applied to aluminium plasmas created by intense X-ray irradiation, and shows excellent agreement with recently obtained experimental results. We find that the continuum lowering for ions in dense plasmas at intermediate temperatures is larger than predicted by standard plasma models and explain this effect through the electronic structure of the valence states in these strong-coupling conditions.

Space-Pseudo-Time Method: Application to the One-Dimensional Coulomb Potential and Density Funtional Theory

NASA Astrophysics Data System (ADS)

Weatherford, Charles; Gebremedhin, Daniel

2016-03-01

A new and efficient way of evolving a solution to an ordinary differential equation is presented. A finite element method is used where we expand in a convenient local basis set of functions that enforce both function and first derivative continuity across the boundaries of each element. We also implement an adaptive step size choice for each element that is based on a Taylor series expansion. The method is applied to solve for the eigenpairs of the one-dimensional soft-coulomb potential and the hard-coulomb limit is studied. The method is then used to calculate a numerical solution of the Kohn-Sham differential equation within the local density approximation is presented and is applied to the helium atom. Supported by the National Nuclear Security Agency, the Nuclear Regulatory Commission, and the Defense Threat Reduction Agency.

Average-atom model for two-temperature states and ionic transport properties of aluminum in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Hou, Yong; Fu, Yongsheng; Bredow, Richard; Kang, Dongdong; Redmer, Ronald; Yuan, Jianmin

2017-03-01

The average-atom model combined with the hyper-netted chain approximation is an efficient tool for electronic and ionic structure calculations for warm dense matter. Here we generalize this method in order to describe non-equilibrium states with different electron and ion temperature as produced in laser-matter interactions on ultra-short time scales. In particular, the electron-ion and ion-ion correlation effects are considered when calculating the electron structure. We derive an effective ion-ion pair-potential using the electron densities in the framework of temperature-depended density functional theory. Using this ion-ion potential we perform molecular dynamics simulations in order to determine the ionic transport properties such as the ionic diffusion coefficient and the shear viscosity through the ionic velocity autocorrelation functions.

Bone density and functional results after femoral revision with a cementless press-fit stem.

PubMed

Canovas, F; Roche, O; Girard, J; Bonnomet, F; Goldschild, M; Le Béguec, P

2015-05-01

The influence of radiographic bone density changes in the area surrounding a total hip arthroplasty (THA) revision with a cementless press-fit stem is unknown, notably in terms of functional results. We have therefore conducted a study aiming to (1) propose a radiographic method to assess bone density, (2) measure the functional effects of reduced bone density, and (3) determine the factors contributing to these modifications. A reduction in radiographic bone density has a negative influence on the functional result after revision using a cementless press-fit stem. We retrospectively assessed 150 THA revisions at a mean follow-up of 6.3 ± 3.2 years (range, 2-15 years). The clinical assessment was based on the Harris Hip Score. Bone density modifications were measured radiographically and the method was evaluated. The change in bone density was classified into two groups: (1) bone density not reduced or < 2 Gruen zones (118 cases [79%]); (2) bone density reduced ≥ 2 zones (32 cases [21%]). The variables showing a potential influence were the Cortical Index (CI), the type of primary stability with the press-fit system, and the femoral implant length. Inter- and intraobserver reliability of radiographic bone density measurement was evaluated as moderate or good (Kappa, 0.58; 0.60 and 0.67, respectively). For the Harris Hip Score at follow-up, there was a borderline statistical relation between stages 1 and 2: for the 118 stage 1 patients, this score was 83.62 ± 11.54 (range, 27-99) versus 78.34 ± 15.98 (range, 62-91) for stage 2 patients (P = 0.09). A CI ≤ 0.44 showed mediocre bone quality contributing to decreased bone density (P < 0.02). On the other hand, there was no statistically significant relation with the type of primary fixation (P = 0.34) or the length of the implant (P = 0.23). A cementless revision femoral stem can induce a reduction in bone density with possible functional effects. The negative role played by bone scarcity on the functional score is confirmed, and even though the difference is not statistically significant, we suggest using a short stem when this is possible. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Phase space explorations in time dependent density functional theory

NASA Astrophysics Data System (ADS)

Rajam, Aruna K.

Time dependent density functional theory (TDDFT) is one of the useful tools for the study of the dynamic behavior of correlated electronic systems under the influence of external potentials. The success of this formally exact theory practically relies on approximations for the exchange-correlation potential which is a complicated functional of the co-ordinate density, non-local in space and time. Adiabatic approximations (such as ALDA), which are local in time, are most commonly used in the increasing applications of the field. Going beyond ALDA, has been proved difficult leading to mathematical inconsistencies. We explore the regions where the theory faces challenges, and try to answer some of them via the insights from two electron model systems. In this thesis work we propose a phase-space extension of the TDDFT. We want to answer the challenges the theory is facing currently by exploring the one-body phase-space. We give a general introduction to this theory and its mathematical background in the first chapter. In second chapter, we carryout a detailed study of instantaneous phase-space densities and argue that the functionals of distributions can be a better alternative to the nonlocality issue of the exchange-correlation potentials. For this we study in detail the interacting and the non-interacting phase-space distributions for Hookes atom model. The applicability of ALDA-based TDDFT for the dynamics in strongfields can become severely problematic due to the failure of single-Slater determinant picture.. In the third chapter, we analyze how the phase-space distributions can shine some light into this problem. We do a comparative study of Kohn-Sham and interacting phase-space and momentum distributions for single ionization and double ionization systems. Using a simple model of two-electron systems, we have showed that the momentum distribution computed directly from the exact KS system contains spurious oscillations: a non-classical description of the essentially classical two-electron dynamics. In Time dependent density matrix functional theory (TDDMFT), the evolution scheme of the 1RDM (first order reduced density matrix) contains second-order reduced density matrix (2RDM), which has to be expressed in terms of 1RDMs. Any non-correlated approximations (Hartree-Fock) for 2RDM would fail to capture the natural occupations of the system. In our fourth chapter, we show that by applying the quasi-classical and semi-classical approximations one can capture the natural occupations of the excited systems. We study a time-dependent Moshinsky atom model for this. The fifth chapter contains a comparative work on the existing non-local exchange-correlation kernels that are based on current density response frame work and the co-moving frame work. We show that the two approaches though coinciding with each other in linear response regime, actually turn out to be different in non-linear regime.

Practical auxiliary basis implementation of Rung 3.5 functionals

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

Janesko, Benjamin G., E-mail: b.janesko@tcu.edu; Scalmani, Giovanni; Frisch, Michael J.

2014-07-21

Approximate exchange-correlation functionals for Kohn-Sham density functional theory often benefit from incorporating exact exchange. Exact exchange is constructed from the noninteracting reference system's nonlocal one-particle density matrix γ(r{sup -vector},r{sup -vector}′). Rung 3.5 functionals attempt to balance the strengths and limitations of exact exchange using a new ingredient, a projection of γ(r{sup -vector},r{sup -vector} ′) onto a semilocal model density matrix γ{sub SL}(ρ(r{sup -vector}),∇ρ(r{sup -vector}),r{sup -vector}−r{sup -vector} ′). γ{sub SL} depends on the electron density ρ(r{sup -vector}) at reference point r{sup -vector}, and is closely related to semilocal model exchange holes. We present a practical implementation of Rung 3.5 functionals, expandingmore » the r{sup -vector}−r{sup -vector} ′ dependence of γ{sub SL} in an auxiliary basis set. Energies and energy derivatives are obtained from 3D numerical integration as in standard semilocal functionals. We also present numerical tests of a range of properties, including molecular thermochemistry and kinetics, geometries and vibrational frequencies, and bandgaps and excitation energies. Rung 3.5 functionals typically provide accuracy intermediate between semilocal and hybrid approximations. Nonlocal potential contributions from γ{sub SL} yield interesting successes and failures for band structures and excitation energies. The results enable and motivate continued exploration of Rung 3.5 functional forms.« less

An improved interatomic potential for xenon in UO2: a combined density functional theory/genetic algorithm approach.

PubMed

Thompson, Alexander E; Meredig, Bryce; Wolverton, C

2014-03-12

We have created an improved xenon interatomic potential for use with existing UO2 potentials. This potential was fit to density functional theory calculations with the Hubbard U correction (DFT + U) using a genetic algorithm approach called iterative potential refinement (IPR). We examine the defect energetics of the IPR-fitted xenon interatomic potential as well as other, previously published xenon potentials. We compare these potentials to DFT + U derived energetics for a series of xenon defects in a variety of incorporation sites (large, intermediate, and small vacant sites). We find the existing xenon potentials overestimate the energy needed to add a xenon atom to a wide set of defect sites representing a range of incorporation sites, including failing to correctly rank the energetics of the small incorporation site defects (xenon in an interstitial and xenon in a uranium site neighboring uranium in an interstitial). These failures are due to problematic descriptions of Xe-O and/or Xe-U interactions of the previous xenon potentials. These failures are corrected by our newly created xenon potential: our IPR-generated potential gives good agreement with DFT + U calculations to which it was not fitted, such as xenon in an interstitial (small incorporation site) and xenon in a double Schottky defect cluster (large incorporation site). Finally, we note that IPR is very flexible and can be applied to a wide variety of potential forms and materials systems, including metals and EAM potentials.

Ion-mediated interactions in suspensions of oppositely charged nanoparticles

NASA Astrophysics Data System (ADS)

Dahirel, Vincent; Hansen, Jean Pierre

2009-08-01

The structure of oppositely charged spherical nanoparticles (polyions), dispersed in ionic solutions with continuous solvent (primitive model), is investigated by Monte Carlo (MC) simulations, within explicit and implicit microion representations, over a range of polyion valences and densities, and microion concentrations. Systems with explicit microions are explored by semigrand canonical MC simulations, and allow density-dependent effective polyion pair potentials vαβeff(r ) to be extracted from measured partial pair distribution functions. Implicit microion MC simulations are based on pair potentials of mean force vαβ(2)(r ) computed by explicit microion simulations of two charged polyions, in the low density limit. In the vicinity of the liquid-gas separation expected for oppositely charged polyions, the implicit microion representation leads to an instability against density fluctuations for polyion valences |Z| significantly below those at which the instability sets in within the exact explicit microion representation. Far from this instability region, the vαβ(2)(r ) are found to be fairly close to but consistently more repulsive than the effective pair potentials vαβeff(r ). This is corroborated by additional calculations of three-body forces between polyion triplets, which are repulsive when one polyion is of opposite charge to the other two. The explicit microion MC data were exploited to determine the ratio of salt concentrations c and co within the dispersion and the reservoir (Donnan effect). c /co is found to first increase before finally decreasing as a function of the polyion packing fraction.

A Gaussian theory for fluctuations in simple liquids.

PubMed

Krüger, Matthias; Dean, David S

2017-04-07

Assuming an effective quadratic Hamiltonian, we derive an approximate, linear stochastic equation of motion for the density-fluctuations in liquids, composed of overdamped Brownian particles. From this approach, time dependent two point correlation functions (such as the intermediate scattering function) are derived. We show that this correlation function is exact at short times, for any interaction and, in particular, for arbitrary external potentials so that it applies to confined systems. Furthermore, we discuss the relation of this approach to previous ones, such as dynamical density functional theory as well as the formally exact treatment. This approach, inspired by the well known Landau-Ginzburg Hamiltonians, and the corresponding "Model B" equation of motion, may be seen as its microscopic version, containing information about the details on the particle level.

A Gaussian theory for fluctuations in simple liquids

NASA Astrophysics Data System (ADS)

Krüger, Matthias; Dean, David S.

2017-04-01

Assuming an effective quadratic Hamiltonian, we derive an approximate, linear stochastic equation of motion for the density-fluctuations in liquids, composed of overdamped Brownian particles. From this approach, time dependent two point correlation functions (such as the intermediate scattering function) are derived. We show that this correlation function is exact at short times, for any interaction and, in particular, for arbitrary external potentials so that it applies to confined systems. Furthermore, we discuss the relation of this approach to previous ones, such as dynamical density functional theory as well as the formally exact treatment. This approach, inspired by the well known Landau-Ginzburg Hamiltonians, and the corresponding "Model B" equation of motion, may be seen as its microscopic version, containing information about the details on the particle level.

Tigers and their prey: Predicting carnivore densities from prey abundance

USGS Publications Warehouse

Karanth, K.U.; Nichols, J.D.; Kumar, N.S.; Link, W.A.; Hines, J.E.

2004-01-01

The goal of ecology is to understand interactions that determine the distribution and abundance of organisms. In principle, ecologists should be able to identify a small number of limiting resources for a species of interest, estimate densities of these resources at different locations across the landscape, and then use these estimates to predict the density of the focal species at these locations. In practice, however, development of functional relationships between abundances of species and their resources has proven extremely difficult, and examples of such predictive ability are very rare. Ecological studies of prey requirements of tigers Panthera tigris led us to develop a simple mechanistic model for predicting tiger density as a function of prey density. We tested our model using data from a landscape-scale long-term (1995-2003) field study that estimated tiger and prey densities in 11 ecologically diverse sites across India. We used field techniques and analytical methods that specifically addressed sampling and detectability, two issues that frequently present problems in macroecological studies of animal populations. Estimated densities of ungulate prey ranged between 5.3 and 63.8 animals per km2. Estimated tiger densities (3.2-16.8 tigers per 100 km2) were reasonably consistent with model predictions. The results provide evidence of a functional relationship between abundances of large carnivores and their prey under a wide range of ecological conditions. In addition to generating important insights into carnivore ecology and conservation, the study provides a potentially useful model for the rigorous conduct of macroecological science.

Elimination of Spurious Fractional Charges in Dissociating Molecules by Correcting the Shape of Approximate Kohn-Sham Potentials.

PubMed

Komsa, Darya N; Staroverov, Viktor N

2016-11-08

Standard density-functional approximations often incorrectly predict that heteronuclear diatomic molecules dissociate into fractionally charged atoms. We demonstrate that these spurious charges can be eliminated by adapting the shape-correction method for Kohn-Sham potentials that was originally introduced to improve Rydberg excitation energies [ Phys. Rev. Lett. 2012 , 108 , 253005 ]. Specifically, we show that if a suitably determined fraction of electron charge is added to or removed from a frontier Kohn-Sham orbital level, the approximate Kohn-Sham potential of a stretched molecule self-corrects by developing a semblance of step structure; if this potential is used to obtain the electron density of the neutral molecule, charge delocalization is blocked and spurious fractional charges disappear beyond a certain internuclear distance.

Vapor-liquid phase equilibria of water modelled by a Kim-Gordon potential

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

Maerzke, Katie A.; McGrath, M. J.; Kuo, I-F W.

2009-09-07

Gibbs ensemble Monte Carlo simulations were carried out to investigate the properties of a frozen-electron-density (or Kim-Gordon, KG) model of water along the vapor-liquid coexistence curve. Because of its theoretical basis, such a KG model provides for seamless coupling to Kohn-Sham density functional theory for use in mixed quantum mechanics/molecular mechanics (QM/MM) implementations. The Gibbs ensemble simulations indicate rather limited transferability of such a simple KG model to other state points. Specifically, a KG model that was parameterized by Barker and Sprik to the properties of liquid water at 300 K, yields saturated vapor pressures and a critical temperature thatmore » are significantly under- and overestimated, respectively. We present a comprehensive density functional theory study to asses the accuracy of two popular exchange correlation functionals on the structure and density of liquid water at ambient conditions This work was supported by the US Department of Energy Office of Basic Energy Science Chemical Sciences Program. Battelle operates Pacific Northwest National Laboratory for the US Department of Energy.« less

Method to study complex systems of mesons in lattice QCD

DOE PAGES

Detmold, William; Savage, Martin J.

2010-07-30

Correlation functions involving many hadrons allow finite density systems to be explored with Lattice QCD. Recently, systems with up to 12more » $$\\pi^+$$'s or $K^+$'s have been studied to determine the the $3$-$$\\pi^+$$ and $3$-$K^+$ interactions and the corresponding chemical potential has been determined as a function of density in each case. We derive recursion relations between correlation functions that allow us to extend this work to systems of arbitrary numbers of mesons and to systems containing arbitrary different types of mesons such as $$\\pi^+$$'s, $K^+$'s, $D^0$'s and $B^+$'s. These relations allow for the study of finite-density systems in arbitrary volumes, and the study of high-density systems. Systems comprised of up to N=12 m mesons can be explored with Lattice QCD calculations utilizing $m$ different sources for the quark propagators. As the recursion relations require only a small, N-independent, number of operations to derive the N+1 meson contractions from the N meson contractions, they are compuationally feasible.« less

Use of the interior cavity of the P22 capsid for site-specific initiation of atom-transfer radical polymerization with high-density cargo loading

NASA Astrophysics Data System (ADS)

Lucon, Janice; Qazi, Shefah; Uchida, Masaki; Bedwell, Gregory J.; Lafrance, Ben; Prevelige, Peter E.; Douglas, Trevor

2012-10-01

Virus-like particles (VLPs) have emerged as important and versatile architectures for chemical manipulation in the development of functional hybrid nanostructures. Here we demonstrate a successful site-selective initiation of atom-transfer radical polymerization reactions to form an addressable polymer constrained within the interior cavity of a VLP. Potentially, this protein-polymer hybrid of P22 and cross-linked poly(2-aminoethyl methacrylate) could be useful as a new high-density delivery vehicle for the encapsulation and delivery of small-molecule cargos. In particular, the encapsulated polymer can act as a scaffold for the attachment of small functional molecules, such as fluorescein dye or the magnetic resonance imaging (MRI) contrast agent Gd-diethylenetriaminepentacetate, through reactions with its pendant primary amine groups. Using this approach, a significant increase in the labelling density of the VLP, compared to that of previous modifications of VLPs, can be achieved. These results highlight the use of multimeric protein-polymer conjugates for their potential utility in the development of VLP-based MRI contrast agents with the possibility of loading other cargos.

Maximizing the potential of cropping systems for nematode management.

PubMed

Noe, J P; Sasser, J N; Imbriani, J L

1991-07-01

Quantitative techniques were used to analyze and determine optimal potential profitability of 3-year rotations of cotton, Gossypium hirsutum cv. Coker 315, and soybean, Glycine max cv. Centennial, with increasing population densities of Hoplolaimus columbus. Data collected from naturally infested on-farm research plots were combined with economic information to construct a microcomputer spreadsheet analysis of the cropping system. Nonlinear mathematical functions were fitted to field data to represent damage functions and population dynamic curves. Maximum yield losses due to H. columbus were estimated to be 20% on cotton and 42% on soybean. Maximum at-harvest population densities were calculated to be 182/100 cm(3) soil for cotton and 149/100 cm(3) soil for soybean. Projected net incomes ranged from a $17.74/ha net loss for the soybean-cotton-soybean sequence to a net profit of $46.80/ha for the cotton-soybean-cotton sequence. The relative profitability of various rotations changed as nematode densities increased, indicating economic thresholds for recommending alternative crop sequences. The utility and power of quantitative optimization was demonstrated for comparisons of rotations under different economic assumptions and with other management alternatives.

DNA Nucleotides Detection via capacitance properties of Graphene

NASA Astrophysics Data System (ADS)

Khadempar, Nahid; Berahman, Masoud; Yazdanpanah, Arash

2016-05-01

In the present paper a new method is suggested to detect the DNA nucleotides on a first-principles calculation of the electronic features of DNA bases which chemisorbed to a graphene sheet placed between two gold electrodes in a contact-channel-contact system. The capacitance properties of graphene in the channel are surveyed using non-equilibrium Green's function coupled with the Density Functional Theory. Thus, the capacitance properties of graphene are theoretically investigated in a biological environment, and, using a novel method, the effect of the chemisorbed DNA nucleotides on electrical charges on the surface of graphene is deciphered. Several parameters in this method are also extracted including Electrostatic energy, Induced density, induced electrostatic potential, Electron difference potential and Electron difference density. The qualitative and quantitative differences among these parameters can be used to identify DNA nucleotides. Some of the advantages of this approach include its ease and high accuracy. What distinguishes the current research is that it is the first experiment to investigate the capacitance properties of gaphene changes in the biological environment and the effect of chemisorbed DNA nucleotides on the surface of graphene on the charge.

Coordination between leaf and stem traits related to leaf carbon gain and hydraulics across 32 drought-tolerant angiosperms.

PubMed

Ishida, Atsushi; Nakano, Takashi; Yazaki, Kenichi; Matsuki, Sawako; Koike, Nobuya; Lauenstein, Diego L; Shimizu, Michiru; Yamashita, Naoko

2008-05-01

We examined 15 traits in leaves and stems related to leaf C economy and water use for 32 co-existing angiosperms at ridge sites with shallow soil in the Bonin Islands. Across species, stem density was positively correlated to leaf mass per area (LMA), leaf lifespan (LLS), and total phenolics and condensed tannins per unit leaf N (N-based), and negatively correlated to leaf osmotic potential and saturated water content in leaves. LMA and LLS were negatively correlated to photosynthetic parameters, such as area-, mass-, and N-based assimilation rates. Although stem density and leaf osmotic potential were not associated with photosynthetic parameters, they were associated with some parameters of the leaf C economy, such as LMA and LLS. In the principal component (PCA) analysis, the first three axes accounted for 74.4% of total variation. Axis 1, which explained 41.8% of the total variation, was well associated with parameters for leaf C and N economy. Similarly, axis 2, which explained 22.3% of the total variation, was associated with parameters for water use. Axis 3, which explained 10.3% of the total variation, was associated with chemical defense within leaves. Axes 1 and 2 separated functional types relatively well, i.e., creeping trees, ruderal trees, other woody plants, C(3) shrubs and forbs, palms, and CAM plants, indicating that plant functional types were characterized by similar attributes of traits related to leaf C and N economy and water use. In addition, when the plot was extended by two unrelated traits, leaf mass-based assimilation rates and stem density, it also separated these functional types. These data indicate that differences in the functional types with contrasting plant strategies can be attributed to functional integration among leaf C economy, hydraulics, and leaf longevity, and that both leaf mass-based assimilation rates and stem density are key factors reflecting the different functions of plant species.

Spin-density functional theory treatment of He+-He collisions

NASA Astrophysics Data System (ADS)

Baxter, Matthew; Kirchner, Tom; Engel, Eberhard

2016-09-01

The He+-He collision system presents an interesting challenge to theory. On one hand, a full treatment of the three-electron dynamics constitutes a massive computational problem that has not been attempted yet; on the other hand, simplified independent-particle-model based descriptions may only provide partial information on either the transitions of the initial target electrons or on the transitions of the projectile electron, depending on the choice of atomic model potentials. We address the He+-He system within the spin-density functional theory framework on the exchange-only level. The Krieger-Li-Iafrate (KLI) approximation is used to calculate the exchange potentials for the spin-up and spin-down electrons, which ensures the correct asymptotic behavior of the effective (Kohn-Sham) potential consisting of exchange, Hartree and nuclear Coulomb potentials. The orbitals are propagated with the two-center basis generator method. In each time step, simplified versions of them are fed into the KLI equations to calculate the Kohn-Sham potential, which, in turn, is used to generate the orbitals in the next time step. First results for the transitions of all electrons and the resulting charge-changing total cross sections will be presented at the conference. Work supported by NSERC, Canada.

Kapton charging characteristics: Effects of material thickness and electron-energy distribution

NASA Technical Reports Server (NTRS)

Williamson, W. S.; Dulgeroff, C. R.; Hymann, J.; Viswanathan, R.

1985-01-01

Charging characteristics of polyimide (Kapton) of varying thicknesses under irradiation by a very-low-curent-density electron beam, with the back surface of the sample grounded are reported. These charging characteristics are in good agreement with a simple analytical model which predicts that in thin samples at low current density, sample surface potential is limited by conduction leakage through the bulk material. The charging of Kapton in a low-current-density electron beam in which the beam energy was modulated to simulate Maxwellian and biMaxwellian distribution functions is measured.

Time dependent-density functional theory (TD-DFT) and experimental studies of UV-Visible spectra and cyclic voltammetry for Cu(II) complex with Et2DTC

NASA Astrophysics Data System (ADS)

Valle, Eliana Maira A.; Maltarollo, Vinicius Gonçalves; Almeida, Michell O.; Honorio, Kathia Maria; dos Santos, Mauro Coelho; Cerchiaro, Giselle

2018-04-01

In this work, we studied the complexation mode between copper(II) ion and the specific ligand investigated as carriers of metals though biological membranes, diethyldithiocarbamate (Et2DTC). It is important to understand how this occurs because it is an important intracellular chelator with potential therapeutic applications. Theoretical and experimental UV visible studies were performed to investigate the complexation mode between copper and the ligand. Electrochemical studies were also performed to complement the spectroscopic analyses. According to the theoretical calculations, using TD-DFT (Time dependent density functional theory), with B3LYP functional and DGDVZP basis set, implemented in Gaussian 03 package, it was observed that the formation of the complex [Cu(Et2DTC)2] is favorable with higher electron density over the sulfur atoms of the ligand. UV/Vis spectra have a charge transfer band at 450 nm, with the DMSO-d6 band shift from 800 to 650 nm. The electrochemical experiments showed the formation of a new redox process, referring to the complex, where the reduction peak potential of copper is displaced to less positive region. Therefore, the results obtained from this study give important insights on possible mechanisms involved in several biological processes related to the studied system.

Wide electrochemical window of supercapacitors from coffee bean-derived phosphorus-rich carbons.

PubMed

Huang, Congcong; Sun, Ting; Hulicova-Jurcakova, Denisa

2013-12-01

Phosphorus-rich carbons (PCs) were prepared by phosphoric acid activation of waste coffee grounds in different impregnation ratios. PCs were characterized by nitrogen and carbon dioxide adsorption and X-ray photoelectron spectroscopy. The results indicate that the activation step not only creates a porous structure, but also introduces various phosphorus and oxygen functional groups to the surface of carbons. As evidenced by cyclic voltammetry, galvanostatic charge/discharge, and wide potential window tests, a supercapacitor constructed from PC-2 (impregnation ratio of 2), with the highest phosphorus content, can operate very stably in 1 M H2 SO4 at 1.5 V with only 18 % degradation after 10 000 cycles at a current density of 5 A g(-1) . Due to the wide electrochemical window, a supercapacitor assembled with PC-2 has a high energy density of 15 Wh kg(-1) at a power density of 75 W kg(-1) . The possibility of widening the potential window above the theoretical potential for the decomposition of water is attributed to reversible electrochemical hydrogen storage in narrow micropores and the positive effect of phosphorus-rich functional groups, particularly the polyphosphates on the carbon surface. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triphenylamine based organic dyes for dye sensitized solar cells: A theoretical approach

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

Mohankumar, V.; Pandian, Muthu Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

The geometry, electronic structure and absorption spectra for newly designed triphenylamine based organic dyes were investigated by density functional theory (DFT) and time dependent density functional theory (TD-DFT) with the Becke 3-Parameter-Lee-Yang-parr(B3LYP) functional, where the 6-31G(d,p) basis set was employed. All calculations were performed using the Gaussian 09 software package. The calculated HOMO and LUMO energies show that charge transfer occurs in the molecule. Ultraviolet–visible (UV–vis) spectrum was simulated by TD-DFT in gas phase. The calculation shows that all of the dyes can potentially be good sensitizers for DSSC. The LUMOs are just above the conduction band of TiO{sub 2}more » and their HOMOs are under the reduction potential energy of the electrolytes (I{sup −}/I{sub 3}{sup −}) which can facilitate electron transfer from the excited dye to TiO{sub 2} and charge regeneration process after photo oxidation respectively. The simulated absorption spectrum of dyes match with solar spectrum. Frontier molecular orbital results show that among all the three dyes, the “dye 3” can be used as potential sensitizer for DSSC.« less

Is the time course of lexical activation and competition in spoken word recognition affected by adult aging? An event-related potential (ERP) study.

PubMed

Hunter, Cynthia R

2016-10-01

Adult aging is associated with decreased accuracy for recognizing speech, particularly in noisy backgrounds and for high neighborhood density words, which sound similar to many other words. In the current study, the time course of neighborhood density effects in young and older adults was compared using event-related potentials (ERP) and behavioral responses in a lexical decision task for spoken words and nonwords presented either in quiet or in noise. Target items sounded similar either to many or to few other words (neighborhood density) but were balanced for the frequency of their component sounds (phonotactic probability). Behavioral effects of density were similar across age groups, but the event-related potential effects of density differed as a function of age group. For young adults, density modulated the amplitude of both the N400 and the later P300 or late positive complex (LPC). For older adults, density modulated only the amplitude of the P300/LPC. Thus, spreading activation to the semantics of lexical neighbors, indexed by the N400 density effect, appears to be reduced or delayed in adult aging. In contrast, effects of density on P300/LPC amplitude were present in both age groups, perhaps reflecting attentional allocation to items that resemble few words in the mental lexicon. The results constitute the first evidence that ERP effects of neighborhood density are affected by adult aging. The age difference may reflect either a unitary density effect that is delayed by approximately 150ms in older adults, or multiple processes that are differentially affected by aging. Copyright © 2016 Elsevier Ltd. All rights reserved.

Probability density function formalism for optical coherence tomography signal analysis: a controlled phantom study.

PubMed

Weatherbee, Andrew; Sugita, Mitsuro; Bizheva, Kostadinka; Popov, Ivan; Vitkin, Alex

2016-06-15

The distribution of backscattered intensities as described by the probability density function (PDF) of tissue-scattered light contains information that may be useful for tissue assessment and diagnosis, including characterization of its pathology. In this Letter, we examine the PDF description of the light scattering statistics in a well characterized tissue-like particulate medium using optical coherence tomography (OCT). It is shown that for low scatterer density, the governing statistics depart considerably from a Gaussian description and follow the K distribution for both OCT amplitude and intensity. The PDF formalism is shown to be independent of the scatterer flow conditions; this is expected from theory, and suggests robustness and motion independence of the OCT amplitude (and OCT intensity) PDF metrics in the context of potential biomedical applications.

Study of half-metallicity in BiMnxFe1-xO3

NASA Astrophysics Data System (ADS)

Ameer, Shaan; Jindal, Kajal; Tomar, Monika; Jha, Pradip K.; Gupta, Vinay

2018-05-01

Spin polarized calculations are performed to study the structural and electronic properties of Mn doped BiFeO3 (BMFO) using simplified local spin density approximation (LSDA) functional under density functional theory (DFT). The B-site doping concentration of Mn in BMFO considered to be 16.7 % (BiMn0.167Fe0.833O3). Density of states calculations are carried out for both ferromagnetic (FM) and anti-ferromagnetic (AFM) order in BMFO. The results predict that BMFO is a half metal for both FM and AFM BMFO with magnetization of 29.0000 µB/cell and 1.0000 µB/cell respectively. The ground state of BMFO is found to be antiferromagnetic and demonstrates BMFO to be a potential candidate for spintronic applications.

Anisotropy-driven transition from the Moore-Read state to quantum Hall stripes

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Sodemann, Inti; Sheng, D. N.; Fu, Liang

2017-05-01

We investigate the nature of the quantum Hall liquid in a half-filled second Landau level (n =1 ) as a function of band mass anisotropy using numerical exact diagonalization and density matrix renormalization group methods. We find increasing the mass anisotropy induces a quantum phase transition from the Moore-Read state to a charge density wave state. By analyzing the energy spectrum, guiding center structure factors, and by adding weak pinning potentials, we show that this charge density wave is a unidirectional quantum Hall stripe, which has a periodicity of a few magnetic lengths and survives in the thermodynamic limit. We find smooth profiles for the guiding center occupation function that reveal the strong coupling nature of the array of chiral Luttinger liquids residing at the stripe edges.

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.

Geographical Distribution of Biomass Carbon in Tropical Southeast Asian Forests: A Database (NPD-068)

DOE Data Explorer

Brown, Sandra [University of Illinois, Urbana, Illinois (USA); Iverson, Louis R. [University of Illinois, Urbana, Illinois (USA); Prasad, Anantha [University of Illinois, Urbana, Illinois (USA); Beaty, Tammy W. [CDIAC, Oak Ridge National Laboratory, Oak Ridge, TN (USA); Olsen, Lisa M. [CDIAC, Oak Ridge National Laboratory, Oak Ridge, TN (USA); Cushman, Robert M. [CDIAC, Oak Ridge National Laboratory, Oak Ridge, TN (USA); Brenkert, Antoinette L. [CDIAC, Oak Ridge National Laboratory, Oak Ridge, TN (USA)

2001-03-01

A database was generated of estimates of geographically referenced carbon densities of forest vegetation in tropical Southeast Asia for 1980. A geographic information system (GIS) was used to incorporate spatial databases of climatic, edaphic, and geomorphological indices and vegetation to estimate potential (i.e., in the absence of human intervention and natural disturbance) carbon densities of forests. The resulting map was then modified to estimate actual 1980 carbon density as a function of population density and climatic zone. The database covers the following 13 countries: Bangladesh, Brunei, Cambodia (Campuchea), India, Indonesia, Laos, Malaysia, Myanmar (Burma), Nepal, the Philippines, Sri Lanka, Thailand, and Vietnam.

Current induced perpendicular-magnetic-anisotropy racetrack memory with magnetic field assistance

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

Zhang, Y.; Klein, J.-O.; Chappert, C.

2014-01-20

High current density is indispensable to shift domain walls (DWs) in magnetic nanowires, which limits the using of racetrack memory (RM) for low power and high density purposes. In this paper, we present perpendicular-magnetic-anisotropy (PMA) Co/Ni RM with global magnetic field assistance, which lowers the current density for DW motion. By using a compact model of PMA RM and 40 nm design kit, we perform mixed simulation to validate the functionality of this structure and analyze its density potential. Stochastic DW motion behavior has been taken into account and statistical Monte-Carlo simulations are carried out to evaluate its reliability performance.

Asymptotic behavior of exact exchange potential of slabs

NASA Astrophysics Data System (ADS)

Engel, E.

2014-06-01

In this contribution the exact exchange potential vx of density functional theory is examined for slabs such as graphene, for which one has a Bravais lattice in the x-y directions, while the electrons are confined to the finite region -L≤z≤L in the z direction. It is demonstrated analytically that the exact vx behaves as -e2/z for z ≫L. This result extends the corresponding statement of Horowitz, Proetto, and Rigamonti [Phys. Rev. Lett. 97, 026802 (2006), 10.1103/PhysRevLett.97.026802] for jellium slabs to slabs with arbitrary periodic density distributions. Application of the exact exchange to a Si(111) slab (within the Krieger-Li-Iafrate approximation) indicates that the corrugation of the exact vx is more pronounced than that of the local density approximation for vx.

Approaching the basis set limit for DFT calculations using an environment-adapted minimal basis with perturbation theory: Formulation, proof of concept, and a pilot implementation

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

Mao, Yuezhi; Horn, Paul R.; Mardirossian, Narbe

2016-07-28

Recently developed density functionals have good accuracy for both thermochemistry (TC) and non-covalent interactions (NC) if very large atomic orbital basis sets are used. To approach the basis set limit with potentially lower computational cost, a new self-consistent field (SCF) scheme is presented that employs minimal adaptive basis (MAB) functions. The MAB functions are optimized on each atomic site by minimizing a surrogate function. High accuracy is obtained by applying a perturbative correction (PC) to the MAB calculation, similar to dual basis approaches. Compared to exact SCF results, using this MAB-SCF (PC) approach with the same large target basis set producesmore » <0.15 kcal/mol root-mean-square deviations for most of the tested TC datasets, and <0.1 kcal/mol for most of the NC datasets. The performance of density functionals near the basis set limit can be even better reproduced. With further improvement to its implementation, MAB-SCF (PC) is a promising lower-cost substitute for conventional large-basis calculations as a method to approach the basis set limit of modern density functionals.« less

Numerical Optimization of Density Functional Tight Binding Models: Application to Molecules Containing Carbon, Hydrogen, Nitrogen, and Oxygen

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

Krishnapriyan, A.; Yang, P.; Niklasson, A. M. N.

New parametrizations for semiempirical density functional tight binding (DFTB) theory have been developed by the numerical optimization of adjustable parameters to minimize errors in the atomization energy and interatomic forces with respect to ab initio calculated data. Initial guesses for the radial dependences of the Slater- Koster bond integrals and overlap integrals were obtained from minimum basis density functional theory calculations. The radial dependences of the pair potentials and the bond and overlap integrals were represented by simple analytic functions. The adjustable parameters in these functions were optimized by simulated annealing and steepest descent algorithms to minimize the value ofmore » an objective function that quantifies the error between the DFTB model and ab initio calculated data. The accuracy and transferability of the resulting DFTB models for the C, H, N, and O system were assessed by comparing the predicted atomization energies and equilibrium molecular geometries of small molecules that were not included in the training data from DFTB to ab initio data. The DFTB models provide accurate predictions of the properties of hydrocarbons and more complex molecules containing C, H, N, and O.« less

Numerical Optimization of Density Functional Tight Binding Models: Application to Molecules Containing Carbon, Hydrogen, Nitrogen, and Oxygen

DOE PAGES

Krishnapriyan, A.; Yang, P.; Niklasson, A. M. N.; ...

2017-10-17

New parametrizations for semiempirical density functional tight binding (DFTB) theory have been developed by the numerical optimization of adjustable parameters to minimize errors in the atomization energy and interatomic forces with respect to ab initio calculated data. Initial guesses for the radial dependences of the Slater- Koster bond integrals and overlap integrals were obtained from minimum basis density functional theory calculations. The radial dependences of the pair potentials and the bond and overlap integrals were represented by simple analytic functions. The adjustable parameters in these functions were optimized by simulated annealing and steepest descent algorithms to minimize the value ofmore » an objective function that quantifies the error between the DFTB model and ab initio calculated data. The accuracy and transferability of the resulting DFTB models for the C, H, N, and O system were assessed by comparing the predicted atomization energies and equilibrium molecular geometries of small molecules that were not included in the training data from DFTB to ab initio data. The DFTB models provide accurate predictions of the properties of hydrocarbons and more complex molecules containing C, H, N, and O.« less

Communication: xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS

NASA Astrophysics Data System (ADS)

Hait, Diptarka; Head-Gordon, Martin

2018-05-01

Double hybrid (DH) density functionals are amongst the most accurate density functional approximations developed so far, largely due to the incorporation of correlation effects from unoccupied orbitals via second order perturbation theory (PT2). The xDH family of DH functionals calculate energy directly from orbitals optimized by a lower level approach like B3LYP, without self-consistent optimization. XYG3 and XYGJ-OS are two widely used xDH functionals that are known to be quite accurate at equilibrium geometries. Here, we show that the XYG3 and XYGJ-OS functionals can be ill behaved for stretched bonds well beyond the Coulson-Fischer point, predicting unphysical dipole moments and humps in potential energy curves for some simple systems like the hydrogen fluoride molecule. Numerical experiments and analysis show that these failures are not due to PT2. Instead, a large mismatch at stretched bond-lengths between the reference B3LYP orbitals and the optimized orbitals associated with the non-PT2 part of XYG3 leads to an unphysically large non-Hellman-Feynman contribution to first order properties like forces and electron densities.

Characterizing water-metal interfaces and machine learning potential energy surfaces

NASA Astrophysics Data System (ADS)

Ryczko, Kevin

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

Time-dependent i-DFT exchange-correlation potentials with memory: applications to the out-of-equilibrium Anderson model

NASA Astrophysics Data System (ADS)

Kurth, Stefan; Stefanucci, Gianluca

2018-06-01

We have recently put forward a steady-state density functional theory (i-DFT) to calculate the transport coefficients of quantum junctions. Within i-DFT it is possible to obtain the steady density on and the steady current through an interacting junction using a fictitious noninteracting junction subject to an effective gate and bias potential. In this work we extend i-DFT to the time domain for the single-impurity Anderson model. By a reverse engineering procedure we extract the exchange-correlation (xc) potential and xc bias at temperatures above the Kondo temperature T K. The derivation is based on a generalization of a recent paper by Dittmann et al. [N. Dittmann et al., Phys. Rev. Lett. 120, 157701 (2018)]. Interestingly the time-dependent (TD) i-DFT potentials depend on the system's history only through the first time-derivative of the density. We perform numerical simulations of the early transient current and investigate the role of the history dependence. We also empirically extend the history-dependent TD i-DFT potentials to temperatures below T K. For this purpose we use a recently proposed parametrization of the i-DFT potentials which yields highly accurate results in the steady state.

Electronic structure of LiCoO2 thin films: A combined photoemission spectroscopy and density functional theory study

NASA Astrophysics Data System (ADS)

Ensling, David; Thissen, Andreas; Laubach, Stefan; Schmidt, Peter C.; Jaegermann, Wolfram

2010-11-01

The electronic properties of LiCoO2 have been studied by theoretical band-structure calculations (using density functional theory) and experimental methods (photoemission). Synchrotron-induced photoelectron spectroscopy, resonant photoemission spectroscopy (ResPES), and soft x-ray absorption (XAS) have been applied to investigate the electronic structure of both occupied and unoccupied states. High-quality PES spectra were obtained from stoichiometric and highly crystalline LiCoO2 thin films deposited “in situ” by rf magnetron sputtering. An experimental approach of separating oxygen- and cobalt-derived (final) states by ResPES in the valence-band region is presented. The procedure takes advantage of an antiresonant behavior of cobalt-derived states at the 3p-3d excitation threshold. Information about the unoccupied density of states has been obtained by OK XAS. The structure of the CoL absorption edge is compared to semiempirical charge-transfer multiplet calculations. The experimental results are furthermore compared with band-structure calculations considering three different exchange potentials [generalized gradient approximation (GGA), using a nonlocal Hubbard U (GGA+U) and using a hybrid functional (Becke, three-parameter, Lee-Yang-Parr [B3LYP])]. For these different approaches total density of states and partial valence-band density of states have been investigated. The best qualitative agreement with experimental results has been obtained by using a GGA+U functional with U=2.9eV .

Polymorphism and thermodynamic ground state of silver fulminate studied from van der Waals density functional calculations

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

Yedukondalu, N.; Vaitheeswaran, G., E-mail: gvsp@uohyd.ernet.in

2014-06-14

Silver fulminate (AgCNO) is a primary explosive, which exists in two polymorphic phases, namely, orthorhombic (Cmcm) and trigonal (R3{sup ¯}) forms at ambient conditions. In the present study, we have investigated the effect of pressure and temperature on relative phase stability of the polymorphs using planewave pseudopotential approaches based on Density Functional Theory (DFT). van der Waals interactions play a significant role in predicting the phase stability and they can be effectively captured by semi-empirical dispersion correction methods in contrast to standard DFT functionals. Based on our total energy calculations using DFT-D2 method, the Cmcm structure is found to bemore » the preferred thermodynamic equilibrium phase under studied pressure and temperature range. Hitherto Cmcm and R3{sup ¯} phases denoted as α- and β-forms of AgCNO, respectively. Also a pressure induced polymorphic phase transition is seen using DFT functionals and the same was not observed with DFT-D2 method. The equation of state and compressibility of both polymorphic phases were investigated. Electronic structure and optical properties were calculated using full potential linearized augmented plane wave method within the Tran-Blaha modified Becke-Johnson potential. The calculated electronic structure shows that α, β phases are indirect bandgap insulators with a bandgap values of 3.51 and 4.43 eV, respectively. The nature of chemical bonding is analyzed through the charge density plots and partial density of states. Optical anisotropy, electric-dipole transitions, and photo sensitivity to light of the polymorphs are analyzed from the calculated optical spectra. Overall, the present study provides an early indication to experimentalists to avoid the formation of unstable β-form of AgCNO.« less

Ambient-Pressure XPS Study of a Ni–Fe Electrocatalyst for the Oxygen Evolution Reaction

DOE PAGES

Ali-Löytty, Harri; Louie, Mary W.; Singh, Meenesh R.; ...

2016-01-05

Chemical analysis of solid–liquid interfaces under electrochemical conditions has recently become feasible due to the development of new synchrotron radiation techniques. In this paper, we report the use of “tender” X-ray ambient-pressure X-ray photoelectron spectroscopy (APXPS) to characterize a thin film of Ni–Fe oxyhydroxide electrodeposited on Au as the working electrode at different applied potentials in 0.1 M KOH as the electrolyte. Our results show that the as-prepared 7 nm thick Ni–Fe (50% Fe) film contains Fe and Ni in both their metallic as well as oxidized states, and undergoes further oxidation when the sample is subjected to electrochemical oxidation–reductionmore » cycles. Metallic Fe is oxidized to Fe 3+ and metallic Ni to Ni 2+/3+. This work shows that it is possible to monitor the chemical nature of the Ni–Fe catalyst as a function of potential when the corresponding current densities are small. This allows for operando measurements just above the onset of OER; however, current densities as they are desired in photoelectrochemical devices (~1–10 mA cm –2) could not be achieved in this work, due to ohmic losses in the thin electrolyte film. We use a two-dimensional model to describe the spatial distribution of the electrochemical potential, current density, and pH as a function of the position above the electrolyte meniscus, to provide guidance toward enabling the acquisition of operando APXPS at high current density. Finally, the shifts in binding energy of water with applied potential predicted by the model are in good agreement with the experimental values.« less

Dependence of Excited State Potential Energy Surfaces on the Spatial Overlap of the Kohn-Sham Orbitals and the Amount of Nonlocal Hartree-Fock Exchange in Time-Dependent Density Functional Theory.

PubMed

Plötner, Jürgen; Tozer, David J; Dreuw, Andreas

2010-08-10

Time-dependent density functional theory (TDDFT) with standard GGA or hybrid exchange-correlation functionals is not capable of describing the potential energy surface of the S1 state of Pigment Yellow 101 correctly; an additional local minimum is observed at a twisted geometry with substantial charge transfer (CT) character. To investigate the influence of nonlocal exact orbital (Hartree-Fock) exchange on the shape of the potential energy surface of the S1 state in detail, it has been computed along the twisting coordinate employing the standard BP86, B3LYP, and BHLYP xc-functionals as well as the long-range separated (LRS) exchange-correlation (xc)-functionals LC-BOP, ωB97X, ωPBE, and CAM-B3LYP and compared to RI-CC2 benchmark results. Additionally, a recently suggested Λ-parameter has been employed that measures the amount of CT in an excited state by calculating the spatial overlap of the occupied and virtual molecular orbitals involved in the transition. Here, the error in the calculated S1 potential energy curves at BP86, B3LYP, and BHLYP can be clearly related to the Λ-parameter, i.e., to the extent of charge transfer. Additionally, it is demonstrated that the CT problem is largely alleviated when the BHLYP xc-functional is employed, although it still exhibits a weak tendency to underestimate the energy of CT states. The situation improves drastically when LRS-functionals are employed within TDDFT excited state calculations. All tested LRS-functionals give qualitatively the correct potential energy curves of the energetically lowest excited states of P. Y. 101 along the twisting coordinate. While LC-BOP and ωB97X overcorrect the CT problem and now tend to give too large excitation energies compared to other non-CT states, ωPBE and CAM-B3LYP are in excellent agreement with the RI-CC2 results, with respect to both the correct shape of the potential energy curve as well as the absolute values of the calculated excitation energies.

Optical properties from time-dependent current-density-functional theory: the case of the alkali metals Na, K, Rb, and Cs

NASA Astrophysics Data System (ADS)

Ferradás, R.; Berger, J. A.; Romaniello, Pina

2018-06-01

We present the optical conductivity as well as the electron-energy loss spectra of the alkali metals Na, K, Rb, and Cs calculated within time-dependent current-density functional theory. Our ab initio formulation describes from first principles both the Drude-tail and the interband absorption of these metals as well as the most dominant relativistic effects. We show that by using a recently derived current functional [Berger, Phys. Rev. Lett. 115, 137402 (2015)] we obtain an overall good agreement with experiment at a computational cost that is equivalent to the random-phase approximation. We also highlight the importance of the choice of the exchange-correlation potential of the ground state.

Structure and orientational ordering in a fluid of elongated quadrupolar molecules

NASA Astrophysics Data System (ADS)

Singh, Ram Chandra

2013-01-01

A second-order density-functional theory is used to study the effect of quadrupolar interactions on the isotropic-nematic transition in a system of fluids of elongated molecules interacting via the Gay-Berne potential. The direct pair-correlation functions of the coexisting isotropic fluid that enter in the theory as input information are obtained by solving the Ornstein-Zernike equation using the Percus-Yevick integral equation theory in the (reduced) temperature range of 1.6≤T∗≤3.0 for different densities, temperatures and quadrupole moments. Using the harmonic coefficients of the direct pair-correlation functions, isotropic-nematic phase coexistence and thermodynamic parameters have been calculated. The theoretical results have been compared with the available computer simulation results.

Nuclear parton density functions from dijet photoproduction at the EIC

NASA Astrophysics Data System (ADS)

Klasen, M.; Kovařík, K.

2018-06-01

We study the potential of dijet photoproduction measurements at a future electron-ion collider (EIC) to better constrain our present knowledge of the nuclear parton distribution functions. Based on theoretical calculations at next-to-leading order and approximate next-to-next-to-leading order of perturbative QCD, we establish the kinematic reaches for three different EIC designs, the size of the parton density function modifications for four different light and heavy nuclei from He-4 over C-12 and Fe-56 to Pb-208 with respect to the free proton, and the improvement of EIC measurements with respect to current determinations from deep-inelastic scattering and Drell-Yan data alone as well as when also considering data from existing hadron colliders.

Grid-based Continual Analysis of Molecular Interior for Drug Discovery, QSAR and QSPR.

PubMed

Potemkin, Andrey V; Grishina, Maria A; Potemkin, Vladimir A

2017-01-01

In 1979, R.D.Cramer and M.Milne made a first realization of 3D comparison of molecules by aligning them in space and by mapping their molecular fields to a 3D grid. Further, this approach was developed as the DYLOMMS (Dynamic Lattice- Oriented Molecular Modelling System) approach. In 1984, H.Wold and S.Wold proposed the use of partial least squares (PLS) analysis, instead of principal component analysis, to correlate the field values with biological activities. Then, in 1988, the method which was called CoMFA (Comparative Molecular Field Analysis) was introduced and the appropriate software became commercially available. Since 1988, a lot of 3D QSAR methods, algorithms and their modifications are introduced for solving of virtual drug discovery problems (e.g., CoMSIA, CoMMA, HINT, HASL, GOLPE, GRID, PARM, Raptor, BiS, CiS, ConGO,). All the methods can be divided into two groups (classes):1. Methods studying the exterior of molecules; 2) Methods studying the interior of molecules. A series of grid-based computational technologies for Continual Molecular Interior analysis (CoMIn) are invented in the current paper. The grid-based analysis is fulfilled by means of a lattice construction analogously to many other grid-based methods. The further continual elucidation of molecular structure is performed in various ways. (i) In terms of intermolecular interactions potentials. This can be represented as a superposition of Coulomb, Van der Waals interactions and hydrogen bonds. All the potentials are well known continual functions and their values can be determined in all lattice points for a molecule. (ii) In the terms of quantum functions such as electron density distribution, Laplacian and Hamiltonian of electron density distribution, potential energy distribution, the highest occupied and the lowest unoccupied molecular orbitals distribution and their superposition. To reduce time of calculations using quantum methods based on the first principles, an original quantum free-orbital approach AlteQ is proposed. All the functions can be calculated using a quantum approach at a sufficient level of theory and their values can be determined in all lattice points for a molecule. Then, the molecules of a dataset can be superimposed in the lattice for the maximal coincidence (or minimal deviations) of the potentials (i) or the quantum functions (ii). The methods and criteria of the superimposition are discussed. After that a functional relationship between biological activity or property and characteristics of potentials (i) or functions (ii) is created. The methods of the quantitative relationship construction are discussed. New approaches for rational virtual drug design based on the intermolecular potentials and quantum functions are invented. All the invented methods are realized at www.chemosophia.com web page. Therefore, a set of 3D QSAR approaches for continual molecular interior study giving a lot of opportunities for virtual drug discovery, virtual screening and ligand-based drug design are invented. The continual elucidation of molecular structure is performed in the terms of intermolecular interactions potentials and in the terms of quantum functions such as electron density distribution, Laplacian and Hamiltonian of electron density distribution, potential energy distribution, the highest occupied and the lowest unoccupied molecular orbitals distribution and their superposition. To reduce time of calculations using quantum methods based on the first principles, an original quantum free-orbital approach AlteQ is proposed. The methods of the quantitative relationship construction are discussed. New approaches for rational virtual drug design based on the intermolecular potentials and quantum functions are invented. All the invented methods are realized at www.chemosophia.com web page. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Vapour-liquid interfacial properties of square-well chains from density functional theory and Monte Carlo simulation.

PubMed

Martínez-Ruiz, Francisco José; Blas, Felipe J; Moreno-Ventas Bravo, A Ignacio; Míguez, José Manuel; MacDowell, Luis G

2017-05-17

The statistical associating fluid theory for attractive potentials of variable range (SAFT-VR) density functional theory (DFT) developed by [Gloor et al., J. Chem. Phys., 2004, 121, 12740-12759] is used to predict the interfacial behaviour of molecules modelled as fully-flexible square-well chains formed from tangentially-bonded monomers of diameter σ and potential range λ = 1.5σ. Four different model systems, comprising 4, 8, 12, and 16 monomers per molecule, are considered. In addition to that, we also compute a number of interfacial properties of molecular chains from direct simulation of the vapour-liquid interface. The simulations are performed in the canonical ensemble, and the vapour-liquid interfacial tension is evaluated using the wandering interface (WIM) method, a technique based on the thermodynamic definition of surface tension. Apart from surface tension, we also obtain density profiles, coexistence densities, vapour pressures, and critical temperature and density, paying particular attention to the effect of the chain length on these properties. According to our results, the main effect of increasing the chain length (at fixed temperature) is to sharpen the vapour-liquid interface and to increase the width of the biphasic coexistence region. As a result, the interfacial thickness decreases and the surface tension increases as the molecular chains get longer. The interfacial thickness and surface tension appear to exhibit an asymptotic limiting behaviour for long chains. A similar behaviour is also observed for the coexistence densities and critical properties. Agreement between theory and simulation results indicates that SAFT-VR DFT is only able to predict qualitatively the interfacial properties of the model. Our results are also compared with simulation data taken from the literature, including the vapour-liquid coexistence densities, vapour pressures, and surface tension.

Thermodynamic neutral density: A new physically-based, energy-constrained, materially conserved neutral density variable for quantifying mixing and tracking water masses in the ocean

NASA Astrophysics Data System (ADS)

Tailleux, R.

2016-02-01

A new materially-conserved quasi-neutral density variable has been constructed, called thermodynamic neutral density. It is composed of two parts. The first part is the Lorenz reference density entering Lorenz theory of available potential energy, which can be interpreted as the potential density of a fluid parcel referenced to the pressure it would have in Lorenz reference state of minimum potential energy. The second part is an empirical correction for pressure, which can be suitably chosen to make thermodynamic neutral density a very good approximation of Jackett and McDougall (1997) neutral density over most of the ocean water masses for which the latter is defined. Thermodynamic neutral density possesses many advantages over the empirically constructed Jackett and McDougall (1997) neutral density: 1) it is physically-based; 2) it is easily computed using fast and efficient methods for arbitrary states of the ocean, not just the present state, using the recently developed methodology by Saenz et al. (2015); 3) it is exactly neutral in a state of rest, and approximately neutral in the present ocean; 4) it is exactly materially conserved (it is a function of salinity and potential temperature only) and not plagued by unphysical nonmaterial effects, so can be used unambiguously to define and diagnose diapycnal and isopycnal mixing; 5) it is based on available potential energy, and therefore is the most suitable variable to discuss the energy cost of adiabatic stirring; 6) it is the variable that should be used to define the isopycnal and diapycnal directions in rotated diffusion tensor, as it can be shown that using the directions defined by the local neutral tangent plane as currently done causes spurious destruction of water masses. References: J. A. Saenz, R. Tailleux, E.D. Butler, G.O. Hughes, and K.I.C. Oliver, 2015: Estimating Lorenz's reference state in an ocean with a nonlinear equation of state for seawater. J. Phys. Oceanogr., 45, 1242—1257

Molecular dynamics simulation of solute diffusion in Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Kimura, Y.; Hirota, N.

We performed a molecular dynamics (MD) simulation for a system of 5 solute molecules in 495 solvent molecules interacting through the Lennard-Jones (LJ) 12-6 potential, in order to study solvent density effects on the diffusion coefficients in supercritical fluids. The effects of the size of the solute and the strength of the solute-solvent attractive interaction on the diffusion coefficient of the solute were examined. The diffusion coefficients of the solute molecules were calculated at T = 1.5 (in the LJ reduced unit), slightly above the critical temperature, from rho = 0.1 to rho = 0.95, where rho is the number density in the LJ reduced unit. The memory function in the generalized Langevin equation was calculated, in order to know the molecular origin of the friction on a solute. The memory function is separated into fast and slow components. The former arises from the solute-solvent repulsive interaction, and is interpreted as collisional Enskog-like friction. The interaction strength dependence of the collisional friction is larger in the low- and medium-density regions, which is consistent with the 'clustering' picture, i.e., the local density enhancement due to the solute-solvent attractive interaction. However, the slow component of the memory function suppresses the effect of the local density on the diffusion coefficients, and as a result the effect of the attractive interaction is smaller on the diffusion coefficients than on the local density. Nonetheless, the solvent density dependence of the effect of the attraction on the diffusion coefficient varies with the local density, and it is concluded that the local density is the principal factor that determines the interaction strength dependence of the diffusion coefficient in the low- and medium-density regions (p < 0.6).

Local density variation of gold nanoparticles in aquatic environments

NASA Astrophysics Data System (ADS)

Hosseinzadeh, F.; Shirazian, F.; Shahsavari, R.; Khoei, A. R.

2016-10-01

Gold (Au) nanoparticles are widely used in diagnosing cancer, imaging, and identification of therapeutic methods due to their particular quantum characteristics. This research presents different types of aqueous models and potentials used in TIP3P, to study the effect of the particle size and density of Au clusters in aquatic environments; so it can be useful to facilitate future investigation of the interaction of proteins with Au nanoparticles. The EAM potential is used to model the structure of gold clusters. It is observed that in the systems with identical gold/water density and different cluster radii, gold particles are distributed in aqueous environment almost identically. Thus, Au particles have identical local densities, and the root mean square displacement (RMSD) increases with a constant slope. However in systems with constant cluster radii and different gold/water densities, Au particle dispersion increases with density; as a result, the local density decreases and the RMSD increases with a larger slope. In such systems, the larger densities result in more blunted second peaks in gold-gold radial distribution functions, owing to more intermixing of the clusters and less FCC crystalline features at longer range, a mechanism that is mediated by the competing effects of gold-water and gold-gold interactions.

Density scaling for multiplets

NASA Astrophysics Data System (ADS)

Nagy, Á.

2011-02-01

Generalized Kohn-Sham equations are presented for lowest-lying multiplets. The way of treating non-integer particle numbers is coupled with an earlier method of the author. The fundamental quantity of the theory is the subspace density. The Kohn-Sham equations are similar to the conventional Kohn-Sham equations. The difference is that the subspace density is used instead of the density and the Kohn-Sham potential is different for different subspaces. The exchange-correlation functional is studied using density scaling. It is shown that there exists a value of the scaling factor ζ for which the correlation energy disappears. Generalized OPM and Krieger-Li-Iafrate (KLI) methods incorporating correlation are presented. The ζKLI method, being as simple as the original KLI method, is proposed for multiplets.

Molecular Excitation Energies from Time-Dependent Density Functional Theory Employing Random-Phase Approximation Hessians with Exact Exchange.

PubMed

Heßelmann, Andreas

2015-04-14

Molecular excitation energies have been calculated with time-dependent density-functional theory (TDDFT) using random-phase approximation Hessians augmented with exact exchange contributions in various orders. It has been observed that this approach yields fairly accurate local valence excitations if combined with accurate asymptotically corrected exchange-correlation potentials used in the ground-state Kohn-Sham calculations. The inclusion of long-range particle-particle with hole-hole interactions in the kernel leads to errors of 0.14 eV only for the lowest excitations of a selection of three alkene, three carbonyl, and five azabenzene molecules, thus surpassing the accuracy of a number of common TDDFT and even some wave function correlation methods. In the case of long-range charge-transfer excitations, the method typically underestimates accurate reference excitation energies by 8% on average, which is better than with standard hybrid-GGA functionals but worse compared to range-separated functional approximations.

SnO as a potential oxide thermoelectric candidate

DOE PAGES

Miller, Samuel A.; Gorai, Prashun; Aydemir, Umut; ...

2017-08-08

Here we search for new thermoelectric materials, high-throughput calculations using a combination of semiempirical models and first principles density functional theory present a path to screen large numbers of compounds for the most promising candidates.

Simulation of electric double-layer capacitors: evaluation of constant potential method

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Laird, Brian; Yang, Yang; Olmsted, David; Asta, Mark

2014-03-01

Atomistic simulations can play an important role in understanding electric double-layer capacitors (EDLCs) at a molecular level. In such simulations, typically the electrode surface is modeled using fixed surface charges, which ignores the charge fluctuation induced by local fluctuations in the electrolyte solution. In this work we evaluate an explicit treatment of charges, namely constant potential method (CPM)[1], in which the electrode charges are dynamically updated to maintain constant electrode potential. We employ a model system with a graphite electrode and a LiClO4/acetonitrile electrolyte, examined as a function of electrode potential differences. Using various molecular and macroscopic properties as metrics, we compare CPM simulations on this system to results using fixed surface charges. Specifically, results for predicted capacity, electric potential gradient and solvent density profile are identical between the two methods; However, ion density profiles and solvation structure yield significantly different results.

Relation between the Dynamics of Glassy Clusters and Characteristic Features of their Energy Landscape

NASA Astrophysics Data System (ADS)

De, Sandip; Schaefer, Bastian; Sadeghi, Ali; Sicher, Michael; Kanhere, D. G.; Goedecker, Stefan

2014-02-01

Based on a recently introduced metric for measuring distances between configurations, we introduce distance-energy (DE) plots to characterize the potential energy surface of clusters. Producing such plots is computationally feasible on the density functional level since it requires only a few hundred stable low energy configurations including the global minimum. By using standard criteria based on disconnectivity graphs and the dynamics of Lennard-Jones clusters, we show that the DE plots convey the necessary information about the character of the potential energy surface and allow us to distinguish between glassy and nonglassy systems. We then apply this analysis to real clusters at the density functional theory level and show that both glassy and nonglassy clusters can be found in simulations. It turns out that among our investigated clusters only those can be synthesized experimentally which exhibit a nonglassy landscape.

Analysis of a photon assisted field emission device

NASA Astrophysics Data System (ADS)

Jensen, K. L.; Lau, Y. Y.; McGregor, D. S.

2000-07-01

A field emitter array held at the threshold of emission by a dc gate potential from which current pulses are triggered by the application of a laser pulse on the backside of the semiconductor may produce electron bunches ("density modulation") at gigahertz frequencies. We develop an analytical model of such optically controlled emission from a silicon tip using a modified Wentzel-Kramers-Brillouin and Airy function approach to solving Schrödinger's equation. Band bending and an approximation to the exchange-correlation effects on the image charge potential are included for an array of hyperbolic emitters with a distribution in tip radii and work function. For a simple relationship between the incident photon flux and the resultant electron density at the emission site, an estimation of the tunneling current is made. An example of the operation and design of such a photon-assisted field emission device is given.

Density functional theory study on the ionic liquid pyridinium hydrogen sulfate

NASA Astrophysics Data System (ADS)

Tankov, Ivaylo; Yankova, Rumyana; Genieva, Svetlana; Mitkova, Magdalena; Stratiev, Dicho

2017-07-01

The geometry, electronic structure and chemical reactivity of a pyridinium-based ionic liquid, pyridinium hydrogen sulfate ([H-Pyr]+[HSO4]-), have been discussed on the basis of quantum chemical density functional theory calculations using B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) approaches. The calculations indicated that [H-Pyr]+[HSO4]- exists in the form of an ion pair. A large electropositive potential was found on the pyridinium ring, while the regions of a negative electrostatic potential is linked with the lone pair of electronegative oxygen atoms in hydrogen sulfate anion ([HSO4]-). Electron transfer both within the anion, and between the anion and cation of an ion pair were described using natural bond orbital theory. The energy values of -7.1375 and -2.8801 eV were related to HOMO and LUMO orbitals, respectively.

Pair potentials for warm dense matter and their application to x-ray Thomson scattering in aluminum and beryllium.

PubMed

Harbour, L; Dharma-Wardana, M W C; Klug, D D; Lewis, L J

2016-11-01

Ultrafast laser experiments yield increasingly reliable data on warm dense matter, but their interpretation requires theoretical models. We employ an efficient density functional neutral-pseudoatom hypernetted-chain (NPA-HNC) model with accuracy comparable to ab initio simulations and which provides first-principles pseudopotentials and pair potentials for warm-dense matter. It avoids the use of (i) ad hoc core-repulsion models and (ii) "Yukawa screening" and (iii) need not assume ion-electron thermal equilibrium. Computations of the x-ray Thomson scattering (XRTS) spectra of aluminum and beryllium are compared with recent experiments and with density-functional-theory molecular-dynamics (DFT-MD) simulations. The NPA-HNC structure factors, compressibilities, phonons, and conductivities agree closely with DFT-MD results, while Yukawa screening gives misleading results. The analysis of the XRTS data for two of the experiments, using two-temperature quasi-equilibrium models, is supported by calculations of their temperature relaxation times.

Experimental and first principle studies on electronic structure of BaTiO{sub 3}

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

Sagdeo, Archna, E-mail: archnaj@rrcat.gov.in; Ghosh, Haranath, E-mail: archnaj@rrcat.gov.in; Chakrabarti, Aparna, E-mail: archnaj@rrcat.gov.in

2014-04-24

We have carried out photoemission experiments to obtain valence band spectra of various crystallographic symmetries of BaTiO{sub 3} system which arise as a function of temperature. We also present results of a detailed first principle study of these symmetries of BaTiO{sub 3} using generalized gradient approximation for the exchange-correlation potential. Here we present theoretical results of density of states obtained from DFT based simulations to compare with the experimental valence band spectra. Further, we also perform calculations using post density functional approaches like GGA + U method as well as non-local hybrid exchange-correlation potentials like PBE0, B3LYP, HSE in ordermore » to understand the extent of effect of correlation on band gaps of different available crystallographic symmetries (5 in number) of BaTiO{sub 3}.« less

Excitation energies of dissociating H2: A problematic case for the adiabatic approximation of time-dependent density functional theory

NASA Astrophysics Data System (ADS)

Gritsenko, O. V.; van Gisbergen, S. J. A.; Görling, A.; Baerends, E. J.

2000-11-01

Time-dependent density functional theory (TDDFT) is applied for calculation of the excitation energies of the dissociating H2 molecule. The standard TDDFT method of adiabatic local density approximation (ALDA) totally fails to reproduce the potential curve for the lowest excited singlet 1Σu+ state of H2. Analysis of the eigenvalue problem for the excitation energies as well as direct derivation of the exchange-correlation (xc) kernel fxc(r,r',ω) shows that ALDA fails due to breakdown of its simple spatially local approximation for the kernel. The analysis indicates a complex structure of the function fxc(r,r',ω), which is revealed in a different behavior of the various matrix elements K1c,1cxc (between the highest occupied Kohn-Sham molecular orbital ψ1 and virtual MOs ψc) as a function of the bond distance R(H-H). The effect of nonlocality of fxc(r,r') is modeled by using different expressions for the corresponding matrix elements of different orbitals. Asymptotically corrected ALDA (ALDA-AC) expressions for the matrix elements K12,12xc(στ) are proposed, while for other matrix elements the standard ALDA expressions are retained. This approach provides substantial improvement over the standard ALDA. In particular, the ALDA-AC curve for the lowest singlet excitation qualitatively reproduces the shape of the exact curve. It displays a minimum and approaches a relatively large positive energy at large R(H-H). ALDA-AC also produces a substantial improvement for the calculated lowest triplet excitation, which is known to suffer from the triplet instability problem of the restricted KS ground state. Failure of the ALDA for the excitation energies is related to the failure of the local density as well as generalized gradient approximations to reproduce correctly the polarizability of dissociating H2. The expression for the response function χ is derived to show the origin of the field-counteracting term in the xc potential, which is lacking in the local density and generalized gradient approximations and which is required to obtain a correct polarizability.

Exact kinetic energy enables accurate evaluation of weak interactions by the FDE-vdW method.

PubMed

Sinha, Debalina; Pavanello, Michele

2015-08-28

The correlation energy of interaction is an elusive and sought-after interaction between molecular systems. By partitioning the response function of the system into subsystem contributions, the Frozen Density Embedding (FDE)-vdW method provides a computationally amenable nonlocal correlation functional based on the adiabatic connection fluctuation dissipation theorem applied to subsystem density functional theory. In reproducing potential energy surfaces of weakly interacting dimers, we show that FDE-vdW, either employing semilocal or exact nonadditive kinetic energy functionals, is in quantitative agreement with high-accuracy coupled cluster calculations (overall mean unsigned error of 0.5 kcal/mol). When employing the exact kinetic energy (which we term the Kohn-Sham (KS)-vdW method), the binding energies are generally closer to the benchmark, and the energy surfaces are also smoother.

Exact kinetic energy enables accurate evaluation of weak interactions by the FDE-vdW method

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

Sinha, Debalina; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu

2015-08-28

The correlation energy of interaction is an elusive and sought-after interaction between molecular systems. By partitioning the response function of the system into subsystem contributions, the Frozen Density Embedding (FDE)-vdW method provides a computationally amenable nonlocal correlation functional based on the adiabatic connection fluctuation dissipation theorem applied to subsystem density functional theory. In reproducing potential energy surfaces of weakly interacting dimers, we show that FDE-vdW, either employing semilocal or exact nonadditive kinetic energy functionals, is in quantitative agreement with high-accuracy coupled cluster calculations (overall mean unsigned error of 0.5 kcal/mol). When employing the exact kinetic energy (which we term themore » Kohn-Sham (KS)-vdW method), the binding energies are generally closer to the benchmark, and the energy surfaces are also smoother.« less

Global hybrids from the semiclassical atom theory satisfying the local density linear response.

PubMed

Fabiano, Eduardo; Constantin, Lucian A; Cortona, Pietro; Della Sala, Fabio

2015-01-13

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 2011, 106, 186406] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetic and structural testing, including thermochemistry and geometry, transition metal complexes, noncovalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semiempirical dispersion corrections are also provided.

Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

NASA Astrophysics Data System (ADS)

Zhuang, Houlong L.; Zhou, Jia

2016-11-01

Searching for two-dimensional (2D) materials with multifunctionality is one of the main goals of current research in 2D materials. Magnetism and semiconducting are certainly two desirable functional properties for a single 2D material. In line with this goal, here we report a density functional theory (DFT) study of bulk and single-layer magnetic semiconductor CrPS4. We find that the ground-state magnetic structure of bulk CrPS4 exhibits the A-type antiferromagnetic ordering, which transforms to ferromagnetic (FM) ordering in single-layer CrPS4. The calculated formation energy and phonon spectrum confirm the stability of single-layer CrPS4. The band gaps of FM single-layer CrPS4 calculated with a hybrid density functional are within the visible-light range. We also study the effects of FM ordering on the optical absorption spectra and band alignments for water splitting, indicating that single-layer CrPS4 could be a potential photocatalyst. Our work opens up ample opportunities of energy-related applications of single-layer CrPS4.

Evolution of the orbitals Dy-4f in the DyB2 compound using the LDA, PBE approximations, and the PBE0 hybrid functional

NASA Astrophysics Data System (ADS)

Rasero Causil, Diego; Ortega López, César; Espitia Rico, Miguel

2018-04-01

Computational calculations of total energy based on density functional theory were used to investigate the structural, electronic, and magnetic properties of the DyB2 compounds in the hexagonal structure. The calculations were carried out by means of the full-potential linearized augmented plane wave (FP-LAPW) method, employing the computational Wien2k package. The local density approximation (LDA) and the generalized gradient approximation (GGA) were used for the electron-electron interactions. Additionally, we used the functional hybrid PBE0 for a better description the electronic and magnetic properties, because the DyB2 compound is a strongly-correlated system. We found that the calculated lattice constant agrees well with the values reported theoretically and experimentally. The density of states (DOS) calculation shows that the compound exhibits a metallic behavior and has magnetic properties, with a total magnetic moment of 5.47 μ0/cell determined mainly by the 4f states of the rare earth elements. The functional PBE0 shows a strong localization of the Dy-4f orbitals.

Numerical methods for the inverse problem of density functional theory

DOE PAGES

Jensen, Daniel S.; Wasserman, Adam

2017-07-17

Here, the inverse problem of Kohn–Sham density functional theory (DFT) is often solved in an effort to benchmark and design approximate exchange-correlation potentials. The forward and inverse problems of DFT rely on the same equations but the numerical methods for solving each problem are substantially different. We examine both problems in this tutorial with a special emphasis on the algorithms and error analysis needed for solving the inverse problem. Two inversion methods based on partial differential equation constrained optimization and constrained variational ideas are introduced. We compare and contrast several different inversion methods applied to one-dimensional finite and periodic modelmore » systems.« less

Path-integral approach to the Wigner-Kirkwood expansion.

PubMed

Jizba, Petr; Zatloukal, Václav

2014-01-01

We study the high-temperature behavior of quantum-mechanical path integrals. Starting from the Feynman-Kac formula, we derive a functional representation of the Wigner-Kirkwood perturbation expansion for quantum Boltzmann densities. As shown by its applications to different potentials, the presented expansion turns out to be quite efficient in generating analytic form of the higher-order expansion coefficients. To put some flesh on the bare bones, we apply the expansion to obtain basic thermodynamic functions of the one-dimensional anharmonic oscillator. Further salient issues, such as generalization to the Bloch density matrix and comparison with the more customary world-line formulation, are discussed.

Vibrational Spectra and Density functional calculation of Organic Nonlinear Optic Crystal p-Amino Acetanilide

NASA Astrophysics Data System (ADS)

Saja, D.; Joe, I. Hubert; Jayakumar, V. S.

2006-01-01

The NIR-FT Raman, FT-IR spectral analysis of potential NLO material P-Amino Acetanilide is carried out by density functional computations. The optimized geometry shows that NH2 and NHCOCH3 groups substituted in para position of phenyl ring are non-planar which predicts maximum conjugation of molecule with donor and acceptor groups. Vibrational analysis reveals that simultaneous IR and Raman activation of the phenyl ring modes also provide evidence for the charge transfer interaction between the donors and the acceptor can make the molecule highly polarized and the intra molecular charge transfer interaction must be responsible for the NLO properties of PAA.

Numerical methods for the inverse problem of density functional theory

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

Jensen, Daniel S.; Wasserman, Adam

Here, the inverse problem of Kohn–Sham density functional theory (DFT) is often solved in an effort to benchmark and design approximate exchange-correlation potentials. The forward and inverse problems of DFT rely on the same equations but the numerical methods for solving each problem are substantially different. We examine both problems in this tutorial with a special emphasis on the algorithms and error analysis needed for solving the inverse problem. Two inversion methods based on partial differential equation constrained optimization and constrained variational ideas are introduced. We compare and contrast several different inversion methods applied to one-dimensional finite and periodic modelmore » systems.« less

Coulomb Impurity Potential RbCl Quantum Pseudodot Qubit

NASA Astrophysics Data System (ADS)

Ma, Xin-Jun; Qi, Bin; Xiao, Jing-Lin

2015-08-01

By employing a variational method of Pekar type, we study the eigenenergies and the corresponding eigenfunctions of the ground and the first-excited states of an electron strongly coupled to electron-LO in a RbCl quantum pseudodot (QPD) with a hydrogen-like impurity at the center. This QPD system may be used as a two-level quantum qubit. The expressions of electron's probability density versus time and the coordinates, and the oscillating period versus the Coulombic impurity potential and the polaron radius have been derived. The investigated results indicate ① that the probability density of the electron oscillates in the QPD with a certain oscillating period of , ② that due to the presence of the asymmetrical potential in the z direction of the RbCl QPD, the electron probability density shows double-peak configuration, whereas there is only one peak if the confinement is a two-dimensional symmetric structure in the xy plane of the QPD, ③ that the oscillation period is a decreasing function of the Coulombic impurity potential, whereas it is an increasing one of the polaron radius.

Engineering Redox Potential of Lithium Clusters for Electrode Material in Lithium-Ion Batteries

DOE PAGES

Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nanda, Jagjit; ...

2017-07-01

Low negative electrode potential and high reactivity makes lithium (Li) ideal candidate for obtaining highest possible energy density among other materials. Here, we show a novel route with which the overall electrode potential could significantly be enhanced through selection of cluster size. In using first principles density functional theory and continuum dielectric model, we studied free energy and redox potential as well as investigated relative stability of Li n (n ≤ 8) clusters in both gas phase and solution. We found that Li 3 has the lowest negative redox potential (thereby highest overall electrode potential) suggesting that cluster based approachmore » could provide a novel way of engineering the next generation battery technology. The microscopic origin of Li 3 cluster’s superior performance is related to two major factors: gas phase ionization and difference between solvation free energy for neutral and positive ion. Taken together, our study provides insight into the engineering of redox potential in battery and could stimulate further work in this direction.« less

Engineering Redox Potential of Lithium Clusters for Electrode Material in Lithium-Ion Batteries

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

Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nanda, Jagjit

Low negative electrode potential and high reactivity makes lithium (Li) ideal candidate for obtaining highest possible energy density among other materials. Here, we show a novel route with which the overall electrode potential could significantly be enhanced through selection of cluster size. In using first principles density functional theory and continuum dielectric model, we studied free energy and redox potential as well as investigated relative stability of Li n (n ≤ 8) clusters in both gas phase and solution. We found that Li 3 has the lowest negative redox potential (thereby highest overall electrode potential) suggesting that cluster based approachmore » could provide a novel way of engineering the next generation battery technology. The microscopic origin of Li 3 cluster’s superior performance is related to two major factors: gas phase ionization and difference between solvation free energy for neutral and positive ion. Taken together, our study provides insight into the engineering of redox potential in battery and could stimulate further work in this direction.« less

The nature of three-body interactions in DFT: Exchange and polarization effects

NASA Astrophysics Data System (ADS)

Hapka, Michał; Rajchel, Łukasz; Modrzejewski, Marcin; Schäffer, Rainer; Chałasiński, Grzegorz; Szcześniak, Małgorzata M.

2017-08-01

We propose a physically motivated decomposition of density functional theory (DFT) 3-body nonadditive interaction energies into the exchange and density-deformation (polarization) components. The exchange component represents the effect of the Pauli exclusion in the wave function of the trimer and is found to be challenging for density functional approximations (DFAs). The remaining density-deformation nonadditivity is less dependent upon the DFAs. Numerical demonstration is carried out for rare gas atom trimers, Ar2-HX (X = F, Cl) complexes, and small hydrogen-bonded and van der Waals molecular systems. None of the tested semilocal, hybrid, and range-separated DFAs properly accounts for the nonadditive exchange in dispersion-bonded trimers. By contrast, for hydrogen-bonded systems, range-separated DFAs achieve a qualitative agreement to within 20% of the reference exchange energy. A reliable performance for all systems is obtained only when the monomers interact through the Hartree-Fock potential in the dispersion-free Pauli blockade scheme. Additionally, we identify the nonadditive second-order exchange-dispersion energy as an important but overlooked contribution in force-field-like dispersion corrections. Our results suggest that range-separated functionals do not include this component, although semilocal and global hybrid DFAs appear to imitate it in the short range.

Combining density functional and incremental post-Hartree-Fock approaches for van der Waals dominated adsorbate-surface interactions: Ag{sub 2}/graphene

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

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Mitrushchenkov, Alexander O.; Stoll, Hermann

2015-09-14

A combined density functional (DFT) and incremental post-Hartree-Fock (post-HF) approach, proven earlier to calculate He-surface potential energy surfaces [de Lara-Castells et al., J. Chem. Phys. 141, 151102 (2014)], is applied to describe the van der Waals dominated Ag{sub 2}/graphene interaction. It extends the dispersionless density functional theory developed by Pernal et al. [Phys. Rev. Lett. 103, 263201 (2009)] by including periodic boundary conditions while the dispersion is parametrized via the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)]. Starting with the elementary cluster unit of the target surface (benzene), continuing through the realistic cluster model (coronene), andmore » ending with the periodic model of the extended system, modern ab initio methodologies for intermolecular interactions as well as state-of-the-art van der Waals-corrected density functional-based approaches are put together both to assess the accuracy of the composite scheme and to better characterize the Ag{sub 2}/graphene interaction. The present work illustrates how the combination of DFT and post-HF perspectives may be efficient to design simple and reliable ab initio-based schemes in extended systems for surface science applications.« less

Massive neutron star with strangeness in a relativistic mean-field model with a high-density cutoff

NASA Astrophysics Data System (ADS)

Zhang, Ying; Hu, Jinniu; Liu, Peng

2018-01-01

The properties of neutron stars with the strangeness degree of freedom are studied in the relativistic mean-field (RMF) model via including a logarithmic interaction as a function of the scalar meson field. This interaction, named the σ -cut potential, can largely reduce the attractive contributions of the scalar meson field at high density without any influence on the properties of nuclear structure around the normal saturation density. In this work, the TM1 parameter set is chosen as the RMF interaction, while the strengths of σ -cut potential are constrained by the properties of finite nuclei so that we can obtain a reasonable effective nucleon-nucleon interaction. The hyperons Λ ,Σ , and Ξ are considered in neutron stars within this framework, whose coupling constants with mesons are determined by the latest hyperon-nucleon and Λ -Λ potentials extracted from the available experimental data of hypernuclei. The maximum mass of neutron star can be larger than 2 M⊙ with these hyperons in the present framework. Furthermore, the nucleon mass at high density will be saturated due to this additional σ -cut potential, which is consistent with the conclusions obtained by other calculations such as Brueckner-Hartree-Fock theory and quark mean-field model.

A density functional theory study of the magnetic exchange coupling in dinuclear manganese(II) inverse crown structures.

PubMed

Vélez, Ederley; Alberola, Antonio; Polo, Víctor

2009-12-17

The magnetic exchange coupling constants between two Mn(II) centers for a set of five inverse crown structures have been investigated by means of a methodology based on broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic "guests" such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands and alkali metals (Na, Li). Magnetic exchange couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via an oxygen atom or hydride and very small antiferromagnetic couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide an understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.

Density-functional theory simulation of large quantum dots

NASA Astrophysics Data System (ADS)

Jiang, Hong; Baranger, Harold U.; Yang, Weitao

2003-10-01

Kohn-Sham spin-density functional theory provides an efficient and accurate model to study electron-electron interaction effects in quantum dots, but its application to large systems is a challenge. Here an efficient method for the simulation of quantum dots using density-function theory is developed; it includes the particle-in-the-box representation of the Kohn-Sham orbitals, an efficient conjugate-gradient method to directly minimize the total energy, a Fourier convolution approach for the calculation of the Hartree potential, and a simplified multigrid technique to accelerate the convergence. We test the methodology in a two-dimensional model system and show that numerical studies of large quantum dots with several hundred electrons become computationally affordable. In the noninteracting limit, the classical dynamics of the system we study can be continuously varied from integrable to fully chaotic. The qualitative difference in the noninteracting classical dynamics has an effect on the quantum properties of the interacting system: integrable classical dynamics leads to higher-spin states and a broader distribution of spacing between Coulomb blockade peaks.

Phonon and magnetic structure in δ-plutonium from density-functional theory

DOE PAGES

Söderlind, Per; Zhou, F.; Landa, A.; ...

2015-10-30

We present phonon properties of plutonium metal obtained from a combination of density-functional-theory (DFT) electronic structure and the recently developed compressive sensing lattice dynamics (CSLD). The CSLD model is here trained on DFT total energies of several hundreds of quasi-random atomic configurations for best possible accuracy of the phonon properties. The calculated phonon dispersions compare better with experiment than earlier results obtained from dynamical mean-field theory. The density-functional model of the electronic structure consists of disordered magnetic moments with all relativistic effects and explicit orbital-orbital correlations. The magnetic disorder is approximated in two ways: (i) a special quasi-random structure andmore » (ii) the disordered-local-moment (DLM) method within the coherent potential approximation. Magnetism in plutonium has been debated intensely, However, the present magnetic approach for plutonium is validated by the close agreement between the predicted magnetic form factor and that of recent neutron-scattering experiments.« less

Global and critical test of the perturbation density-functional theory based on extensive simulation of Lennard-Jones fluid near an interface and in confined systems.

PubMed

Zhou, Shiqi; Jamnik, Andrej

2005-09-22

The structure of a Lennard-Jones (LJ) fluid subjected to diverse external fields maintaining the equilibrium with the bulk LJ fluid is studied on the basis of the third-order+second-order perturbation density-functional approximation (DFA). The chosen density and potential parameters for the bulk fluid correspond to the conditions situated at "dangerous" regions of the phase diagram, i.e., near the critical temperature or close to the gas-liquid coexistence curve. The accuracy of DFA predictions is tested against the results of a grand canonical ensemble Monte Carlo simulation. It is found that the DFA theory presented in this work performs successfully for the nonuniform LJ fluid only on the condition of high accuracy of the required bulk second-order direct correlation function. The present report further indicates that the proposed perturbation DFA is efficient and suitable for both supercritical and subcritical temperatures.

Relative binding affinity of carboxylate-, phosphonate-, and bisphosphonate-functionalized gold nanoparticles targeted to damaged bone tissue

NASA Astrophysics Data System (ADS)

Ross, Ryan D.; Cole, Lisa E.; Roeder, Ryan K.

2012-10-01

Functionalized Au NPs have received considerable recent interest for targeting and labeling cells and tissues. Damaged bone tissue can be targeted by functionalizing Au NPs with molecules exhibiting affinity for calcium. Therefore, the relative binding affinity of Au NPs surface functionalized with either carboxylate ( l-glutamic acid), phosphonate (2-aminoethylphosphonic acid), or bisphosphonate (alendronate) was investigated for targeted labeling of damaged bone tissue in vitro. Targeted labeling of damaged bone tissue was qualitatively verified by visual observation and backscattered electron microscopy, and quantitatively measured by the surface density of Au NPs using field-emission scanning electron microscopy. The surface density of functionalized Au NPs was significantly greater within damaged tissue compared to undamaged tissue for each functional group. Bisphosphonate-functionalized Au NPs exhibited a greater surface density labeling damaged tissue compared to glutamic acid- and phosphonic acid-functionalized Au NPs, which was consistent with the results of previous work comparing the binding affinity of the same functionalized Au NPs to synthetic hydroxyapatite crystals. Targeted labeling was enabled not only by the functional groups but also by the colloidal stability in solution. Functionalized Au NPs were stabilized by the presence of the functional groups, and were shown to remain well dispersed in ionic (phosphate buffered saline) and serum (fetal bovine serum) solutions for up to 1 week. Therefore, the results of this study suggest that bisphosphonate-functionalized Au NPs have potential for targeted delivery to damaged bone tissue in vitro and provide motivation for in vivo investigation.

Ion and electron sheath characteristics in a low density and low temperature plasma

NASA Astrophysics Data System (ADS)

Borgohain, Binita; Bailung, H.

2017-11-01

Ion and electron sheath characteristics in a low electron temperature (Te ˜ 0.25-0.40 eV) and density (ne ˜ 106-107 cm-3) plasma are described. The plasma is produced in the experimental volume through diffusion from a hot cathode discharge plasma source by using a magnetic filter. The electron energy distribution function in the experimental plasma volume is measured to be a narrow Maxwellian distribution indicating the absence of primary and energetic electrons which are decoupled in the source side by the cusp magnetic field near the filter. An emissive probe is used to measure the sheath potential profiles in front of a metal plate biased negative and positive with respect to the plasma potential. For a positive plate bias, the electron density decreases considerably and the electron sheath expands with a longer presheath region compared to the ion sheath. The sheath potential structures are found to follow the Debye sheath model.

Electrostatic potential barrier for electron emission at graphene edges induced by the nearly free electron states

NASA Astrophysics Data System (ADS)

Gao, Yanlin; Okada, Susumu

2017-05-01

Using the density functional theory, we studied the electronic structures of zigzag graphene nanoribbons with hydroxyl, H, ketone, aldehyde, or carboxyl terminations under a lateral electric field. The critical electric field for electron emission is proportional to the work function of the functionalized edges except the hydroxylated edge, which leads to the anomalous electric field outside the edge, owing to the electrons in the nearly free electron (NFE) state in the vacuum region. The strong electric field also causes a potential barrier for the electron emission from the H-terminated edge owing to the downward shift of the NFE state.

Cyanographone and isocyanographone — Two asymmetrically functionalized graphene pseudohalides and their potential use in chemical sensing

NASA Astrophysics Data System (ADS)

Marsoner Steinkasserer, Lukas Eugen; Pohl, Vincent; Paulus, Beate

2018-02-01

Graphene pseudohalides are natural candidates for use in molecular sensing due to their greater chemical activity as compared to both graphene halides and pristine graphene. Though their study is still in its infancy, being hindered until recently by the unavailability of both selective and efficient procedures for their synthesis, they promise to considerably widen the application potential of chemically modified graphenes. Herein, we employ van der Waals density functional theory to study the structural and electronic properties of two selected graphene pseudohalides, namely, cyanographone and isocyanographone and investigate the potential use of the latter as a chemical sensor via electron transport calculations.

A potential half-Heusler thermoelectric material ScAuSn: A first principle study

NASA Astrophysics Data System (ADS)

Joshi, H.; Rai, D. P.; Thapa, R. K.

2018-04-01

Density Functional Theory along with semi classical Boltzmann transport theory have been applied to study the electronic and thermoelectric property of the Heusler alloy ScAuSn. It has been found that ScAuSn is an indirect band gap semiconductor with a gap of 0.344 eV. The thermoelectric properties such as electrical conductivity (σ), Seebeck coefficient (S), electronic thermal conductivity (κ) etc. are reported as a function of chemical potential in the region ± 2.0 eV, with respect to constant temperature. The calculated ZT value is almost equal to 1, thus making ScAuSn a potential thermoelectric candidate.

The role of nurse functional types in seedling recruitment dynamics of alternative states in rangelands

NASA Astrophysics Data System (ADS)

López, Dardo R.; Cavallero, Laura

2017-02-01

In arid ecosystems, recruitment dynamics are limited by harsh environmental conditions and greatly depend on the net outcome of the balance between facilitation and competition. This outcome can change as a consequence of degradation caused by livestock overgrazing. Also, distinct plant species may show a differential response to a common neighbour under the same environmental conditions. Therefore, ecosystem degradation could affect the net balance of plant-plant interactions, which can also depend on the functional traits of potential nurse species. The aim of this study is to assess the influence of alternative degradation states on (i) the density of seedlings of perennial species emerging in four microsite types, and on (ii) the relative interaction intensity (RII) between seedlings and potential nurses belonging to three functional types (deep- and shallow-rooted shrubs, and tussock grasses). During three years, we recorded seedling density of perennial species in four alternative degradation states in grass-shrubby steppes from northwestern Patagonia. The density of emerged seedlings of perennial species decreased sharply as degradation increased, showing non-linear responses in most microsites. Seedling density underneath deep-rooted shrubs was higher than underneath shallow-rooted shrubs and tussock grasses. Also, deep-rooted shrubs were the only functional type that recorded seedling emergence in highly degraded states. Deep-rooted shrubs had facilitative effects on the seedlings emerging and surviving underneath them, independently of ecosystem degradation. In contrast, RII between shallow-rooted shrubs and recently emerged seedlings, switched from positive effects in the less degraded states, to negative effects in the most degraded state. Tussock grasses recorded the weakest intensity of facilitative interactions with recently emerged seedlings, switching to competitive interactions as degradation increased. Our results suggest that species with key functional traits should be considered in management and restoration plans for rangelands with different degradation levels, since they have a strong influence in the net outcome of plant-plant interactions and in the recruitment dynamics of arid ecosystems.

Evolution equation of population genetics: Relation to the density-matrix theory of quasiparticles with general dispersion laws

NASA Astrophysics Data System (ADS)

Bezák, V.

2003-02-01

The Waxman-Peck theory of population genetics is discussed in regard of soil bacteria. Each bacterium is understood as a carrier of a phenotypic parameter p. The central objective is the calculation of the probability density with respect to p, Φ(p,t;p0), of the carriers living at time t>0, provided that initially at t0=0, all bacteria carried the phenotypic parameter p0=0. The theory involves two small parameters: the mutation probability μ and a parameter γ involved in a function w(p) defining the fitness of the bacteria to survive the generation time τ and give birth to an offspring. The mutation from a state p to a state q is defined by a Gaussian with a dispersion σ2m. The author focuses our attention on a function φ(p,t) which determines uniquely the function Φ(p,t;p0) and satisfies a linear equation (Waxman’s equation). The Green function of this equation is mathematically identical with the one-particle Bloch density matrix, where μ characterizes the order of magnitude of the potential energy. (In the x representation, the potential energy is proportional to the inverted Gaussian with the dispersion σ2m). The author solves Waxman’s equation in the standard style of a perturbation theory and discusses how the solution depends on the choice of the fitness function w(p). In a sense, the function c(p)=1-w(p)/w(0) is analogous to the dispersion function E(p) of fictitious quasiparticles. In contrast to Waxman’s approximation, where c(p) was taken as a quadratic function, c(p)≈γp2, the author exemplifies the problem with another function, c(p)=γ[1-exp(-ap2)], where γ is small but a may be large. The author shows that the use of this function in the theory of the population genetics is the same as the use of a nonparabolic dispersion law E=E(p) in the density-matrix theory. With a general function c(p), the distribution function Φ(p,t;0) is composed of a δ-function component, N(t)δ(p), and a blurred component. When discussing the limiting transition for t→∞, the author shows that his function c(p) implies that N(t)→N(∞)≠0 in contrast with the asymptotics N(t)→0 resulting from the use of Waxman’s function c(p)˜p2.

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes.

PubMed

Thostenson, James O; Ngaboyamahina, Edgard; Sellgren, Katelyn L; Hawkins, Brian T; Piascik, Jeffrey R; Klem, Ethan J D; Parker, Charles B; Deshusses, Marc A; Stoner, Brian R; Glass, Jeffrey T

2017-05-17

This work investigates the surface chemistry of H 2 O 2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H 2 O 2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H 2 O 2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H 2 O 2 . Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H 2 O 2 more efficiently compared to static potential methods.

Embedded-atom-method interatomic potentials from lattice inversion.

PubMed

Yuan, Xiao-Jian; Chen, Nan-Xian; Shen, Jiang; Hu, Wangyu

2010-09-22

The present work develops a physically reliable procedure for building the embedded-atom-method (EAM) interatomic potentials for the metals with fcc, bcc and hcp structures. This is mainly based on Chen-Möbius lattice inversion (Chen et al 1997 Phys. Rev. E 55 R5) and first-principles calculations. Following Baskes (Baskes et al 2007 Phys. Rev. B 75 094113), this new version of the EAM eliminates all of the prior arbitrary choices in the determination of the atomic electron density and pair potential functions. Parameterizing the universal form deduced from the calculations within the density-functional scheme for homogeneous electron gas as the embedding function, the new-type EAM potentials for Cu, Fe and Ti metals have successfully been constructed by considering interatomic interactions up to the fifth neighbor, the third neighbor and the seventh neighbor, respectively. The predictions of elastic constants, structural energy difference, vacancy formation energy and migration energy, activation energy of vacancy diffusion, latent heat of melting and relative volume change on melting all satisfactorily agree with the experimental results available or first-principles calculations. The predicted surface energies for low-index crystal faces and the melting point are in agreement with the experimental data to the same extent as those calculated by other EAM-type potentials such as the FBD-EAM, 2NN MEAM and MS-EAM. In addition, the order among the predicted low-index surface energies is also consistent with the experimental information.

You can't run but you can hide: refuge use in frog tadpoles elicits density-dependent predation by dragonfly larvae.

PubMed

Hossie, Thomas John; Murray, Dennis L

2010-06-01

The potential role of prey refuges in stabilizing predator-prey interactions is of longstanding interest to ecologists, but mechanisms underlying a sigmoidal predator functional response remain to be fully elucidated. Authors have disagreed on whether the stabilizing effect of prey refuges is driven by prey- versus predator-centric mechanisms, but to date few studies have married predator and prey behavioural observations to distinguish between these possibilities. We used a dragonfly nymph-tadpole system to study the effect of a structural refuge (leaf litter) on the predator's functional response, and paired this with behavioural observations of both predator and prey. Our study confirmed that hyperbolic (type II) functional responses were characteristic of foraging predators when structural cover was low or absent, whereas the functional response was sigmoidal (type III) when prey were provided with sufficient refuge. Prey activity and refuge use were density independent across cover treatments, thereby eliminating a prey-centric mechanism as being the genesis for density-dependent predation. In contrast, the predator's pursuit length, capture success, and handling time were altered by the amount of structure implying that observed shifts in density-dependent predation likely were related to predator hunting efficiency. Our study advances current theory by revealing that despite fixed-proportion refuge use by prey, presence of a prey refuge can induce density-dependent predation through its effect on predator hunting strategy. Ultimately, responses of predator foraging decisions in response to changes in prey availability and search efficiency may be more important in producing density-dependent predation than the form of prey refuge use.

Optical properties of an indium doped CdSe nanocrystal: A density functional approach

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

Salini, K.; Mathew, Vincent, E-mail: vincent@cukerala.ac.in; Mathew, Thomas

2016-05-06

We have studied the electronic and optical properties of a CdSe nanocrystal doped with n-type impurity atom. First principle calculations of the CdSe nanocrystal based on the density functional theory (DFT), as implemented in the Vienna Ab Initio Simulation Package (VASP) was used in the calculations. We have introduced a single Indium impurity atom into CdSe nanocrystal with 1.3 nm diameter. Nanocrystal surface dangling bonds are passivated with hydrogen atom. The band-structure, density of states and absorption spectra of the doped and undopted nanocrystals were discussed. Inclusion of the n-type impurity atom introduces an additional electron in conduction band, and significantlymore » alters the electronic and optical properties of undoped CdSe nanocrystal. Indium doped CdSe nannocrystal have potential applications in optoelectronic devices.« less

Radial basis function network learns ceramic processing and predicts related strength and density

NASA Technical Reports Server (NTRS)

Cios, Krzysztof J.; Baaklini, George Y.; Vary, Alex; Tjia, Robert E.

1993-01-01

Radial basis function (RBF) neural networks were trained using the data from 273 Si3N4 modulus of rupture (MOR) bars which were tested at room temperature and 135 MOR bars which were tested at 1370 C. Milling time, sintering time, and sintering gas pressure were the processing parameters used as the input features. Flexural strength and density were the outputs by which the RBF networks were assessed. The 'nodes-at-data-points' method was used to set the hidden layer centers and output layer training used the gradient descent method. The RBF network predicted strength with an average error of less than 12 percent and density with an average error of less than 2 percent. Further, the RBF network demonstrated a potential for optimizing and accelerating the development and processing of ceramic materials.

Co-altered functional networks and brain structure in unmedicated patients with bipolar and major depressive disorders.

PubMed

He, Hao; Sui, Jing; Du, Yuhui; Yu, Qingbao; Lin, Dongdong; Drevets, Wayne C; Savitz, Jonathan B; Yang, Jian; Victor, Teresa A; Calhoun, Vince D

2017-12-01

Bipolar disorder (BD) and major depressive disorder (MDD) share similar clinical characteristics that often obscure the diagnostic distinctions between their depressive conditions. Both functional and structural brain abnormalities have been reported in these two disorders. However, the direct link between altered functioning and structure in these two diseases is unknown. To elucidate this relationship, we conducted a multimodal fusion analysis on the functional network connectivity (FNC) and gray matter density from MRI data from 13 BD, 40 MDD, and 33 matched healthy controls (HC). A data-driven fusion method called mCCA+jICA was used to identify the co-altered FNC and gray matter components. Comparing to HC, BD exhibited reduced gray matter density in the parietal and occipital cortices, which correlated with attenuated functional connectivity within sensory and motor networks, as well as hyper-connectivity in regions that are putatively engaged in cognitive control. In addition, lower gray matter density was found in MDD in the amygdala and cerebellum. High accuracy in discriminating across groups was also achieved by trained classification models, implying that features extracted from the fusion analysis hold the potential to ultimately serve as diagnostic biomarkers for mood disorders.

Acute Ischemia Induced by High-Density Culture Increases Cytokine Expression and Diminishes the Function and Viability of Highly Purified Human Islets of Langerhans.

PubMed

Smith, Kate E; Kelly, Amy C; Min, Catherine G; Weber, Craig S; McCarthy, Fiona M; Steyn, Leah V; Badarinarayana, Vasudeo; Stanton, J Brett; Kitzmann, Jennifer P; Strop, Peter; Gruessner, Angelika C; Lynch, Ronald M; Limesand, Sean W; Papas, Klearchos K

2017-11-01

Encapsulation devices have the potential to enable cell-based insulin replacement therapies (such as human islet or stem cell-derived β cell transplantation) without immunosuppression. However, reasonably sized encapsulation devices promote ischemia due to high β cell densities creating prohibitively large diffusional distances for nutrients. It is hypothesized that even acute ischemic exposure will compromise the therapeutic potential of cell-based insulin replacement. In this study, the acute effects of high-density ischemia were investigated in human islets to develop a detailed profile of early ischemia induced changes and targets for intervention. Human islets were exposed in a pairwise model simulating high-density encapsulation to normoxic or ischemic culture for 12 hours, after which viability and function were measured. RNA sequencing was conducted to assess transcriptome-wide changes in gene expression. Islet viability after acute ischemic exposure was reduced compared to normoxic culture conditions (P < 0.01). Insulin secretion was also diminished, with ischemic β cells losing their insulin secretory response to stimulatory glucose levels (P < 0.01). RNA sequencing revealed 657 differentially expressed genes following ischemia, with many that are associated with increased inflammatory and hypoxia-response signaling and decreased nutrient transport and metabolism. In order for cell-based insulin replacement to be applied as a treatment for type 1 diabetes, oxygen and nutrient delivery to β cells will need to be maintained. We demonstrate that even brief ischemic exposure such as would be experienced in encapsulation devices damages islet viability and β cell function and leads to increased inflammatory signaling.

Reexamination of the interaction of atoms with a LiF(001) surface

NASA Astrophysics Data System (ADS)

Miraglia, J. E.; Gravielle, M. S.

2017-02-01

Pairwise additive potentials for multielectronic atoms interacting with a LiF(001) surface are revisited by including an improved description of the electron density associated with the different lattice sites, as well as nonlocal electron density contributions. Within this model, the electron distribution around each ionic site of the crystal is described by means of a so-called "onion" approach that accounts for the influence of the Madelung potential. From such densities, binary interatomic potentials are then derived by using well-known nonlocal functionals. Rumpling and long-range contributions due to projectile polarization and van der Waals forces are also included. We apply this pairwise additive approximation to evaluate the interaction potential between closed-shell (He, Ne, Ar, Kr, and Xe) and open-shell (N, S, and Cl) atoms and the LiF surface, analyzing the relative importance of the different contributions. The performance of the proposed potentials is assessed by contrasting angular positions of rainbow and supernumerary rainbow maxima produced by fast grazing incidence with available experimental data. One important result of our model is that both van der Waals contributions and thermal lattice vibrations play a negligible role for normal energies in the eV range.

Linear and quadratic static response functions and structure functions in Yukawa liquids.

PubMed

Magyar, Péter; Donkó, Zoltán; Kalman, Gabor J; Golden, Kenneth I

2014-08-01

We compute linear and quadratic static density response functions of three-dimensional Yukawa liquids by applying an external perturbation potential in molecular dynamics simulations. The response functions are also obtained from the equilibrium fluctuations (static structure factors) in the system via the fluctuation-dissipation theorems. The good agreement of the quadratic response functions, obtained in the two different ways, confirms the quadratic fluctuation-dissipation theorem. We also find that the three-point structure function may be factorizable into two-point structure functions, leading to a cluster representation of the equilibrium triplet correlation function.

On the ground state energy of the δ-function Bose gas

NASA Astrophysics Data System (ADS)

Tracy, Craig A.; Widom, Harold

2016-07-01

The weak coupling asymptotics, to order {(c/ρ )}2, of the ground state energy of the delta-function Bose gas is derived. Here 2c≥slant 0 is the delta-function potential amplitude and ρ the density of the gas in the thermodynamic limit. The analysis uses the electrostatic interpretation of the Lieb-Liniger integral equation. Dedicated to Professor Tony Guttmann on the occasion of his 70th birthday.

Density of states, optical and thermoelectric properties of perovskite vanadium fluorides Na3VF6

NASA Astrophysics Data System (ADS)

Reshak, A. H.; Azam, Sikander

2014-05-01

The electronic structure, charge density and Fermi surface of Na3VF6 compound have been examined with the support of density functional theory (DFT). Using the full potential linear augmented plane wave method, we employed the local density approximation (LDA), generalized gradient approximation (GGA) and Engel-Vosko GGA (EVGGA) to treat the exchange correlation potential to solve Kohn-Sham equations. The calculation show that Na3VF6 compound has metallic nature and the Fermi energy (EF) is assessed by overlapping of V-d state. The calculated density of states at the EF are about 18.655, 51.932 and 13.235 states/eV, and the bare linear low-temperature electronic specific heat coefficient (γ) is found to be 3.236 mJ/mol-K2, 9.008 mJ/mol-K2 and 2.295 mJ/mol-K2 for LDA, GGA and EVGGA, respectively. The Fermi surface is composed of two sheets. The chemical bonding of Na3VF6 compound is analyzed through the electronic charge density in the (1 1 0) crystallographic plane. The optical constants and thermal properties were also calculated and discussed.

Optimised effective potential for ground states, excited states, and time-dependent phenomena

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

Gross, E.K.U.

1996-12-31

(1) The optimized effective potential method is a variant of the traditional Kohn-Sham scheme. In this variant, the exchange-correlation energy E{sub xc} is an explicit functional of single-particle orbitals. The exchange-correlation potential, given as usual by the functional derivative v{sub xc} = {delta}E{sub xc}/{delta}{rho}, then satisfies as integral equation involving the single-particle orbitals. This integral equation in solved semi-analytically using a scheme recently proposed by Krieger, Li and Iafrate. If the exact (Fock) exchange-energy functional is employed together with the Colle-Salvetti orbital functional for the correlation energy, the mean absolute deviation of the resulting ground-state energies from the exact nonrelativisticmore » values is CT mH for the first-row atoms, as compared to 4.5 mH in a state-of-the-art CI calculation. The proposed scheme is thus significantly more accurate than the conventional Kohn-Sham method while the numerical effort involved is about the same as for an ordinary Hanree-Fock calculation. (2) A time-dependent generalization of the optimized-potential method is presented and applied to the linear-response regime. Since time-dependent density functional theory leads to a formally exact representation of the frequency-dependent linear density response and since the latter, as a function of frequency, has poles at the excitation energies of the fully interacting system, the formalism is suitable for the calculation of excitation energies. A simple additive correction to the Kohn-Sham single-particle excitation energies will be deduced and first results for atomic and molecular singlet and triplet excitation energies will be presented. (3) Beyond the regime of linear response, the time-dependent optimized-potential method is employed to describe atoms in strong emtosecond laser pulses. Ionization yields and harmonic spectra will be presented and compared with experimental data.« less

Anisotropy of the elastic properties of crystalline cellulose Iß from first principles density functional theory with Van der Waals interactions

Treesearch

Fernando L. Dri; Louis G. Jr. Hector; Robert J. Moon; Pablo D. Zavattieri

2013-01-01

In spite of the significant potential of cellulose nanocrystals as functional nanoparticles for numerous applications, a fundamental understanding of the mechanical properties of defect-free, crystalline cellulose is still lacking. In this paper, the elasticity matrix for cellulose Iß with hydrogen bonding network A was calculated using ab initio...

Functional convergence in hydraulic architecture and water relations of tropical savanna trees: from leaf to whole plant.

Treesearch

S.J. Bucci; G. Goldstein; F.C. Meinzer; F.G. Scholz; A.C. France; M. Bustamante

2004-01-01

Functional convergence in hydraulic architecture and water relations, and potential trade-offs in resource allocation were investigated in six dominant neotropical savanna tree species from central Brazil during the peak of the dry season. Common relationships between wood density and several aspects of plant water relations and hydraulic architecture were observed....

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

Generalized Freud's equation and level densities with polynomial potential

NASA Astrophysics Data System (ADS)

Boobna, Akshat; Ghosh, Saugata

2013-08-01

We study orthogonal polynomials with weight $\\exp[-NV(x)]$, where $V(x)=\\sum_{k=1}^{d}a_{2k}x^{2k}/2k$ is a polynomial of order 2d. We derive the generalised Freud's equations for $d=3$, 4 and 5 and using this obtain $R_{\\mu}=h_{\\mu}/h_{\\mu -1}$, where $h_{\\mu}$ is the normalization constant for the corresponding orthogonal polynomials. Moments of the density functions, expressed in terms of $R_{\\mu}$, are obtained using Freud's equation and using this, explicit results of level densities as $N\\rightarrow\\infty$ are derived.

Ground-state properties of trapped Bose-Fermi mixtures: Role of exchange correlation

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

Albus, Alexander P.; Wilkens, Martin; Illuminati, Fabrizio

2003-06-01

We introduce density-functional theory for inhomogeneous Bose-Fermi mixtures, derive the associated Kohn-Sham equations, and determine the exchange-correlation energy in local-density approximation. We solve numerically the Kohn-Sham system, and determine the boson and fermion density distributions and the ground-state energy of a trapped, dilute mixture beyond mean-field approximation. The importance of the corrections due to exchange correlation is discussed by a comparison with current experiments; in particular, we investigate the effect of the repulsive potential-energy contribution due to exchange correlation on the stability of the mixture against collapse.

A multiscale quasi-continuum theory to determine thermodynamic properties of fluid mixtures in nanochannels

NASA Astrophysics Data System (ADS)

Motevaselian, Mohammad Hossein; Mashayak, Sikandar Y.; Aluru, Narayana R.

2015-11-01

We present an empirical potential-based quasi-continuum theory (EQT) that seamlessly integrates the interatomic potentials into a continuum framework such as the Nernst-Planck equation. EQT is a simple and fast approach, which provides accurate predictions of potential of mean force (PMF) and density distribution of confined fluids at multiple length-scales, ranging from few Angstroms to macro meters. The EQT potentials can be used to construct the excess free energy functional in the classical density functional theory (cDFT). The combination of EQT and cDFT (EQT-cDFT), allows one to predict the thermodynamic properties of confined fluids. Recently, the EQT-cDFT framework was developed for single component LJ fluids confined in slit-like graphene channels. In this work, we extend the framework to confined LJ fluid mixtures and demonstrate it by simulating a mixture of methane and hydrogen molecules inside slit-like graphene channels. We show that the EQT-cDFT predictions for the structure of the confined fluid mixture compare well with the MD simulations. In addition, our results show that graphene nanochannels exhibit a selective adsorption of methane over hydrogen.

Sedimentation of a two-dimensional colloidal mixture exhibiting liquid-liquid and gas-liquid phase separation: a dynamical density functional theory study.

PubMed

Malijevský, Alexandr; Archer, Andrew J

2013-10-14

We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.

Low density mesostructures of confined dipolar particles in an external field

NASA Astrophysics Data System (ADS)

Richardi, J.; Weis, J.-J.

2011-09-01

Mesostructures formed by dipolar particles confined between two parallel walls and subjected to an external field are studied by Monte Carlo simulations. The main focus of the work is the structural behavior of the Stockmayer fluid in the low density regime. The dependence of cluster thickness and ordering is estimated as a function of density and wall separation, the two most influential parameters, for large dipole moments and high field strengths. The great sensitivity of the structure to details of the short-range part of the interactions is pointed out. In particular, the attractive part of the Lennard-Jones potential is shown to play a major role in driving chain aggregation. The effect of confinement, evaluated by comparison with results for a bulk system, is most pronounced for a short range hard sphere potential. No evidence is found for a novel "gel-like" phase recently uncovered in low density dipolar colloidal suspensions [A. K. Agarwal and A. Yethiraj, Phys. Rev. Lett. 102, 198301 (2009), 10.1103/PhysRevLett.102.198301].

Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials

NASA Astrophysics Data System (ADS)

Jin, Ye; Yang, Yang; Zhang, Du; Peng, Degao; Yang, Weitao

2017-10-01

The optimized effective potential (OEP) that gives accurate Kohn-Sham (KS) orbitals and orbital energies can be obtained from a given reference electron density. These OEP-KS orbitals and orbital energies are used here for calculating electronic excited states with the particle-particle random phase approximation (pp-RPA). Our calculations allow the examination of pp-RPA excitation energies with the exact KS density functional theory (DFT). Various input densities are investigated. Specifically, the excitation energies using the OEP with the electron densities from the coupled-cluster singles and doubles method display the lowest mean absolute error from the reference data for the low-lying excited states. This study probes into the theoretical limit of the pp-RPA excitation energies with the exact KS-DFT orbitals and orbital energies. We believe that higher-order correlation contributions beyond the pp-RPA bare Coulomb kernel are needed in order to achieve even higher accuracy in excitation energy calculations.

Size-Dependent Surface Energy Density of Spherical Face-Centered-Cubic Metallic Nanoparticles.

PubMed

Wei, Yaochi; Chen, Shaohua

2015-12-01

The surface energy density of nano-sized elements exhibits a significantly size-dependent behavior. Spherical nanoparticle, as an important element in nano-devices and nano-composites, has attracted many interesting studies on size effect, most of which are molecular dynamics (MD) simulations. However, the existing MD calculations yield two opposite size-dependent trends of surface energy density of nanoparticles. In order to clarify such a real underlying problem, atomistic calculations are carried out in the present paper for various spherical face-centered-cubic (fcc) metallic nanoparticles. Both the embedded atom method (EAM) potential and the modified embedded atom method (MEAM) one are adopted. It is found that the size-dependent trend of surface energy density of nanoparticles is not governed by the chosen potential function or variation trend of surface energy, but by the defined radius of spherical nanoparticles in MD models. The finding in the present paper should be helpful for further theoretical studies on surface/interface effect of nanoparticles and nanoparticle-reinforced composites.

DFT benchmark study for the oxidative addition of CH 4 to Pd. Performance of various density functionals

NASA Astrophysics Data System (ADS)

de Jong, G. Theodoor; Geerke, Daan P.; Diefenbach, Axel; Matthias Bickelhaupt, F.

2005-06-01

We have evaluated the performance of 24 popular density functionals for describing the potential energy surface (PES) of the archetypal oxidative addition reaction of the methane C-H bond to the palladium atom by comparing the results with our recent ab initio [CCSD(T)] benchmark study of this reaction. The density functionals examined cover the local density approximation (LDA), the generalized gradient approximation (GGA), meta-GGAs as well as hybrid density functional theory. Relativistic effects are accounted for through the zeroth-order regular approximation (ZORA). The basis-set dependence of the density-functional-theory (DFT) results is assessed for the Becke-Lee-Yang-Parr (BLYP) functional using a hierarchical series of Slater-type orbital (STO) basis sets ranging from unpolarized double-ζ (DZ) to quadruply polarized quadruple-ζ quality (QZ4P). Stationary points on the reaction surface have been optimized using various GGA functionals, all of which yield geometries that differ only marginally. Counterpoise-corrected relative energies of stationary points are converged to within a few tenths of a kcal/mol if one uses the doubly polarized triple-ζ (TZ2P) basis set and the basis-set superposition error (BSSE) drops to 0.0 kcal/mol for our largest basis set (QZ4P). Best overall agreement with the ab initio benchmark PES is achieved by functionals of the GGA, meta-GGA, and hybrid-DFT type, with mean absolute errors of 1.3-1.4 kcal/mol and errors in activation energies ranging from +0.8 to -1.4 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with an only slightly larger mean absolute error of 2.5 kcal/mol and an underestimation by -1.9 kcal/mol of the overall barrier (i.e., the difference in energy between the TS and the separate reactants). For comparison, with B3LYP we arrive at a mean absolute error of 3.8 kcal/mol and an overestimation of the overall barrier by 4.5 kcal/mol.

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

Filinov, A.V.; Golubnychiy, V.O.; Bonitz, M.

Extending our previous work [A.V. Filinov et al., J. Phys. A 36, 5957 (2003)], we present a detailed discussion of accuracy and practical applications of finite-temperature pseudopotentials for two-component Coulomb systems. Different pseudopotentials are discussed: (i) the diagonal Kelbg potential, (ii) the off-diagonal Kelbg potential, (iii) the improved diagonal Kelbg potential, (iv) an effective potential obtained with the Feynman-Kleinert variational principle, and (v) the 'exact' quantum pair potential derived from the two-particle density matrix. For the improved diagonal Kelbg potential, a simple temperature-dependent fit is derived which accurately reproduces the 'exact' pair potential in the whole temperature range. The derivedmore » pseudopotentials are then used in path integral Monte Carlo and molecular-dynamics (MD) simulations to obtain thermodynamical properties of strongly coupled hydrogen. It is demonstrated that classical MD simulations with spin-dependent interaction potentials for the electrons allow for an accurate description of the internal energy of hydrogen in the difficult regime of partial ionization down to the temperatures of about 60 000 K. Finally, we point out an interesting relationship between the quantum potentials and the effective potentials used in density-functional theory.« less

Lung function reductions associated with motor vehicle density in chronic obstructive pulmonary disease: a cross-sectional study.

PubMed

Nitschke, Monika; Appleton, Sarah L; Li, Qiaoyu; Tucker, Graeme R; Shah, Pushan; Bi, Peng; Pisaniello, Dino L; Adams, Robert J

2016-10-24

Motor vehicle-related air pollution can potentially impair lung function. The effect of pollution in people with compromised pulmonary function such as in COPD has not been previously investigated. To examine the association of lung function with motor vehicle density in people with spirometrically determined COPD in a cross-sectional study. In 2004-06, The North West Adelaide Health Study (NWAHS), a biomedical cohort of adults assessed pre and post-bronchodilator spirometry (n = 3,103). Traffic density, obtained from the motor vehicle inventory maintained by the South Australian Environment Protection Authority, was expressed as the daily numbers of vehicles travelling within a 200 m diameter zone around participants' geocoded residences. In subjects with COPD (FEV 1 /FVC <0.7, n = 221, 7.1 %), increasing daily vehicle density was associated with statistically significant decreases in lung function parameters after adjustment for smoking and socio-economic variables. Mean (95 % CI) post-bronchodilator % predicted FEV 1 was 81 % (76-87) in the low (≤7179/day) compared with 71 % (67-75) in the high (≥15,270/day) vehicle exposure group (p < 0.05). Linear regression analysis in all subjects with COPD showed significant decrements in post-bronchodilator FEV 1 /FVC ratio and % predicted FEV 1 of 0.03 and 0.05 % respectively per daily increase in 1000 vehicles. In men with COPD (n = 150), the corresponding reductions were 0.03 and 0.06 %. Smaller, non-significant decrements were seen in females. No difference was seen in those without COPD. Vehicle traffic density was associated with significant reductions in lung function in people with COPD. Urban planning should consider the health impacts for those with pre-existing respiratory conditions.

The Impact of Alcohol Outlet Density on the Geographic Clustering of Underage Drinking Behaviors within Census Tracts

PubMed Central

Reboussin, Beth A.; Song, Eun-Young; Wolfson, Mark

2011-01-01

Background The regulation of alcohol outlet density has been considered as a potential means of reducing alcohol consumption and related harms among underage youth. Whereas prior studies have examined whether alcohol outlet density was associated with an individual’s alcohol consumption and related harms, this study examines whether it is related to the co-occurrence, or clustering, of these behaviors within geographic areas, specifically census tracts. Methods The Enforcing Underage Drinking Laws Randomized Community Trial provided cross-sectional telephone survey data in 2006 and 2007 from 10,754 youth aged 14–20 from 5 states residing in 1556 census tracts. The alternating logistic regression approach was used to estimate pairwise odds ratios between responses from youth residing in the same census tract and to model them as a function of alcohol outlet density. Results Riding with a drinking driver, making an alcohol purchase attempt and making a successful alcohol purchase attempt clustered significantly within census tracts with the highest off-premise alcohol outlet density while frequent drinking clustered within census tracts with the greatest on-premise density. Driving after drinking and experiencing non-violent alcohol-related consequences clustered marginally within census tracts with the greatest on-premise and off-premise alcohol outlet density, respectively. Conclusions Although youth primarily receive alcohol from social sources, commercial alcohol access is geographically concentrated within census tracts with the greatest off-premise outlet density. A potentially greater concern is the clustering of more frequent drinking and drinking and driving within census tracts with the greatest on-premise outlet density which may necessitate alternative census tract level initiatives to reduce these potentially harmful behaviors. PMID:21463343

Multiple density dependence in two sub-populations of the amphipod Monoporeia affinis: a potential for alternative equilibria.

PubMed

Leonardsson, Kjell

1994-02-01

Possible mechanisms for differences in population densities and dynamics were investigated in the amphipod Monoporeia affinis at two deep sites in the northern Bothnian Sea. The two sites were sampled yearly for 10 years. Average sizes, growth and mortality of the different age-classes were estimated from the cohort structure of the two populations. Laboratory experiments also investigated the ability of the common predatory isopod Saduria entomon to cause densitydependent (DD) mortality of the prey M. affinis. At site A, 43 m depth, the average density of M. affinis was twice as high as at site B, 81 m depth. The fluctuations in density were asynchronous between the two sites. Recruitment and subadult sizes of Monoporeia affinis were density dependent at both sites. The main functional difference between the two populations seemed to be the DD mortality of the 1 + cohort that occurred only at the low-density site B. A corresponding DD mortality was found in the predation experiments at densities of 1 + m. affinis corresponding to those found at site B. The potential importance of the predator was also indicated by a significant negative correlation between the biomass of S. entomon and the rate of change in M. affinis density in the field. The similarities in the abiotic factors between the two sites suggested that differences in carrying capacity should be small. The results could be explained by the predation regulation hypothesis for the low-density population at site B, while at site A M. affinis seemed to be regulated by intra-specific competition and limited by predation. It is suggested that in this simple predator-prey system there is potential for the existence of alternative equilibria.

Generalized non-equilibrium vertex correction method in coherent medium theory for quantum transport simulation of disordered nanoelectronics

NASA Astrophysics Data System (ADS)

Yan, Jiawei; Ke, Youqi

In realistic nanoelectronics, disordered impurities/defects are inevitable and play important roles in electron transport. However, due to the lack of effective quantum transport method, the important effects of disorders remain poorly understood. Here, we report a generalized non-equilibrium vertex correction (NVC) method with coherent potential approximation to treat the disorder effects in quantum transport simulation. With this generalized NVC method, any averaged product of two single-particle Green's functions can be obtained by solving a set of simple linear equations. As a result, the averaged non-equilibrium density matrix and various important transport properties, including averaged current, disordered induced current fluctuation and the averaged shot noise, can all be efficiently computed in a unified scheme. Moreover, a generalized form of conditionally averaged non-equilibrium Green's function is derived to incorporate with density functional theory to enable first-principles simulation. We prove the non-equilibrium coherent potential equals the non-equilibrium vertex correction. Our approach provides a unified, efficient and self-consistent method for simulating non-equilibrium quantum transport through disorder nanoelectronics. Shanghaitech start-up fund.

Ionic structures and transport properties of hot dense W and U plasmas

NASA Astrophysics Data System (ADS)

Hou, Yong; Yuan, Jianmin

2016-10-01

We have combined the average-atom model with the hyper-netted chain approximation (AAHNC) to describe the electronic and ionic structure of uranium and tungsten in the hot dense matter regime. When the electronic structure is described within the average-atom model, the effects of others ions on the electronic structure are considered by the correlation functions. And the ionic structure is calculated though using the hyper-netted chain (HNC) approximation. The ion-ion pair potential is calculated using the modified Gordon-Kim model based on the electronic density distribution in the temperature-depended density functional theory. And electronic and ionic structures are determined self-consistently. On the basis of the ion-ion pair potential, we perform the classical (CMD) and Langevin (LMD) molecular dynamics to simulate the ionic transport properties, such as ionic self-diffusion and shear viscosity coefficients, through the ionic velocity correlation functions. Due that the free electrons become more and more with increasing the plasma temperature, the influence of the electron-ion collisions on the transport properties become more and more important.

Analysis of nanopore arrangement of porous alumina layers formed by anodizing in oxalic acid at relatively high temperatures

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Stępniowski, Wojciech J.; Jaskuła, Marian; Sulka, Grzegorz D.

2014-06-01

Anodic aluminum oxide (AAO) layers were formed by a simple two-step anodization in 0.3 M oxalic acid at relatively high temperatures (20-30 °C) and various anodizing potentials (30-65 V). The effect of anodizing conditions on structural features of as-obtained oxides was carefully investigated. A linear and exponential relationships between cell diameter, pore density and anodizing potential were confirmed, respectively. On the other hand, no effect of temperature and duration of anodization on pore spacing and pore density was found. Detailed quantitative and qualitative analyses of hexagonal arrangement of nanopore arrays were performed for all studied samples. The nanopore arrangement was evaluated using various methods based on the fast Fourier transform (FFT) images, Delaunay triangulations (defect maps), pair distribution functions (PDF), and angular distribution functions (ADF). It was found that for short anodizations performed at relatively high temperatures, the optimal anodizing potential that results in formation of nanostructures with the highest degree of pore order is 45 V. No direct effect of temperature and time of anodization on the nanopore arrangement was observed.

Effect of the nonlocal exchange on the performance of the orbital-dependent correlation functionals from second-order perturbation theory.

PubMed

Schweigert, Igor V; Bartlett, Rodney J

2008-09-28

Adding a fraction of the nonlocal exchange operator to the local orbital-dependent exchange potential improves the many-body perturbation expansion based on the Kohn-Sham determinant. The effect of such a hybrid scheme on the performance of the orbital-dependent correlation functional from the second-order perturbation theory (PT2H) is investigated numerically. A small fraction of the nonlocal exchange is often sufficient to ensure the existence of the self-consistent solution for the PT2H potential. In the He and Be atoms, including 37% of the nonlocal exchange leads to the correlation energies and electronic densities that are very close to the exact ones. In molecules, varying the fraction of the nonlocal exchange may result in the PT2H energy closely reproducing the CCSD(T) value; however such a fraction depends on the system and does not always result in an accurate electronic density. We also numerically verify that the "semicanonical" perturbation series includes most of the beneficial effects of the nonlocal exchange without sacrificing the locality of the exchange potential.

Vibrational spectra, DFT quantum chemical calculations and conformational analysis of P-iodoanisole.

PubMed

Arivazhagan, M; Anitha Rexalin, D; Geethapriya, J

2013-09-01

The solid phase FT-IR and FT-Raman spectra of P-iodoanisole (P-IA) 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 ab initio (HF) and density functional theory (B3LYP) methods with LanL2DZ as basis set. The potential energy surface scan for the selected dihedral angle of P-IA has been performed to identify stable conformer. The optimized structure parameters and vibrational wavenumbers of stable conformer have been predicted by density functional B3LYP method with LanL2DZ (with effective core potential representations of electrons near the nuclei for post-third row atoms) basis set. The nucleophilic and electrophilic sites obtained from the molecular electrostatic potential (MEP) surface were calculated. The temperature dependence of thermodynamic properties has been analyzed. Several thermodynamic parameters have been calculated using B3LYP with LanL2DZ basis set. Copyright © 2013 Elsevier B.V. All rights reserved.

Rationally designed polyimides for high-energy density capacitor applications.

PubMed

Ma, Rui; Baldwin, Aaron F; Wang, Chenchen; Offenbach, Ido; Cakmak, Mukerrem; Ramprasad, Rampi; Sotzing, Gregory A

2014-07-09

Development of new dielectric materials is of great importance for a wide range of applications for modern electronics and electrical power systems. The state-of-the-art polymer dielectric is a biaxially oriented polypropylene (BOPP) film having a maximal energy density of 5 J/cm(3) and a high breakdown field of 700 MV/m, but with a limited dielectric constant (∼2.2) and a reduced breakdown strength above 85 °C. Great effort has been put into exploring other materials to fulfill the demand of continuous miniaturization and improved functionality. In this work, a series of polyimides were investigated as potential polymer materials for this application. Polyimide with high dielectric constants of up to 7.8 that exhibits low dissipation factors (<1%) and high energy density around 15 J/cm(3), which is 3 times that of BOPP, was prepared. Our syntheses were guided by high-throughput density functional theory calculations for rational design in terms of a high dielectric constant and band gap. Correlations of experimental and theoretical results through judicious variations of polyimide structures allowed for a clear demonstration of the relationship between chemical functionalities and dielectric properties.

Binary collision approximations for the memory function for density fluctuations in equilibrium atomic liquids

NASA Astrophysics Data System (ADS)

Noah, Joyce E.

Time correlation functions of density fluctuations of liquids at equilibrium can be used to relate the microscopic dynamics of a liquid to its macroscopic transport properties. Time correlation functions are especially useful since they can be generated in a variety of ways, from scattering experiments to computer simulation to analytic theory. The kinetic theory of fluctuations in equilibrium liquids is an analytic theory for calculating correlation functions using memory functions. In this work, we use a diagrammatic formulation of the kinetic theory to develop a series of binary collision approximations for the collisional part of the memory function. We define binary collisions as collisions between two distinct density fluctuations whose identities are fixed during the duration of a collsion. R approximations are for the short time part of the memory function, and build upon the work of Ranganathan and Andersen. These approximations have purely repulsive interactions between the fluctuations. The second type of approximation, RA approximations, is for the longer time part of the memory function, where the density fluctuations now interact via repulsive and attractive forces. Although RA approximations are a natural extension of R approximations, they permit two density fluctuations to become trapped in the wells of the interaction potential, leading to long-lived oscillatory behavior, which is unphysical. Therefore we consider S approximations which describe binary particles which experience the random effect of the surroundings while interacting via repulsive or repulsive and attractive interactions. For each of these approximations for the memory function we numerically solve the kinetic equation to generate correlation functions. These results are compared to molecular dynamics results for the correlation functions. Comparing the successes and failures of the different approximations, we conclude that R approximations give more accurate intermediate and long time results while RA and S approximations do particularly well at predicting the short time behavior. Lastly, we also develop a series of non-graphically derived approximations and use an optimization procedure to determine the underlying memory function from the simulation data. These approaches provide valuable information about the memory function that will be used in the development of future kinetic theories.

Ab Initio Optimized Effective Potentials for Real Molecules in Optical Cavities: Photon Contributions to the Molecular Ground State

PubMed Central

2018-01-01

We introduce a simple scheme to efficiently compute photon exchange-correlation contributions due to the coupling to transversal photons as formulated in the newly developed quantum-electrodynamical density-functional theory (QEDFT).1−5 Our construction employs the optimized-effective potential (OEP) approach by means of the Sternheimer equation to avoid the explicit calculation of unoccupied states. We demonstrate the efficiency of the scheme by applying it to an exactly solvable GaAs quantum ring model system, a single azulene molecule, and chains of sodium dimers, all located in optical cavities and described in full real space. While the first example is a two-dimensional system and allows to benchmark the employed approximations, the latter two examples demonstrate that the correlated electron-photon interaction appreciably distorts the ground-state electronic structure of a real molecule. By using this scheme, we not only construct typical electronic observables, such as the electronic ground-state density, but also illustrate how photon observables, such as the photon number, and mixed electron-photon observables, for example, electron–photon correlation functions, become accessible in a density-functional theory (DFT) framework. This work constitutes the first three-dimensional ab initio calculation within the new QEDFT formalism and thus opens up a new computational route for the ab initio study of correlated electron–photon systems in quantum cavities. PMID:29594185

Microhartree precision in density functional theory calculations

NASA Astrophysics Data System (ADS)

Gulans, Andris; Kozhevnikov, Anton; Draxl, Claudia

2018-04-01

To address ultimate precision in density functional theory calculations we employ the full-potential linearized augmented plane-wave + local-orbital (LAPW + lo) method and justify its usage as a benchmark method. LAPW + lo and two completely unrelated numerical approaches, the multiresolution analysis (MRA) and the linear combination of atomic orbitals, yield total energies of atoms with mean deviations of 0.9 and 0.2 μ Ha , respectively. Spectacular agreement with the MRA is reached also for total and atomization energies of the G2-1 set consisting of 55 molecules. With the example of α iron we demonstrate the capability of LAPW + lo to reach μ Ha /atom precision also for periodic systems, which allows also for the distinction between the numerical precision and the accuracy of a given functional.

Formation of the Electric Double Layer and its Effects on Moving Bodies in a Space Plasma Environment

NASA Technical Reports Server (NTRS)

Yang, Qianli; Wu, S. T.; Stone, N. H.; Li, Xiaoquing

1996-01-01

In this paper we solve the self-consistent Vlasov and Poisson equations by a numerical method to determine the local distribution function of the ion and the electron, within a thin layer near the moving body, respectively. Using these ion and electron distributions, the number density for the ions and electrons are determined, such that, the electric potential is obtained within this thin layer (i.e., measured by Debye length). Numerical results are presented for temporal evolution of the electron and ion density and its corresponding electric potential within the layer which shows the formation of electric double layer and its structures. From these numerical results, we are able to determine the maximum conditions of the electric potential, it may create satellite anomaly.

Numerical experiment to estimate the validity of negative ion diagnostic using photo-detachment combined with Langmuir probing

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

Oudini, N.; Sirse, N.; Ellingboe, A. R.

2015-07-15

This paper presents a critical assessment of the theory of photo-detachment diagnostic method used to probe the negative ion density and electronegativity α = n{sub -}/n{sub e}. In this method, a laser pulse is used to photo-detach all negative ions located within the electropositive channel (laser spot region). The negative ion density is estimated based on the assumption that the increase of the current collected by an electrostatic probe biased positively to the plasma is a result of only the creation of photo-detached electrons. In parallel, the background electron density and temperature are considered as constants during this diagnostics. While the numericalmore » experiments performed here show that the background electron density and temperature increase due to the formation of an electrostatic potential barrier around the electropositive channel. The time scale of potential barrier rise is about 2 ns, which is comparable to the time required to completely photo-detach the negative ions in the electropositive channel (∼3 ns). We find that neglecting the effect of the potential barrier on the background plasma leads to an erroneous determination of the negative ion density. Moreover, the background electron velocity distribution function within the electropositive channel is not Maxwellian. This is due to the acceleration of these electrons through the electrostatic potential barrier. In this work, the validity of the photo-detachment diagnostic assumptions is questioned and our results illustrate the weakness of these assumptions.« less

Calculation of the dielectric properties of semiconductors

NASA Astrophysics Data System (ADS)

Engel, G. E.; Farid, Behnam

1992-12-01

We report on numerical calculations of the dynamical dielectric function in silicon, using a continued-fraction expansion of the polarizability and a recently proposed representation of the inverse dielectric function in terms of plasmonlike excitations. A number of important technical refinements to further improve the computational efficiency of the method are introduced, making the ab initio calculation of the full energy dependence of the dielectric function comparable in cost to calculation of its static value. Physical results include the observation of previously unresolved features in the random-phase approximated dielectric function and its inverse within the framework of density-functional theory in the local-density approximation, which may be accessible to experiment. We discuss the dispersion of plasmon energies in silicon along the Λ and Δ directions and find improved agreement with experiment compared to earlier calculations. We also present quantitative evidence indicating the degree of violation of the Johnson f-sum rule for the dielectric function due to the nonlocality of the one-electron potential used in the underlying band-structure calculations.

Phytochemical, spectroscopic and density functional theory study of Diospyrin, and non-bonding interactions of Diospyrin with atmospheric gases

NASA Astrophysics Data System (ADS)

Fazl-i-Sattar; Ullah, Zakir; Ata-ur-Rahman; Rauf, Abdur; Tariq, Muhammad; Tahir, Asif Ali; Ayub, Khurshid; Ullah, Habib

2015-04-01

Density functional theory (DFT) and phytochemical study of a natural product, Diospyrin (DO) have been carried out. A suitable level of theory was developed, based on correlating the experimental and theoretical data. Hybrid DFT method at B3LYP/6-31G (d,p) level of theory is employed for obtaining the electronic, spectroscopic, inter-molecular interaction and thermodynamic properties of DO. The exact structure of DO is confirmed from the nice validation of the theory and experiment. Non-covalent interactions of DO with different atmospheric gases such as NH3, CO2, CO, and H2O were studied to find out its electroactive nature. The experimental and predicted geometrical parameters, IR and UV-vis spectra (B3LYP/6-31+G (d,p) level of theory) show excellent correlation. Inter-molecular non-bonding interaction of DO with atmospheric gases is investigated through geometrical parameters, electronic properties, charge analysis, and thermodynamic parameters. Electronic properties include, ionization potential (I.P.), electron affinities (E.A.), electrostatic potential (ESP), density of states (DOS), HOMO, LUMO, and band gap. All these characterizations have corroborated each other and confirmed the presence of non-covalent nature in DO with the mentioned gases.

Development of Colle-Salvetti type electron-nucleus correlation functional for MC-DFT

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

Udagawa, Taro; Tsuneda, Takao; Tachikawa, Masanori

2015-12-31

A Colle-Salvetti type electron-nucleus correlation functional for multicomponent density-functional theory is proposed. We demonstrate that our correlation functional quantitatively reproduces the quantum nuclear effects of protons; the mean absolute deviation value is 2.8 millihartrees for the optimized structure of hydrogen-containing molecules. We also show other practical calculations with our new electron-deuteron and electron-triton correlation functionals. Since this functional is derived without any unphysical assumption, the strategy taken in this development will be a promising recipe to make new functionals for the potentials of other particles’ interactions.

Use of Two-Body Correlated Basis Functions with van der Waals Interaction to Study the Shape-Independent Approximation for a Large Number of Trapped Interacting Bosons

NASA Astrophysics Data System (ADS)

Lekala, M. L.; Chakrabarti, B.; Das, T. K.; Rampho, G. J.; Sofianos, S. A.; Adam, R. M.; Haldar, S. K.

2017-05-01

We study the ground-state and the low-lying excitations of a trapped Bose gas in an isotropic harmonic potential for very small (˜ 3) to very large (˜ 10^7) particle numbers. We use the two-body correlated basis functions and the shape-dependent van der Waals interaction in our many-body calculations. We present an exhaustive study of the effect of inter-atomic correlations and the accuracy of the mean-field equations considering a wide range of particle numbers. We calculate the ground-state energy and the one-body density for different values of the van der Waals parameter C6. We compare our results with those of the modified Gross-Pitaevskii results, the correlated Hartree hypernetted-chain equations (which also utilize the two-body correlated basis functions), as well as of the diffusion Monte Carlo for hard sphere interactions. We observe the effect of the attractive tail of the van der Waals potential in the calculations of the one-body density over the truly repulsive zero-range potential as used in the Gross-Pitaevskii equation and discuss the finite-size effects. We also present the low-lying collective excitations which are well described by a hydrodynamic model in the large particle limit.

Optical-model potential for electron and positron elastic scattering by atoms

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

Salvat, Francesc

2003-07-01

An optical-model potential for systematic calculations of elastic scattering of electrons and positrons by atoms and positive ions is proposed. The electrostatic interaction is determined from the Dirac-Hartree-Fock self-consistent atomic electron density. In the case of electron projectiles, the exchange interaction is described by means of the local-approximation of Furness and McCarthy. The correlation-polarization potential is obtained by combining the correlation potential derived from the local density approximation with a long-range polarization interaction, which is represented by means of a Buckingham potential with an empirical energy-dependent cutoff parameter. The absorption potential is obtained from the local-density approximation, using the Born-Ochkurmore » approximation and the Lindhard dielectric function to describe the binary collisions with a free-electron gas. The strength of the absorption potential is adjusted by means of an empirical parameter, which has been determined by fitting available absolute elastic differential cross-section data for noble gases and mercury. The Dirac partial-wave analysis with this optical-model potential provides a realistic description of elastic scattering of electrons and positrons with energies in the range from {approx}100 eV up to {approx}5 keV. At higher energies, correlation-polarization and absorption corrections are small and the usual static-exchange approximation is sufficiently accurate for most practical purposes.« less

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

Huang, Chen, E-mail: chuang3@fsu.edu

A key element in the density functional embedding theory (DFET) is the embedding potential. We discuss two major issues related to the embedding potential: (1) its non-uniqueness and (2) the numerical difficulty for solving for it, especially for the spin-polarized systems. To resolve the first issue, we extend DFET to finite temperature: all quantities, such as the subsystem densities and the total system’s density, are calculated at a finite temperature. This is a physical extension since materials work at finite temperatures. We show that the embedding potential is strictly unique at T > 0. To resolve the second issue, wemore » introduce an efficient iterative embedding potential solver. We discuss how to relax the magnetic moments in subsystems and how to equilibrate the chemical potentials across subsystems. The solver is robust and efficient for several non-trivial examples, in all of which good quality spin-polarized embedding potentials were obtained. We also demonstrate the solver on an extended periodic system: iron body-centered cubic (110) surface, which is related to the modeling of the heterogeneous catalysis involving iron, such as the Fischer-Tropsch and the Haber processes. This work would make it efficient and accurate to perform embedding simulations of some challenging material problems, such as the heterogeneous catalysis and the defects of complicated spin configurations in electronic materials.« less

Robust determination of the chemical potential in the pole expansion and selected inversion method for solving Kohn-Sham density functional theory

NASA Astrophysics Data System (ADS)

Jia, Weile; Lin, Lin

2017-10-01

Fermi operator expansion (FOE) methods are powerful alternatives to diagonalization type methods for solving Kohn-Sham density functional theory (KSDFT). One example is the pole expansion and selected inversion (PEXSI) method, which approximates the Fermi operator by rational matrix functions and reduces the computational complexity to at most quadratic scaling for solving KSDFT. Unlike diagonalization type methods, the chemical potential often cannot be directly read off from the result of a single step of evaluation of the Fermi operator. Hence multiple evaluations are needed to be sequentially performed to compute the chemical potential to ensure the correct number of electrons within a given tolerance. This hinders the performance of FOE methods in practice. In this paper, we develop an efficient and robust strategy to determine the chemical potential in the context of the PEXSI method. The main idea of the new method is not to find the exact chemical potential at each self-consistent-field (SCF) iteration but to dynamically and rigorously update the upper and lower bounds for the true chemical potential, so that the chemical potential reaches its convergence along the SCF iteration. Instead of evaluating the Fermi operator for multiple times sequentially, our method uses a two-level strategy that evaluates the Fermi operators in parallel. In the regime of full parallelization, the wall clock time of each SCF iteration is always close to the time for one single evaluation of the Fermi operator, even when the initial guess is far away from the converged solution. We demonstrate the effectiveness of the new method using examples with metallic and insulating characters, as well as results from ab initio molecular dynamics.

Robust determination of the chemical potential in the pole expansion and selected inversion method for solving Kohn-Sham density functional theory.

PubMed

Jia, Weile; Lin, Lin

2017-10-14

Fermi operator expansion (FOE) methods are powerful alternatives to diagonalization type methods for solving Kohn-Sham density functional theory (KSDFT). One example is the pole expansion and selected inversion (PEXSI) method, which approximates the Fermi operator by rational matrix functions and reduces the computational complexity to at most quadratic scaling for solving KSDFT. Unlike diagonalization type methods, the chemical potential often cannot be directly read off from the result of a single step of evaluation of the Fermi operator. Hence multiple evaluations are needed to be sequentially performed to compute the chemical potential to ensure the correct number of electrons within a given tolerance. This hinders the performance of FOE methods in practice. In this paper, we develop an efficient and robust strategy to determine the chemical potential in the context of the PEXSI method. The main idea of the new method is not to find the exact chemical potential at each self-consistent-field (SCF) iteration but to dynamically and rigorously update the upper and lower bounds for the true chemical potential, so that the chemical potential reaches its convergence along the SCF iteration. Instead of evaluating the Fermi operator for multiple times sequentially, our method uses a two-level strategy that evaluates the Fermi operators in parallel. In the regime of full parallelization, the wall clock time of each SCF iteration is always close to the time for one single evaluation of the Fermi operator, even when the initial guess is far away from the converged solution. We demonstrate the effectiveness of the new method using examples with metallic and insulating characters, as well as results from ab initio molecular dynamics.

Self-consistent implementation of meta-GGA functionals for the ONETEP linear-scaling electronic structure package.

PubMed

Womack, James C; Mardirossian, Narbe; Head-Gordon, Martin; Skylaris, Chris-Kriton

2016-11-28

Accurate and computationally efficient exchange-correlation functionals are critical to the successful application of linear-scaling density functional theory (DFT). Local and semi-local functionals of the density are naturally compatible with linear-scaling approaches, having a general form which assumes the locality of electronic interactions and which can be efficiently evaluated by numerical quadrature. Presently, the most sophisticated and flexible semi-local functionals are members of the meta-generalized-gradient approximation (meta-GGA) family, and depend upon the kinetic energy density, τ, in addition to the charge density and its gradient. In order to extend the theoretical and computational advantages of τ-dependent meta-GGA functionals to large-scale DFT calculations on thousands of atoms, we have implemented support for τ-dependent meta-GGA functionals in the ONETEP program. In this paper we lay out the theoretical innovations necessary to implement τ-dependent meta-GGA functionals within ONETEP's linear-scaling formalism. We present expressions for the gradient of the τ-dependent exchange-correlation energy, necessary for direct energy minimization. We also derive the forms of the τ-dependent exchange-correlation potential and kinetic energy density in terms of the strictly localized, self-consistently optimized orbitals used by ONETEP. To validate the numerical accuracy of our self-consistent meta-GGA implementation, we performed calculations using the B97M-V and PKZB meta-GGAs on a variety of small molecules. Using only a minimal basis set of self-consistently optimized local orbitals, we obtain energies in excellent agreement with large basis set calculations performed using other codes. Finally, to establish the linear-scaling computational cost and applicability of our approach to large-scale calculations, we present the outcome of self-consistent meta-GGA calculations on amyloid fibrils of increasing size, up to tens of thousands of atoms.

Self-consistent implementation of meta-GGA functionals for the ONETEP linear-scaling electronic structure package

NASA Astrophysics Data System (ADS)

Womack, James C.; Mardirossian, Narbe; Head-Gordon, Martin; Skylaris, Chris-Kriton

2016-11-01

Accurate and computationally efficient exchange-correlation functionals are critical to the successful application of linear-scaling density functional theory (DFT). Local and semi-local functionals of the density are naturally compatible with linear-scaling approaches, having a general form which assumes the locality of electronic interactions and which can be efficiently evaluated by numerical quadrature. Presently, the most sophisticated and flexible semi-local functionals are members of the meta-generalized-gradient approximation (meta-GGA) family, and depend upon the kinetic energy density, τ, in addition to the charge density and its gradient. In order to extend the theoretical and computational advantages of τ-dependent meta-GGA functionals to large-scale DFT calculations on thousands of atoms, we have implemented support for τ-dependent meta-GGA functionals in the ONETEP program. In this paper we lay out the theoretical innovations necessary to implement τ-dependent meta-GGA functionals within ONETEP's linear-scaling formalism. We present expressions for the gradient of the τ-dependent exchange-correlation energy, necessary for direct energy minimization. We also derive the forms of the τ-dependent exchange-correlation potential and kinetic energy density in terms of the strictly localized, self-consistently optimized orbitals used by ONETEP. To validate the numerical accuracy of our self-consistent meta-GGA implementation, we performed calculations using the B97M-V and PKZB meta-GGAs on a variety of small molecules. Using only a minimal basis set of self-consistently optimized local orbitals, we obtain energies in excellent agreement with large basis set calculations performed using other codes. Finally, to establish the linear-scaling computational cost and applicability of our approach to large-scale calculations, we present the outcome of self-consistent meta-GGA calculations on amyloid fibrils of increasing size, up to tens of thousands of atoms.

Assessment of strontium oxide functionalized graphene nanoflakes for enhanced photocatalytic activity: A density functional theory approach

NASA Astrophysics Data System (ADS)

Divya, A.; Mathavan, T.; Asath, R. Mohamed; Archana, J.; Hayakawa, Y.; Benial, A. Milton Franklin

2016-05-01

A series of strontium oxide functionalized graphene nanoflakes were designed and their optoelectronic properties were studied for enhanced photocatalytic activity. The efficiency of designed molecules was studied using various parameters such as HOMO-LUMO energy gap, light harvesting efficiency and exciton binding energy. The computed results show that by increasing the degree of functionalization of strontium oxide leads to lowering the band gap of hydrogen terminated graphene nanoflakes. Furthermore, the study explores the role of strontium oxide functionalization in Frontier Molecular Orbitals, ionization potential, electron affinity, exciton binding energy and light harvesting efficiency of designed molecules. The infrared and Raman spectra were simulated for pure and SrO functionalized graphene nanoflakes. The electron rich and electron deficient regions which are favorable for electrophilic and nucleophilic attacks respectively were analyzed using molecular electrostatic potential surface analysis.

High density lipoprotein and metabolic disease: Potential benefits of restoring its functional properties

PubMed Central

Klancic, Teja; Woodward, Lavinia; Hofmann, Susanna M.; Fisher, Edward A.

2016-01-01

Background High density lipoproteins (HDLs) are thought to be atheroprotective and to reduce the risk of cardiovascular disease (CVD). Besides their antioxidant, antithrombotic, anti-inflammatory, anti-apoptotic properties in the vasculature, HDLs also improve glucose metabolism in skeletal muscle. Scope of the review Herein, we review the functional role of HDLs to improve metabolic disorders, especially those involving insulin resistance and to induce regression of CVD with a particular focus on current pharmacological treatment options as well as lifestyle interventions, particularly exercise. Major conclusions Functional properties of HDLs continue to be considered important mediators to reverse metabolic dysfunction and to regress atherosclerotic cardiovascular disease. Lifestyle changes are often recommended to reduce the risk of CVD, with exercise being one of the most important of these. Understanding how exercise improves HDL function will likely lead to new approaches to battle the expanding burden of obesity and the metabolic syndrome. PMID:27110484

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

Theophilou, Iris; Helbig, Nicole; Lathiotakis, Nektarios N.

Functionals of the one-body reduced density matrix (1-RDM) are routinely minimized under Coleman’s ensemble N-representability conditions. Recently, the topic of pure-state N-representability conditions, also known as generalized Pauli constraints, received increased attention following the discovery of a systematic way to derive them for any number of electrons and any finite dimensionality of the Hilbert space. The target of this work is to assess the potential impact of the enforcement of the pure-state conditions on the results of reduced density-matrix functional theory calculations. In particular, we examine whether the standard minimization of typical 1-RDM functionals under the ensemble N-representability conditions violatesmore » the pure-state conditions for prototype 3-electron systems. We also enforce the pure-state conditions, in addition to the ensemble ones, for the same systems and functionals and compare the correlation energies and optimal occupation numbers with those obtained by the enforcement of the ensemble conditions alone.« less

Constraining cosmology with the velocity function of low-mass galaxies

NASA Astrophysics Data System (ADS)

Schneider, Aurel; Trujillo-Gomez, Sebastian

2018-04-01

The number density of field galaxies per rotation velocity, referred to as the velocity function, is an intriguing statistical measure probing the smallest scales of structure formation. In this paper we point out that the velocity function is sensitive to small shifts in key cosmological parameters such as the amplitude of primordial perturbations (σ8) or the total matter density (Ωm). Using current data and applying conservative assumptions about baryonic effects, we show that the observed velocity function of the Local Volume favours cosmologies in tension with the measurements from Planck but in agreement with the latest findings from weak lensing surveys. While the current systematics regarding the relation between observed and true rotation velocities are potentially important, upcoming data from H I surveys as well as new insights from hydrodynamical simulations will dramatically improve the situation in the near future.