WorldWideScience

Sample records for energy density theory

  1. Single-particle energies and density of states in density functional theory

    Science.gov (United States)

    van Aggelen, H.; Chan, G. K.-L.

    2015-07-01

    Time-dependent density functional theory (TD-DFT) is commonly used as the foundation to obtain neutral excited states and transition weights in DFT, but does not allow direct access to density of states and single-particle energies, i.e. ionisation energies and electron affinities. Here we show that by extending TD-DFT to a superfluid formulation, which involves operators that break particle-number symmetry, we can obtain the density of states and single-particle energies from the poles of an appropriate superfluid response function. The standard Kohn- Sham eigenvalues emerge as the adiabatic limit of the superfluid response under the assumption that the exchange- correlation functional has no dependence on the superfluid density. The Kohn- Sham eigenvalues can thus be interpreted as approximations to the ionisation energies and electron affinities. Beyond this approximation, the formalism provides an incentive for creating a new class of density functionals specifically targeted at accurate single-particle eigenvalues and bandgaps.

  2. Rydberg energies using excited state density functional theory

    International Nuclear Information System (INIS)

    Cheng, C.-L.; Wu Qin; Van Voorhis, Troy

    2008-01-01

    We utilize excited state density functional theory (eDFT) to study Rydberg states in atoms. We show both analytically and numerically that semilocal functionals can give quite reasonable Rydberg energies from eDFT, even in cases where time dependent density functional theory (TDDFT) fails catastrophically. We trace these findings to the fact that in eDFT the Kohn-Sham potential for each state is computed using the appropriate excited state density. Unlike the ground state potential, which typically falls off exponentially, the sequence of excited state potentials has a component that falls off polynomially with distance, leading to a Rydberg-type series. We also address the rigorous basis of eDFT for these systems. Perdew and Levy have shown using the constrained search formalism that every stationary density corresponds, in principle, to an exact stationary state of the full many-body Hamiltonian. In the present context, this means that the excited state DFT solutions are rigorous as long as they deliver the minimum noninteracting kinetic energy for the given density. We use optimized effective potential techniques to show that, in some cases, the eDFT Rydberg solutions appear to deliver the minimum kinetic energy because the associated density is not pure state v-representable. We thus find that eDFT plays a complementary role to constrained DFT: The former works only if the excited state density is not the ground state of some potential while the latter applies only when the density is a ground state density.

  3. Lower Bound on the Energy Density in Classical and Quantum Field Theories.

    Science.gov (United States)

    Wall, Aron C

    2017-04-14

    A novel method for deriving energy conditions in stable field theories is described. In a local classical theory with one spatial dimension, a local energy condition always exists. For a relativistic field theory, one obtains the dominant energy condition. In a quantum field theory, there instead exists a quantum energy condition, i.e., a lower bound on the energy density that depends on information-theoretic quantities. Some extensions to higher dimensions are briefly discussed.

  4. Gaussian-3 theory using density functional geometries and zero-point energies

    International Nuclear Information System (INIS)

    Baboul, A.G.; Curtiss, L.A.; Redfern, P.C.; Raghavachari, K.

    1999-01-01

    A variation of Gaussian-3 (G3) theory is presented in which the geometries and zero-point energies are obtained from B3LYP density functional theory [B3LYP/6-31G(d)] instead of geometries from second-order perturbation theory [MP2(FU)/6-31G(d)] and zero-point energies from Hartree - Fock theory [HF/6-31G(d)]. This variation, referred to as G3//B3LYP, is assessed on 299 energies (enthalpies of formation, ionization potentials, electron affinities, proton affinities) from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The G3//B3LYP average absolute deviation from experiment for the 299 energies is 0.99 kcal/mol compared to 1.01 kcal/mol for G3 theory. Generally, the results from the two methods are similar, with some exceptions. G3//B3LYP theory gives significantly improved results for several cases for which MP2 theory is deficient for optimized geometries, such as CN and O 2 + . However, G3//B3LYP does poorly for ionization potentials that involve a Jahn - Teller distortion in the cation (CH 4 + , BF 3 + , BCl 3 + ) because of the B3LYP/6-31G(d) geometries. The G3(MP2) method is also modified to use B3LYP/6-31G(d) geometries and zero-point energies. This variation, referred to as G3(MP2)//B3LYP, has an average absolute deviation of 1.25 kcal/mol compared to 1.30 kcal/mol for G3(MP2) theory. Thus, use of density functional geometries and zero-point energies in G3 and G3(MP2) theories is a useful alternative to MP2 geometries and HF zero-point energies. copyright 1999 American Institute of Physics

  5. An interface energy density-based theory considering the coherent interface effect in nanomaterials

    Science.gov (United States)

    Yao, Yin; Chen, Shaohua; Fang, Daining

    2017-02-01

    To characterize the coherent interface effect conveniently and feasibly in nanomaterials, a continuum theory is proposed that is based on the concept of the interface free energy density, which is a dominant factor affecting the mechanical properties of the coherent interface in materials of all scales. The effect of the residual strain caused by self-relaxation and the lattice misfit of nanomaterials, as well as that due to the interface deformation induced by an external load on the interface free energy density is considered. In contrast to the existing theories, the stress discontinuity at the interface is characterized by the interface free energy density through an interface-induced traction. As a result, the interface elastic constant introduced in previous theories, which is not easy to determine precisely, is avoided in the present theory. Only the surface energy density of the bulk materials forming the interface, the relaxation parameter induced by surface relaxation, and the mismatch parameter for forming a coherent interface between the two surfaces are involved. All the related parameters are far easier to determine than the interface elastic constants. The effective bulk and shear moduli of a nanoparticle-reinforced nanocomposite are predicted using the proposed theory. Closed-form solutions are achieved, demonstrating the feasibility and convenience of the proposed model for predicting the interface effect in nanomaterials.

  6. Alternative definitions of the frozen energy in energy decomposition analysis of density functional theory calculations.

    Science.gov (United States)

    Horn, Paul R; Head-Gordon, Martin

    2016-02-28

    In energy decomposition analysis (EDA) of intermolecular interactions calculated via density functional theory, the initial supersystem wavefunction defines the so-called "frozen energy" including contributions such as permanent electrostatics, steric repulsions, and dispersion. This work explores the consequences of the choices that must be made to define the frozen energy. The critical choice is whether the energy should be minimized subject to the constraint of fixed density. Numerical results for Ne2, (H2O)2, BH3-NH3, and ethane dissociation show that there can be a large energy lowering associated with constant density orbital relaxation. By far the most important contribution is constant density inter-fragment relaxation, corresponding to charge transfer (CT). This is unwanted in an EDA that attempts to separate CT effects, but it may be useful in other contexts such as force field development. An algorithm is presented for minimizing single determinant energies at constant density both with and without CT by employing a penalty function that approximately enforces the density constraint.

  7. Density-functional theory for internal magnetic fields

    Science.gov (United States)

    Tellgren, Erik I.

    2018-01-01

    A density-functional theory is developed based on the Maxwell-Schrödinger equation with an internal magnetic field in addition to the external electromagnetic potentials. The basic variables of this theory are the electron density and the total magnetic field, which can equivalently be represented as a physical current density. Hence, the theory can be regarded as a physical current density-functional theory and an alternative to the paramagnetic current density-functional theory due to Vignale and Rasolt. The energy functional has strong enough convexity properties to allow a formulation that generalizes Lieb's convex analysis formulation of standard density-functional theory. Several variational principles as well as a Hohenberg-Kohn-like mapping between potentials and ground-state densities follow from the underlying convex structure. Moreover, the energy functional can be regarded as the result of a standard approximation technique (Moreau-Yosida regularization) applied to the conventional Schrödinger ground-state energy, which imposes limits on the maximum curvature of the energy (with respect to the magnetic field) and enables construction of a (Fréchet) differentiable universal density functional.

  8. Statistical theory of electron densities

    International Nuclear Information System (INIS)

    Pratt, L.R.; Hoffman, G.G.; Harris, R.A.

    1988-01-01

    An optimized Thomas--Fermi theory is proposed which retains the simplicity of the original theory and is a suitable reference theory for Monte Carlo density functional treatments of condensed materials. The key ingredient of the optimized theory is a neighborhood sampled potential which contains effects of the inhomogeneities in the one-electron potential. In contrast to the traditional Thomas--Fermi approach, the optimized theory predicts a finite electron density in the vicinity of a nucleus. Consideration of the example of an ideal electron gas subject to a central Coulomb field indicates that implementation of the approach is straightforward. The optimized theory is found to fail completely when a classically forbidden region is approached. However, these circumstances are not of primary interest for calculations of interatomic forces. It is shown how the energy functional of the density may be constructed by integration of a generalized Hellmann--Feynman relation. This generalized Hellmann--Feynman relation proves to be equivalent to the variational principle of density functional quantum mechanics, and, therefore, the present density theory can be viewed as a variational consequence of the constructed energy functional

  9. The use of perturbation theory in density-functional theory

    International Nuclear Information System (INIS)

    Goerling, A.

    1996-01-01

    Perturbation theory with respect to the electron-electron interaction leads to expressions for the exchange and correlation energies and potentials in terms of Kohn-Sham orbitals and Kohn-Sham eigenvalues. An exact open-quote exchange-only close-quote procedure for solids is introduced. Results for several semiconductors are presented. Perturbation theory expansions for the hardness of molecules and the bad gap of solids are given. Density-functional exchange and correlation energies for excited states are defined and a perturbation theory based Kohn-Sham formalism to treat excited states within density-functional theory is introduced

  10. Descriptions of carbon isotopes within the energy density functional theory

    International Nuclear Information System (INIS)

    Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana; Tammam, M.

    2014-01-01

    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in 15 C, 17 C and 19 C, and the two-neutron halo structures in 16 C and 22 C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations

  11. Descriptions of carbon isotopes within the energy density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Atef [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia and Department of Physics, Al-Azhar University, 71524 Assiut (Egypt); Cheong, Lee Yen; Yahya, Noorhana [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Tammam, M. [Department of Physics, Al-Azhar University, 71524 Assiut (Egypt)

    2014-10-24

    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.

  12. Local density approximation for exchange in excited-state density functional theory

    OpenAIRE

    Harbola, Manoj K.; Samal, Prasanjit

    2004-01-01

    Local density approximation for the exchange energy is made for treatment of excited-states in density-functional theory. It is shown that taking care of the state-dependence of the LDA exchange energy functional leads to accurate excitation energies.

  13. Density dependent hadron field theory

    International Nuclear Information System (INIS)

    Fuchs, C.; Lenske, H.; Wolter, H.H.

    1995-01-01

    A fully covariant approach to a density dependent hadron field theory is presented. The relation between in-medium NN interactions and field-theoretical meson-nucleon vertices is discussed. The medium dependence of nuclear interactions is described by a functional dependence of the meson-nucleon vertices on the baryon field operators. As a consequence, the Euler-Lagrange equations lead to baryon rearrangement self-energies which are not obtained when only a parametric dependence of the vertices on the density is assumed. It is shown that the approach is energy-momentum conserving and thermodynamically consistent. Solutions of the field equations are studied in the mean-field approximation. Descriptions of the medium dependence in terms of the baryon scalar and vector density are investigated. Applications to infinite nuclear matter and finite nuclei are discussed. Density dependent coupling constants obtained from Dirac-Brueckner calculations with the Bonn NN potentials are used. Results from Hartree calculations for energy spectra, binding energies, and charge density distributions of 16 O, 40,48 Ca, and 208 Pb are presented. Comparisons to data strongly support the importance of rearrangement in a relativistic density dependent field theory. Most striking is the simultaneous improvement of charge radii, charge densities, and binding energies. The results indicate the appearance of a new ''Coester line'' in the nuclear matter equation of state

  14. Total-energy Assisted Tight-binding Method Based on Local Density Approximation of Density Functional Theory

    Science.gov (United States)

    Fujiwara, Takeo; Nishino, Shinya; Yamamoto, Susumu; Suzuki, Takashi; Ikeda, Minoru; Ohtani, Yasuaki

    2018-06-01

    A novel tight-binding method is developed, based on the extended Hückel approximation and charge self-consistency, with referring the band structure and the total energy of the local density approximation of the density functional theory. The parameters are so adjusted by computer that the result reproduces the band structure and the total energy, and the algorithm for determining parameters is established. The set of determined parameters is applicable to a variety of crystalline compounds and change of lattice constants, and, in other words, it is transferable. Examples are demonstrated for Si crystals of several crystalline structures varying lattice constants. Since the set of parameters is transferable, the present tight-binding method may be applicable also to molecular dynamics simulations of large-scale systems and long-time dynamical processes.

  15. Virial theorem in the Kohn-Sham density-functional theory formalism: Accurate calculation of the atomic quantum theory of atoms in molecules energies

    NARCIS (Netherlands)

    Rodriguez, A.; Ayers, P.W.; Gotz, A.W.; Castillo-Alvarado, F.L.

    2009-01-01

    A new approach for computing the atom-in-molecule [quantum theory of atoms in molecule (QTAIM)] energies in Kohn-Sham density-functional theory is presented and tested by computing QTAIM energies for a set of representative molecules. In the new approach, the contribution for the correlation-kinetic

  16. Dynamical density functional theory for dense atomic liquids

    International Nuclear Information System (INIS)

    Archer, A J

    2006-01-01

    Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse grained fluid density and show that the theory can be used (making further approximations) to derive the standard mode coupling theory that is used to describe the glass transition. The present theory should provide a useful starting point for describing the dynamics of inhomogeneous atomic fluids

  17. Range-separated density-functional theory for molecular excitation energies

    International Nuclear Information System (INIS)

    Rebolini, E.

    2014-01-01

    Linear-response time-dependent density-functional theory (TDDFT) is nowadays a method of choice to compute molecular excitation energies. However, within the usual adiabatic semi-local approximations, it is not able to describe properly Rydberg, charge-transfer or multiple excitations. Range separation of the electronic interaction allows one to mix rigorously density-functional methods at short range and wave function or Green's function methods at long range. When applied to the exchange functional, it already corrects most of these deficiencies but multiple excitations remain absent as they need a frequency-dependent kernel. In this thesis, the effects of range separation are first assessed on the excitation energies of a partially-interacting system in an analytic and numerical study in order to provide guidelines for future developments of range-separated methods for excitation energy calculations. It is then applied on the exchange and correlation TDDFT kernels in a single-determinant approximation in which the long-range part of the correlation kernel vanishes. A long-range frequency-dependent second-order correlation kernel is then derived from the Bethe-Salpeter equation and added perturbatively to the range-separated TDDFT kernel in order to take into account the effects of double excitations. (author)

  18. Excited-state density functional theory

    International Nuclear Information System (INIS)

    Harbola, Manoj K; Hemanadhan, M; Shamim, Md; Samal, P

    2012-01-01

    Starting with a brief introduction to excited-state density functional theory, we present our method of constructing modified local density approximated (MLDA) energy functionals for the excited states. We show that these functionals give accurate results for kinetic energy and exchange energy compared to the ground state LDA functionals. Further, with the inclusion of GGA correction, highly accurate total energies for excited states are obtained. We conclude with a brief discussion on the further direction of research that include the construction of correlation energy functional and exchange potential for excited states.

  19. Simulation of electron energy loss spectra of nanomaterials with linear-scaling density functional theory

    International Nuclear Information System (INIS)

    Tait, E W; Payne, M C; Ratcliff, L E; Haynes, P D; Hine, N D M

    2016-01-01

    Experimental techniques for electron energy loss spectroscopy (EELS) combine high energy resolution with high spatial resolution. They are therefore powerful tools for investigating the local electronic structure of complex systems such as nanostructures, interfaces and even individual defects. Interpretation of experimental electron energy loss spectra is often challenging and can require theoretical modelling of candidate structures, which themselves may be large and complex, beyond the capabilities of traditional cubic-scaling density functional theory. In this work, we present functionality to compute electron energy loss spectra within the onetep linear-scaling density functional theory code. We first demonstrate that simulated spectra agree with those computed using conventional plane wave pseudopotential methods to a high degree of precision. The ability of onetep to tackle large problems is then exploited to investigate convergence of spectra with respect to supercell size. Finally, we apply the novel functionality to a study of the electron energy loss spectra of defects on the (1 0 1) surface of an anatase slab and determine concentrations of defects which might be experimentally detectable. (paper)

  20. Density functional theory and parallel processing

    International Nuclear Information System (INIS)

    Ward, R.C.; Geist, G.A.; Butler, W.H.

    1987-01-01

    The authors demonstrate a method for obtaining the ground state energies and charge densities of a system of atoms described within density functional theory using simulated annealing on a parallel computer

  1. Density functional theory of nuclei

    International Nuclear Information System (INIS)

    Terasaki, Jun

    2008-01-01

    The density functional theory of nuclei has come to draw attention of scientists in the field of nuclear structure because the theory is expected to provide reliable numerical data in wide range on the nuclear chart. This article is organized to present an overview of the theory to the people engaged in the theory of other fields as well as those people in the nuclear physics experiments. At first, the outline of the density functional theory widely used in the electronic systems (condensed matter, atoms, and molecules) was described starting from the Kohn-Sham equation derived on the variational principle. Then the theory used in the field of nuclear physics was presented. Hartree-Fock and Hartree-Fock-Bogolyubov approximation by using Skyrme interaction was explained. Comparison of the results of calculations and experiments of binding energies and ground state mean square charge radii of some magic number nuclei were shown. The similarity and dissimilarity between the two streams were summarized. Finally the activities of the international project of Universal Nuclear Energy Density Functional (UNEDF) which was started recently lead by US scientist was reported. This project is programmed for five years. One of the applications of the project is the calculation of the neutron capture cross section of nuclei on the r-process, which is absolutely necessary for the nucleosynthesis research. (S. Funahashi)

  2. Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies.

    Science.gov (United States)

    Yang, Yang; Culpitt, Tanner; Hammes-Schiffer, Sharon

    2018-04-05

    The quantum mechanical treatment of both electrons and protons in the calculation of excited state properties is critical for describing nonadiabatic processes such as photoinduced proton-coupled electron transfer. Multicomponent density functional theory enables the consistent quantum mechanical treatment of more than one type of particle and has been implemented previously for studying ground state molecular properties within the nuclear-electronic orbital (NEO) framework, where all electrons and specified protons are treated quantum mechanically. To enable the study of excited state molecular properties, herein the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. Initial applications to FHF - and HCN illustrate that NEO-TDDFT provides accurate proton and electron excitation energies within a single calculation. As its computational cost is similar to that of conventional electronic TDDFT, the NEO-TDDFT approach is promising for diverse applications, particularly nonadiabatic proton transfer reactions, which may exhibit mixed electron-proton vibronic excitations.

  3. Quantal density functional theory

    CERN Document Server

    Sahni, Viraht

    2016-01-01

    This book deals with quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The treated time-independent QDFT constitutes a special case. In the 2nd edition, the theory is extended to include the presence of external magnetostatic fields. The theory is a description of matter based on the ‘quantal Newtonian’ first and second laws which is in terms of “classical” fields that pervade all space, and their quantal sources. The fields, which are explicitly defined, are separately representative of electron correlations due to the Pauli exclusion principle, Coulomb repulsion, correlation-kinetic, correlation-current-density, and correlation-magnetic effects. The book further describes Schrödinger theory from the new physical perspective of fields and quantal sources. It also describes traditional Hohenberg-Kohn-Sham DFT, and explains via QDFT the physics underlying the various energy functionals and functional derivatives o...

  4. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben; Zhu, Zhiyong; Al-Kassab, Talaat; Schwingenschlö gl, Udo

    2012-01-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations

  5. Application of an excited state LDA exchange energy functional for the calculation of transition energy of atoms within time-independent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Shamim, Md; Harbola, Manoj K, E-mail: sami@iitk.ac.i, E-mail: mkh@iitk.ac.i [Department of Physics, Indian Institute of Technology, Kanpur 208 016 (India)

    2010-11-14

    Transition energies of a new class of excited states (two-gap systems) of various atoms are calculated in time-independent density functional formalism by using a recently proposed local density approximation exchange energy functional for excited states. It is shown that the excitation energies calculated with this functional compare well with those calculated with exact exchange theories.

  6. Application of an excited state LDA exchange energy functional for the calculation of transition energy of atoms within time-independent density functional theory

    International Nuclear Information System (INIS)

    Shamim, Md; Harbola, Manoj K

    2010-01-01

    Transition energies of a new class of excited states (two-gap systems) of various atoms are calculated in time-independent density functional formalism by using a recently proposed local density approximation exchange energy functional for excited states. It is shown that the excitation energies calculated with this functional compare well with those calculated with exact exchange theories.

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

    Science.gov (United States)

    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.

  8. Interpretation of monoclinic hafnia valence electron energy-loss spectra by time-dependent density functional theory

    Science.gov (United States)

    Hung, L.; Guedj, C.; Bernier, N.; Blaise, P.; Olevano, V.; Sottile, F.

    2016-04-01

    We present the valence electron energy-loss spectrum and the dielectric function of monoclinic hafnia (m -HfO2) obtained from time-dependent density-functional theory (TDDFT) predictions and compared to energy-filtered spectroscopic imaging measurements in a high-resolution transmission-electron microscope. Fermi's golden rule density-functional theory (DFT) calculations can capture the qualitative features of the energy-loss spectrum, but we find that TDDFT, which accounts for local-field effects, provides nearly quantitative agreement with experiment. Using the DFT density of states and TDDFT dielectric functions, we characterize the excitations that result in the m -HfO2 energy-loss spectrum. The sole plasmon occurs between 13 and 16 eV, although the peaks ˜28 and above 40 eV are also due to collective excitations. We furthermore elaborate on the first-principles techniques used, their accuracy, and remaining discrepancies among spectra. More specifically, we assess the influence of Hf semicore electrons (5 p and 4 f ) on the energy-loss spectrum, and find that the inclusion of transitions from the 4 f band damps the energy-loss intensity in the region above 13 eV. We study the impact of many-body effects in a DFT framework using the adiabatic local-density approximation (ALDA) exchange-correlation kernel, as well as from a many-body perspective using "scissors operators" matched to an ab initio G W calculation to account for self-energy corrections. These results demonstrate some cancellation of errors between self-energy and excitonic effects, even for excitations from the Hf 4 f shell. We also simulate the dispersion with increasing momentum transfer for plasmon and collective excitation peaks.

  9. Complex-energy approach to sum rules within nuclear density functional theory

    Science.gov (United States)

    Hinohara, Nobuo; Kortelainen, Markus; Nazarewicz, Witold; Olsen, Erik

    2015-04-01

    Background: The linear response of the nucleus to an external field contains unique information about the effective interaction, the correlations governing the behavior of the many-body system, and the properties of its excited states. To characterize the response, it is useful to use its energy-weighted moments, or sum rules. By comparing computed sum rules with experimental values, the information content of the response can be utilized in the optimization process of the nuclear Hamiltonian or the nuclear energy density functional (EDF). But the additional information comes at a price: compared to the ground state, computation of excited states is more demanding. Purpose: To establish an efficient framework to compute energy-weighted sum rules of the response that is adaptable to the optimization of the nuclear EDF and large-scale surveys of collective strength, we have developed a new technique within the complex-energy finite-amplitude method (FAM) based on the quasiparticle random-phase approximation (QRPA). Methods: To compute sum rules, we carry out contour integration of the response function in the complex-energy plane. We benchmark our results against the conventional matrix formulation of the QRPA theory, the Thouless theorem for the energy-weighted sum rule, and the dielectric theorem for the inverse-energy-weighted sum rule. Results: We derive the sum-rule expressions from the contour integration of the complex-energy FAM. We demonstrate that calculated sum-rule values agree with those obtained from the matrix formulation of the QRPA. We also discuss the applicability of both the Thouless theorem about the energy-weighted sum rule and the dielectric theorem for the inverse-energy-weighted sum rule to nuclear density functional theory in cases when the EDF is not based on a Hamiltonian. Conclusions: The proposed sum-rule technique based on the complex-energy FAM is a tool of choice when optimizing effective interactions or energy functionals. The method

  10. Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

    Science.gov (United States)

    Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

    2015-08-11

    The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

  11. Extending density functional embedding theory for covalently bonded systems.

    Science.gov (United States)

    Yu, Kuang; Carter, Emily A

    2017-12-19

    Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix-based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

  12. Four-loop vacuum energy density of the SU(Nc) + adjoint Higgs theory

    International Nuclear Information System (INIS)

    Kajantie, K.; Rummukainen, K.; Schroder, Y.; Laine, M.

    2003-01-01

    We compute the dimensionally regularised four-loop vacuum energy density of the SU(N c ) gauge + adjoint Higgs theory, in the disordered phase. 'Scalarisation', or reduction to a small set of master integrals of the type appearing in scalar field theories, is carried out in d dimensions, employing general partial integration identities through an algorithm developed by Laporta, while the remaining scalar integrals are evaluated in d=3-2ε dimensions, by expanding in ε 6 ln(1/g)), O(g 6 ) to the pressure, while the general methods are applicable also to studies of critical phenomena in QED-like statistical physics systems. (author)

  13. Energy landscapes of nucleophilic substitution reactions: a comparison of density functional theory and coupled cluster methods

    NARCIS (Netherlands)

    Swart, M.; Sola, M.; Bickelhaupt, F.M.

    2007-01-01

    We have carried out a detailed evaluation of the performance of all classes of density functional theory (DFT) for describing the potential energy surface (PES) of a wide range of nucleophilic substitution (S

  14. Uniform magnetic fields in density-functional theory

    Science.gov (United States)

    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.

  15. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    Science.gov (United States)

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

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

    Science.gov (United States)

    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.

  17. Derivation of the density functional theory from the cluster expansion.

    Science.gov (United States)

    Hsu, J Y

    2003-09-26

    The density functional theory is derived from a cluster expansion by truncating the higher-order correlations in one and only one term in the kinetic energy. The formulation allows self-consistent calculation of the exchange correlation effect without imposing additional assumptions to generalize the local density approximation. The pair correlation is described as a two-body collision of bound-state electrons, and modifies the electron- electron interaction energy as well as the kinetic energy. The theory admits excited states, and has no self-interaction energy.

  18. The problem of the universal density functional and the density matrix functional theory

    International Nuclear Information System (INIS)

    Bobrov, V. B.; Trigger, S. A.

    2013-01-01

    The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the hypothesis of the existence of the universal density functional. Based on the obtained explicit expression for the nonrel-ativistic particle energy in a local external field, we prove that the energy of the system of more than two non-interacting electrons cannot be a functional of the inhomogeneous density. This result is generalized to the system of interacting electrons. It means that the Hohenberg-Kohn lemma cannot provide justification of the universal density functional for fermions. At the same time, statements of the density functional theory remain valid when considering any number of noninteracting ground-state bosons due to the Bose condensation effect. In the framework of the density matrix functional theory, the hypothesis of the existence of the universal density matrix functional corresponds to the cases of noninteracting particles and to interaction in the Hartree-Fock approximation.

  19. Microscopically-constrained Fock energy density functionals from chiral effective field theory. I. Two-nucleon interactions

    International Nuclear Information System (INIS)

    Gebremariam, B.; Bogner, S.K.; Duguet, T.

    2011-01-01

    The density matrix expansion (DME) of Negele and Vautherin is a convenient tool to map finite-range physics associated with vacuum two- and three-nucleon interactions into the form of a Skyrme-like energy density functional (EDF) with density-dependent couplings. In this work, we apply the improved formulation of the DME proposed recently in (arXiv:0910.4979) by Gebremariam et al. to the non-local Fock energy obtained from chiral effective field theory (EFT) two-nucleon (NN) interactions at next-to-next-to-leading-order (N 2 LO). The structure of the chiral interactions is such that each coupling in the DME Fock functional can be decomposed into a coupling constant arising from zero-range contact interactions and a coupling function of the density arising from the universal long-range pion exchanges. This motivates a new microscopically-guided Skyrme phenomenology where the density-dependent couplings associated with the underlying pion-exchange interactions are added to standard empirical Skyrme functionals, and the density-independent Skyrme parameters subsequently refit to data. A link to a downloadable Mathematica notebook containing the novel density-dependent couplings is provided.

  20. Alternative separation of exchange and correlation energies in multi-configuration range-separated density-functional theory.

    Science.gov (United States)

    Stoyanova, Alexandrina; Teale, Andrew M; Toulouse, Julien; Helgaker, Trygve; Fromager, Emmanuel

    2013-10-07

    The alternative separation of exchange and correlation energies proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] is explored in the context of multi-configuration range-separated density-functional theory. The new decomposition of the short-range exchange-correlation energy relies on the auxiliary long-range interacting wavefunction rather than the Kohn-Sham (KS) determinant. The advantage, relative to the traditional KS decomposition, is that the wavefunction part of the energy is now computed with the regular (fully interacting) Hamiltonian. One potential drawback is that, because of double counting, the wavefunction used to compute the energy cannot be obtained by minimizing the energy expression with respect to the wavefunction parameters. The problem is overcome by using short-range optimized effective potentials (OEPs). The resulting combination of OEP techniques with wavefunction theory has been investigated in this work, at the Hartree-Fock (HF) and multi-configuration self-consistent-field (MCSCF) levels. In the HF case, an analytical expression for the energy gradient has been derived and implemented. Calculations have been performed within the short-range local density approximation on H2, N2, Li2, and H2O. Significant improvements in binding energies are obtained with the new decomposition of the short-range energy. The importance of optimizing the short-range OEP at the MCSCF level when static correlation becomes significant has also been demonstrated for H2, using a finite-difference gradient. The implementation of the analytical gradient for MCSCF wavefunctions is currently in progress.

  1. Quantal density functional theory II. Approximation methods and applications

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2010-01-01

    This book is on approximation methods and applications of Quantal Density Functional Theory (QDFT), a new local effective-potential-energy theory of electronic structure. What distinguishes the theory from traditional density functional theory is that the electron correlations due to the Pauli exclusion principle, Coulomb repulsion, and the correlation contribution to the kinetic energy -- the Correlation-Kinetic effects -- are separately and explicitly defined. As such it is possible to study each property of interest as a function of the different electron correlations. Approximations methods based on the incorporation of different electron correlations, as well as a many-body perturbation theory within the context of QDFT, are developed. The applications are to the few-electron inhomogeneous electron gas systems in atoms and molecules, as well as to the many-electron inhomogeneity at metallic surfaces. (orig.)

  2. Density-functional theory in one dimension for contact-interacting fermions

    International Nuclear Information System (INIS)

    Magyar, R.J.; Burke, K.

    2004-01-01

    A density-functional theory is developed for fermions in one dimension, interacting via a δ function. Such systems provide a natural testing ground for questions of principle, as the local-density approximation should be highly accurate since for this interaction type the exchange contribution to the local-density approximation is intrinsically self-interaction-free. The exact-exchange contribution to the total energy is a local functional of the density. A local-density approximation for correlation is obtained using perturbation theory and Bethe ansatz results for the one-dimensional contact-interacting uniform Fermi gas. The ground-state energies are calculated for two finite systems, the analogs of helium and of Hooke's atom. The local-density approximation is shown to be excellent as expected

  3. Relativistic many-body theory of high density matter

    International Nuclear Information System (INIS)

    Chin, S.A.

    1977-01-01

    A fully relativistic quantum many-body theory is applied to the study of high-density matter. The latter is identified with the zero-temperature ground state of a system of interacting baryons. In accordance with the observed short-range repulsive and long-range attractive character of the nucleon--nucleon force, baryons are described as interacting with each other via a massive scalar and a massive vector meson exchange. In the Hartree approximation, the theory yields the same result as the mean-field theory, but with additional vacuum fluctuation corrections. The resultant equation of state for neutron matter is used to determine properties of neutron stars. The relativistic exchange energy, its corresponding single-particle excitation spectrum, and its effect on the neutron matter equation of state, are calculated. The correlation energy from summing the set of ring diagrams is derived directly from the energy-momentum tensor, with renormalization carried out by adding counterterms to the original Lagrangian and subtracting purely vacuum expectation values. Terms of order g 4 lng 2 are explicitly given. Effects of scalar-vector mixing are discussed. Collective modes corresponding to macroscopic density fluctuation are investigated. Two basic modes are found, a plasma-like mode and zero sound, with the latter dominant at high density. The stability and damping of these modes are studied. Last, the effect of vacuum polarization in high-density matter is examined

  4. Intuitive Density Functional Theory-Based Energy Decomposition Analysis for Protein-Ligand Interactions.

    Science.gov (United States)

    Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

    2017-04-11

    First-principles quantum mechanical calculations with methods such as density functional theory (DFT) allow the accurate calculation of interaction energies between molecules. These interaction energies can be dissected into chemically relevant components such as electrostatics, polarization, and charge transfer using energy decomposition analysis (EDA) approaches. Typically EDA has been used to study interactions between small molecules; however, it has great potential to be applied to large biomolecular assemblies such as protein-protein and protein-ligand interactions. We present an application of EDA calculations to the study of ligands that bind to the thrombin protein, using the ONETEP program for linear-scaling DFT calculations. Our approach goes beyond simply providing the components of the interaction energy; we are also able to provide visual representations of the changes in density that happen as a result of polarization and charge transfer, thus pinpointing the functional groups between the ligand and protein that participate in each kind of interaction. We also demonstrate with this approach that we can focus on studying parts (fragments) of ligands. The method is relatively insensitive to the protocol that is used to prepare the structures, and the results obtained are therefore robust. This is an application to a real protein drug target of a whole new capability where accurate DFT calculations can produce both energetic and visual descriptors of interactions. These descriptors can be used to provide insights for tailoring interactions, as needed for example in drug design.

  5. Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction

    DEFF Research Database (Denmark)

    Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.

    2008-01-01

    Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole...

  6. Energy in the Einstein-aether theory

    International Nuclear Information System (INIS)

    Eling, Christopher

    2006-01-01

    We investigate the energy of a theory with a unit vector field (the aether) coupled to gravity. Both the Weinberg and Einstein type energy-momentum pseudotensors are employed. In the linearized theory we find expressions for the energy density of the 5 wave modes. The requirement that the modes have positive energy is then used to constrain the theory. In the fully nonlinear theory we compute the total energy of an asymptotically flat spacetime. The resulting energy expression is modified by the presence of the aether due to the nonzero value of the unit vector at infinity and its 1/r falloff. The question of nonlinear energy positivity is also discussed, but not resolved

  7. Density Functional Theory Calculations of Activation Energies for Carrier Capture by Defects in Semiconductors

    Science.gov (United States)

    Modine, N. A.; Wright, A. F.; Lee, S. R.

    The rate of defect-induced carrier recombination is determined by both defect levels and carrier capture cross-sections. Density functional theory (DFT) has been widely and successfully used to predict defect levels, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry developed the theory of carrier-capture by multiphonon emission in the 1970s and showed that carrier-capture cross-sections differ between defects primarily due to differences in their carrier capture activation energies. We present an approach to using DFT to calculate carrier capture activation energies that does not depend on an assumed configuration coordinate and that fully accounts for anharmonic effects, which can substantially modify carrier activation energies. We demonstrate our approach for intrinisic defects in GaAs and GaN and discuss how our results depend on the choice of exchange-correlation functional and the treatment of spin polarization. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  8. Four-loop vacuum energy density of the SU($N_c$) + adjoint Higgs theory

    CERN Document Server

    Kajantie, Keijo; Rummukainen, K; Schröder, Y

    2003-01-01

    We compute the dimensionally regularised four-loop vacuum energy density of the SU(N_c) gauge + adjoint Higgs theory, in the disordered phase. ``Scalarisation'', or reduction to a small set of master integrals of the type appearing in scalar field theories, is carried out in d dimensions, employing general partial integration identities through an algorithm developed by Laporta, while the remaining scalar integrals are evaluated in d = 3 - 2\\epsilon dimensions, by expanding in \\epsilon << 1 and evaluating a number of coefficients. The results have implications for the thermodynamics of finite temperature QCD, allowing to determine perturbative contributions of orders O(g^6 ln(1/g)), O(g^6) to the pressure, while the general methods are applicable also to studies of critical phenomena in QED-like statistical physics systems.

  9. Orbital functionals in density-matrix- and current-density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Helbig, N

    2006-05-15

    Density-Functional Theory (DFT), although widely used and very successful in the calculation of several observables, fails to correctly describe strongly correlated materials. In the first part of this work we, therefore, introduce reduced-densitymatrix- functional theory (RDMFT) which is one possible way to treat electron correlation beyond DFT. Within this theory the one-body reduced density matrix (1- RDM) is used as the basic variable. Our main interest is the calculation of the fundamental gap which proves very problematic within DFT. In order to calculate the fundamental gap we generalize RDMFT to fractional particle numbers M by describing the system as an ensemble of an N and an N+1 particle system (with N{<=}M{<=}N+1). For each fixed particle number, M, the total energy is minimized with respect to the natural orbitals and their occupation numbers. This leads to the total energy as a function of M. The derivative of this function with respect to the particle number has a discontinuity at integer particle number which is identical to the gap. In addition, we investigate the necessary and sufficient conditions for the 1- RDM of a system with fractional particle number to be N-representable. Numerical results are presented for alkali atoms, small molecules, and periodic systems. Another problem within DFT is the description of non-relativistic many-electron systems in the presence of magnetic fields. It requires the paramagnetic current density and the spin magnetization to be used as basic variables besides the electron density. However, electron-gas-based functionals of current-spin-density-functional Theory (CSDFT) exhibit derivative discontinuities as a function of the magnetic field whenever a new Landau level is occupied, which makes them difficult to use in practice. Since the appearance of Landau levels is, intrinsically, an orbital effect it is appealing to use orbital-dependent functionals. We have developed a CSDFT version of the optimized

  10. Periodic subsystem density-functional theory

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2014-01-01

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

  11. Periodic subsystem density-functional theory

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2014-11-01

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

  12. Bayesian error estimation in density-functional theory

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Kaasbjerg, Kristen; Frederiksen, Søren Lund

    2005-01-01

    We present a practical scheme for performing error estimates for density-functional theory calculations. The approach, which is based on ideas from Bayesian statistics, involves creating an ensemble of exchange-correlation functionals by comparing with an experimental database of binding energies...

  13. Modeling of Materials for Energy Storage: A Challenge for Density Functional Theory

    Science.gov (United States)

    Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

    Hollandite α-MnO2 is a promising material for rechargeable batteries and is studied extensively in the community because of its interesting tunnel structure and the corresponding large capacity for lithium as well as sodium ions. However, the presence of partially reduced Mn ions due to doping with Ag or during lithiation makes hollandite a challenging system for density functional theory and the conventionally employed PBE+U method. A naive attempt to model the ternary system LixAgyMnO2 with density functionals, similar to those employed for the case y = 0 , fails and predicts a strong monoclinic distortion of the experimentally observed tetragonal unit cell for Ag2Mn8O16. Structure and binding energies are compared with experimental data and show the importance of van der Waals interactions as well as the necessity for an accurate description of the cooperative Jan-Teller effects for silver hollandite AgyMnO2. Based on these observations a ternary phase diagram is calculated allowing to predict the physical and chemical properties of LixAgyMnO2, such as stable stoichiometries, open circuit voltages, the formation of Ag metal and the structural change during lithiation. Department of Energy (DOE) under award #DE-SC0012673.

  14. Ultra-stiff metallic glasses through bond energy density design.

    Science.gov (United States)

    Schnabel, Volker; Köhler, Mathias; Music, Denis; Bednarcik, Jozef; Clegg, William J; Raabe, Dierk; Schneider, Jochen M

    2017-07-05

    The elastic properties of crystalline metals scale with their valence electron density. Similar observations have been made for metallic glasses. However, for metallic glasses where covalent bonding predominates, such as metalloid metallic glasses, this relationship appears to break down. At present, the reasons for this are not understood. Using high energy x-ray diffraction analysis of melt spun and thin film metallic glasses combined with density functional theory based molecular dynamics simulations, we show that the physical origin of the ultrahigh stiffness in both metalloid and non-metalloid metallic glasses is best understood in terms of the bond energy density. Using the bond energy density as novel materials design criterion for ultra-stiff metallic glasses, we are able to predict a Co 33.0 Ta 3.5 B 63.5 short range ordered material by density functional theory based molecular dynamics simulations with a high bond energy density of 0.94 eV Å -3 and a bulk modulus of 263 GPa, which is 17% greater than the stiffest Co-B based metallic glasses reported in literature.

  15. SURFACE SYMMETRY ENERGY OF NUCLEAR ENERGY DENSITY FUNCTIONALS

    Energy Technology Data Exchange (ETDEWEB)

    Nikolov, N; Schunck, N; Nazarewicz, W; Bender, M; Pei, J

    2010-12-20

    We study the bulk deformation properties of the Skyrme nuclear energy density functionals. Following simple arguments based on the leptodermous expansion and liquid drop model, we apply the nuclear density functional theory to assess the role of the surface symmetry energy in nuclei. To this end, we validate the commonly used functional parametrizations against the data on excitation energies of superdeformed band-heads in Hg and Pb isotopes, and fission isomers in actinide nuclei. After subtracting shell effects, the results of our self-consistent calculations are consistent with macroscopic arguments and indicate that experimental data on strongly deformed configurations in neutron-rich nuclei are essential for optimizing future nuclear energy density functionals. The resulting survey provides a useful benchmark for further theoretical improvements. Unlike in nuclei close to the stability valley, whose macroscopic deformability hangs on the balance of surface and Coulomb terms, the deformability of neutron-rich nuclei strongly depends on the surface-symmetry energy; hence, its proper determination is crucial for the stability of deformed phases of the neutron-rich matter and description of fission rates for r-process nucleosynthesis.

  16. Knot soliton in DNA and geometric structure of its free-energy density.

    Science.gov (United States)

    Wang, Ying; Shi, Xuguang

    2018-03-01

    In general, the geometric structure of DNA is characterized using an elastic rod model. The Landau model provides us a new theory to study the geometric structure of DNA. By using the decomposition of the arc unit in the helical axis of DNA, we find that the free-energy density of DNA is similar to the free-energy density of a two-condensate superconductor. By using the φ-mapping topological current theory, the torus knot soliton hidden in DNA is demonstrated. We show the relation between the geometric structure and free-energy density of DNA and the Frenet equations in differential geometry theory are considered. Therefore, the free-energy density of DNA can be expressed by the curvature and torsion of the helical axis.

  17. High energy density propulsion systems and small engine dynamometer

    Science.gov (United States)

    Hays, Thomas

    2009-07-01

    Scope and Method of Study. This study investigates all possible methods of powering small unmanned vehicles, provides reasoning for the propulsion system down select, and covers in detail the design and production of a dynamometer to confirm theoretical energy density calculations for small engines. Initial energy density calculations are based upon manufacturer data, pressure vessel theory, and ideal thermodynamic cycle efficiencies. Engine tests are conducted with a braking type dynamometer for constant load energy density tests, and show true energy densities in excess of 1400 WH/lb of fuel. Findings and Conclusions. Theory predicts lithium polymer, the present unmanned system energy storage device of choice, to have much lower energy densities than other conversion energy sources. Small engines designed for efficiency, instead of maximum power, would provide the most advantageous method for powering small unmanned vehicles because these engines have widely variable power output, loss of mass during flight, and generate rotational power directly. Theoretical predictions for the energy density of small engines has been verified through testing. Tested values up to 1400 WH/lb can be seen under proper operating conditions. The implementation of such a high energy density system will require a significant amount of follow-on design work to enable the engines to tolerate the higher temperatures of lean operation. Suggestions are proposed to enable a reliable, small-engine propulsion system in future work. Performance calculations show that a mature system is capable of month long flight times, and unrefueled circumnavigation of the globe.

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

    Science.gov (United States)

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

    2014-10-28

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

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

    Science.gov (United States)

    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)].

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

    Science.gov (United States)

    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.

  1. Spectral function from Reduced Density Matrix Functional Theory

    Science.gov (United States)

    Romaniello, Pina; di Sabatino, Stefano; Berger, Jan A.; Reining, Lucia

    2015-03-01

    In this work we focus on the calculation of the spectral function, which determines, for example, photoemission spectra, from reduced density matrix functional theory. Starting from its definition in terms of the one-body Green's function we derive an expression for the spectral function that depends on the natural occupation numbers and on an effective energy which accounts for all the charged excitations. This effective energy depends on the two-body as well as higher-order density matrices. Various approximations to this expression are explored by using the exactly solvable Hubbard chains.

  2. Energy vs. density on paths toward more exact density functionals.

    Science.gov (United States)

    Kepp, Kasper P

    2018-03-14

    Recently, the progression toward more exact density functional theory has been questioned, implying a need for more formal ways to systematically measure progress, i.e. a "path". Here I use the Hohenberg-Kohn theorems and the definition of normality by Burke et al. to define a path toward exactness and "straying" from the "path" by separating errors in ρ and E[ρ]. A consistent path toward exactness involves minimizing both errors. Second, a suitably diverse test set of trial densities ρ' can be used to estimate the significance of errors in ρ without knowing the exact densities which are often inaccessible. To illustrate this, the systems previously studied by Medvedev et al., the first ionization energies of atoms with Z = 1 to 10, the ionization energy of water, and the bond dissociation energies of five diatomic molecules were investigated using CCSD(T)/aug-cc-pV5Z as benchmark at chemical accuracy. Four functionals of distinct designs was used: B3LYP, PBE, M06, and S-VWN. For atomic cations regardless of charge and compactness up to Z = 10, the energy effects of the different ρ are energy-wise insignificant. An interesting oscillating behavior in the density sensitivity is observed vs. Z, explained by orbital occupation effects. Finally, it is shown that even large "normal" problems such as the Co-C bond energy of cobalamins can use simpler (e.g. PBE) trial densities to drastically speed up computation by loss of a few kJ mol -1 in accuracy. The proposed method of using a test set of trial densities to estimate the sensitivity and significance of density errors of functionals may be useful for testing and designing new balanced functionals with more systematic improvement of densities and energies.

  3. Analysis of self-consistency effects in range-separated density-functional theory with Møller-Plesset perturbation theory

    DEFF Research Database (Denmark)

    Fromager, Emmanuel; Jensen, Hans Jørgen Aagaard

    2011-01-01

    Range-separated density-functional theory combines wave function theory for the long-range part of the two-electron interaction with density-functional theory for the short-range part. When describing the long-range interaction with non-variational methods, such as perturbation or coupled......-cluster theories, self-consistency effects are introduced in the density functional part, which for an exact solution requires iterations. They are generally assumed to be small but no detailed study has been performed so far. Here, the authors analyze self-consistency when using Møller-Plesset-type (MP......) perturbation theory for the long range interaction. The lowest-order self-consistency corrections to the wave function and the energy, that enter the perturbation expansions at the second and fourth order, respectively, are both expressed in terms of the one-electron reduced density matrix. The computational...

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

    Science.gov (United States)

    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.

  5. Density functional theory

    International Nuclear Information System (INIS)

    Das, M.P.

    1984-07-01

    The state of the art of the density functional formalism (DFT) is reviewed. The theory is quantum statistical in nature; its simplest version is the well-known Thomas-Fermi theory. The DFT is a powerful formalism in which one can treat the effect of interactions in inhomogeneous systems. After some introductory material, the DFT is outlined from the two basic theorems, and various generalizations of the theorems appropriate to several physical situations are pointed out. Next, various approximations to the density functionals are presented and some practical schemes, discussed; the approximations include an electron gas of almost constant density and an electron gas of slowly varying density. Then applications of DFT in various diverse areas of physics (atomic systems, plasmas, liquids, nuclear matter) are mentioned, and its strengths and weaknesses are pointed out. In conclusion, more recent developments of DFT are indicated

  6. Collision dynamics of H+ + N2 at low energies based on time-dependent density-functional theory

    Science.gov (United States)

    Yu, W.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Gao, C.-Z.; Wei, B.

    2018-02-01

    Using time-dependent density-functional theory at the level of local density approximation augmented by a self-interaction correction and coupled non-adiabatically to molecular dynamics, we study, from a theoretical perspective, scattering dynamics of the proton in collisions with the N2 molecule at 30 eV. Nine different collision configurations are employed to analyze the proton energy loss spectra, electron depletion, scattering angles and self-interaction effects. Our results agree qualitatively with the experimental data and previous theoretical calculations. The discrepancies are ascribed to the limitation of the theoretical models in use. We find that self-interaction effects can significantly influence the electron capture and the excited diatomic vibrational motion, which is in consistent with other calculations. In addition, it is found that the molecular structure can be readily retrieved from the proton energy loss spectra due to a significant momentum transfer in head-on collisions.

  7. Strontium, nickel, cadmium, and lead substitution into calcite, studied by density functional theory

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Sakuma, Hiroshi; Stipp, Susan Louise Svane

    2014-01-01

    We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid inte......We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral...

  8. Covariant density functional theory: The role of the pion

    International Nuclear Information System (INIS)

    Lalazissis, G. A.; Karatzikos, S.; Serra, M.; Otsuka, T.; Ring, P.

    2009-01-01

    We investigate the role of the pion in covariant density functional theory. Starting from conventional relativistic mean field (RMF) theory with a nonlinear coupling of the σ meson and without exchange terms we add pions with a pseudovector coupling to the nucleons in relativistic Hartree-Fock approximation. In order to take into account the change of the pion field in the nuclear medium the effective coupling constant of the pion is treated as a free parameter. It is found that the inclusion of the pion to this sort of density functionals does not destroy the overall description of the bulk properties by RMF. On the other hand, the noncentral contribution of the pion (tensor coupling) does have effects on single particle energies and on binding energies of certain nuclei.

  9. Functional renormalization group and Kohn-Sham scheme in density functional theory

    Science.gov (United States)

    Liang, Haozhao; Niu, Yifei; Hatsuda, Tetsuo

    2018-04-01

    Deriving accurate energy density functional is one of the central problems in condensed matter physics, nuclear physics, and quantum chemistry. We propose a novel method to deduce the energy density functional by combining the idea of the functional renormalization group and the Kohn-Sham scheme in density functional theory. The key idea is to solve the renormalization group flow for the effective action decomposed into the mean-field part and the correlation part. Also, we propose a simple practical method to quantify the uncertainty associated with the truncation of the correlation part. By taking the φ4 theory in zero dimension as a benchmark, we demonstrate that our method shows extremely fast convergence to the exact result even for the highly strong coupling regime.

  10. Chemical theory and modelling through density across length scales

    International Nuclear Information System (INIS)

    Ghosh, Swapan K.

    2016-01-01

    One of the concepts that has played a major role in the conceptual as well as computational developments covering all the length scales of interest in a number of areas of chemistry, physics, chemical engineering and materials science is the concept of single-particle density. Density functional theory has been a versatile tool for the description of many-particle systems across length scales. Thus, in the microscopic length scale, an electron density based description has played a major role in providing a deeper understanding of chemical binding in atoms, molecules and solids. Density concept has been used in the form of single particle number density in the intermediate mesoscopic length scale to obtain an appropriate picture of the equilibrium and dynamical processes, dealing with a wide class of problems involving interfacial science and soft condensed matter. In the macroscopic length scale, however, matter is usually treated as a continuous medium and a description using local mass density, energy density and other related property density functions has been found to be quite appropriate. The basic ideas underlying the versatile uses of the concept of density in the theory and modelling of materials and phenomena, as visualized across length scales, along with selected illustrative applications to some recent areas of research on hydrogen energy, soft matter, nucleation phenomena, isotope separation, and separation of mixture in condensed phase, will form the subject matter of the talk. (author)

  11. Theory of coherent resonance energy transfer

    International Nuclear Information System (INIS)

    Jang, Seogjoo; Cheng, Y.-C.; Reichman, David R.; Eaves, Joel D.

    2008-01-01

    A theory of coherent resonance energy transfer is developed combining the polaron transformation and a time-local quantum master equation formulation, which is valid for arbitrary spectral densities including common modes. The theory contains inhomogeneous terms accounting for nonequilibrium initial preparation effects and elucidates how quantum coherence and nonequilibrium effects manifest themselves in the coherent energy transfer dynamics beyond the weak resonance coupling limit of the Foerster and Dexter (FD) theory. Numerical tests show that quantum coherence can cause significant changes in steady state donor/acceptor populations from those predicted by the FD theory and illustrate delicate cooperation of nonequilibrium and quantum coherence effects on the transient population dynamics.

  12. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben

    2012-10-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations are based on the Müller-Schottky equation, which is modified to include different atomic neighborhoods and their characteristic bonds. The local environment is considered up to the fifth next nearest neighbors. To compare the experimental with simulated APT data, the AtomVicinity algorithm, which provides statistical information about the positions of the neighboring atoms, is applied. The quality of this information is influenced by the field evaporation behavior of the different species, which is connected to the bonding energies. © Microscopy Society of America 2012.

  13. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry.

    Science.gov (United States)

    Domingo, Luis R

    2016-09-30

    A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

  14. Density Functional Methods for Shock Physics and High Energy Density Science

    Science.gov (United States)

    Desjarlais, Michael

    2017-06-01

    Molecular dynamics with density functional theory has emerged over the last two decades as a powerful and accurate framework for calculating thermodynamic and transport properties with broad application to dynamic compression, high energy density science, and warm dense matter. These calculations have been extensively validated against shock and ramp wave experiments, are a principal component of high-fidelity equation of state generation, and are having wide-ranging impacts on inertial confinement fusion, planetary science, and shock physics research. In addition to thermodynamic properties, phase boundaries, and the equation of state, one also has access to electrical conductivity, thermal conductivity, and lower energy optical properties. Importantly, all these properties are obtained within the same theoretical framework and are manifestly consistent. In this talk I will give a brief history and overview of molecular dynamics with density functional theory and its use in calculating a wide variety of thermodynamic and transport properties for materials ranging from ambient to extreme conditions and with comparisons to experimental data. I will also discuss some of the limitations and difficulties, as well as active research areas. Sandia is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  15. Efficacy of surface error corrections to density functional theory calculations of vacancy formation energy in transition metals.

    Science.gov (United States)

    Nandi, Prithwish Kumar; Valsakumar, M C; Chandra, Sharat; Sahu, H K; Sundar, C S

    2010-09-01

    We calculate properties like equilibrium lattice parameter, bulk modulus and monovacancy formation energy for nickel (Ni), iron (Fe) and chromium (Cr) using Kohn-Sham density functional theory (DFT). We compare the relative performance of local density approximation (LDA) and generalized gradient approximation (GGA) for predicting such physical properties for these metals. We also make a relative study between two different flavors of GGA exchange correlation functional, namely PW91 and PBE. These calculations show that there is a discrepancy between DFT calculations and experimental data. In order to understand this discrepancy in the calculation of vacancy formation energy, we introduce a correction for the surface intrinsic error corresponding to an exchange correlation functional using the scheme implemented by Mattsson et al (2006 Phys. Rev. B 73 195123) and compare the effectiveness of the correction scheme for Al and the 3d transition metals.

  16. Building a universal nuclear energy density functional

    International Nuclear Information System (INIS)

    Bertsch, G F

    2007-01-01

    This talk describes a new project in SciDAC II in the area of low-energy nuclear physics. The motivation and goals of the SciDAC are presented as well as an outline of the theoretical and computational methodology that will be employed. An important motivation is to have more accurate and reliable predictions of nuclear properties including their binding energies and low-energy reaction rates. The theoretical basis is provided by density functional theory, which the only available theory that can be systematically applied to all nuclei. However, other methodologies based on wave function methods are needed to refine the functionals and to make applications to dynamic processes

  17. Nuclear energy density functional from chiral pion-nucleon dynamics revisited

    Science.gov (United States)

    Kaiser, N.; Weise, W.

    2010-05-01

    We use a recently improved density-matrix expansion to calculate the nuclear energy density functional in the framework of in-medium chiral perturbation theory. Our calculation treats systematically the effects from 1 π-exchange, iterated 1 π-exchange, and irreducible 2 π-exchange with intermediate Δ-isobar excitations, including Pauli-blocking corrections up to three-loop order. We find that the effective nucleon mass M(ρ) entering the energy density functional is identical to the one of Fermi-liquid theory when employing the improved density-matrix expansion. The strength F(ρ) of the ( surface-term as provided by the pion-exchange dynamics is in good agreement with that of phenomenological Skyrme forces in the density region ρ/2short-range spin-orbit interaction. The strength function F(ρ) multiplying the square of the spin-orbit density comes out much larger than in phenomenological Skyrme forces and it has a pronounced density dependence.

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

    Science.gov (United States)

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

    2005-05-13

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

  19. Exploration of Plasma Jets Approach to High Energy Density Physics. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chiping [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

    2013-08-26

    High-energy-density laboratory plasma (HEDLP) physics is an emerging, important area of research in plasma physics, nuclear physics, astrophysics, and particle acceleration. While the HEDLP regime occurs at extreme conditions which are often found naturally in space but not on the earth, it may be accessible by colliding high intensity plasmas such as high-energy-density plasma jets, plasmoids or compact toroids from plasma guns. The physics of plasma jets is investigated in the context of high energy density laboratory plasma research. This report summarizes results of theoretical and computational investigation of a plasma jet undergoing adiabatic compression and adiabatic expansion. A root-mean-squared (rms) envelope theory of plasma jets is developed. Comparison between theory and experiment is made. Good agreement between theory and experiment is found.

  20. Density functional theory in surface science and heterogeneous catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Scheffler, M.; Toulhoat, H.

    2006-01-01

    Solid surfaces are used extensively as catalysts throughout the chemical industry, in the energy sector, and in environmental protection. Recently, density functional theory has started providing new insight into the atomic-scale mechanisms of heterogeneous catalysis, helping to interpret the large...

  1. A-centers in silicon studied with hybrid density functional theory

    KAUST Repository

    Wang, Hao; Chroneos, Alexander; Londos, C. A.; Schwingenschlö gl, Udo; Sgourou, E. N.

    2013-01-01

    Density functional theory employing hybrid functional is used to gain fundamental insight into the interaction of vacancies with oxygen interstitials to form defects known as A-centers in silicon. We calculate the formation energy of the defect with respect to the Fermi energy for all possible charge states. It is found that the neutral and doubly negatively charged A-centers dominate. The findings are analyzed in terms of the density of states and discussed in view of previous experimental and theoretical studies.

  2. A-centers in silicon studied with hybrid density functional theory

    KAUST Repository

    Wang, Hao

    2013-07-29

    Density functional theory employing hybrid functional is used to gain fundamental insight into the interaction of vacancies with oxygen interstitials to form defects known as A-centers in silicon. We calculate the formation energy of the defect with respect to the Fermi energy for all possible charge states. It is found that the neutral and doubly negatively charged A-centers dominate. The findings are analyzed in terms of the density of states and discussed in view of previous experimental and theoretical studies.

  3. Locating the rate-limiting step for the interaction of hydrogen with Mg(0001) using density-functional theory calculations and rate theory

    DEFF Research Database (Denmark)

    Vegge, Tejs

    2004-01-01

    The dissociation of molecular hydrogen on a Mgs0001d surface and the subsequent diffusion of atomic hydrogen into the magnesium substrate is investigated using Density Functional Theory (DFT) calculations and rate theory. The minimum energy path and corresponding transition states are located usi...... to be rate-limiting for the ab- and desorption of hydrogen, respectively. Zero-point energy contributions are found to be substantial for the diffusion of atomic hydrogen, but classical rates are still found to be within an order of magnitude at room temperature.......The dissociation of molecular hydrogen on a Mgs0001d surface and the subsequent diffusion of atomic hydrogen into the magnesium substrate is investigated using Density Functional Theory (DFT) calculations and rate theory. The minimum energy path and corresponding transition states are located using...

  4. Quantum Chromodynamics and Nuclear Physics at Extreme Energy Density

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, B.; Bass, S.A.; Chandrasekharan, S.; Mehen, T.; Springer, R.P.

    2005-11-07

    The report describes research in theoretical quantum chromodynamics, including effective field theories of hadronic interactions, properties of strongly interacting matter at extreme energy density, phenomenology of relativistic heavy ion collisions, and algorithms and numerical simulations of lattice gauge theory and other many-body systems.

  5. Quantum Chromodynamics and Nuclear Physics at Extreme Energy Density

    International Nuclear Information System (INIS)

    Mueller, B.; Bass, S.A.; Chandrasekharan, S.; Mehen, T.; Springer, R.P.

    2005-01-01

    The report describes research in theoretical quantum chromodynamics, including effective field theories of hadronic interactions, properties of strongly interacting matter at extreme energy density, phenomenology of relativistic heavy ion collisions, and algorithms and numerical simulations of lattice gauge theory and other many-body systems.

  6. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry

    Directory of Open Access Journals (Sweden)

    Luis R. Domingo

    2016-09-01

    Full Text Available A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT, is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT, the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

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

    Science.gov (United States)

    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.

  8. 2nd derivatives of the electronic energy in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Dam, H. van

    2001-08-01

    This document details the equations needed to implement the calculation of vibrational frequencies within the density functional formalism of electronic structure theory. This functionality has been incorporated into the CCP1 DFT module and the required changes to the application programmers interface are outlined. Throughout it is assumed that an implementation of Hartree-Fock vibrational frequencies is available that can be modified to incorporate the density functional formalism. Employing GAMESS-UK as an example the required changes to the Hartree-Fock code are outlined. (author)

  9. The topology of the Coulomb potential density. A comparison with the electron density, the virial energy density, and the Ehrenfest force density.

    Science.gov (United States)

    Ferreira, Lizé-Mari; Eaby, Alan; Dillen, Jan

    2017-12-15

    The topology of the Coulomb potential density has been studied within the context of the theory of Atoms in Molecules and has been compared with the topologies of the electron density, the virial energy density and the Ehrenfest force density. The Coulomb potential density is found to be mainly structurally homeomorphic with the electron density. The Coulomb potential density reproduces the non-nuclear attractor which is observed experimentally in the molecular graph of the electron density of a Mg dimer, thus, for the first time ever providing an alternative and energetic foundation for the existence of this critical point. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  10. Nuclear energy density functional from chiral pion-nucleon dynamics revisited

    OpenAIRE

    Kaiser, N.; Weise, W.

    2009-01-01

    We use a recently improved density-matrix expansion to calculate the nuclear energy density functional in the framework of in-medium chiral perturbation theory. Our calculation treats systematically the effects from $1\\pi$-exchange, iterated $1\\pi$-exchange, and irreducible $2\\pi$-exchange with intermediate $\\Delta$-isobar excitations, including Pauli-blocking corrections up to three-loop order. We find that the effective nucleon mass $M^*(\\rho)$ entering the energy density functional is iden...

  11. Stochastic density functional theory at finite temperatures

    Science.gov (United States)

    Cytter, Yael; Rabani, Eran; Neuhauser, Daniel; Baer, Roi

    2018-03-01

    Simulations in the warm dense matter regime using finite temperature Kohn-Sham density functional theory (FT-KS-DFT), while frequently used, are computationally expensive due to the partial occupation of a very large number of high-energy KS eigenstates which are obtained from subspace diagonalization. We have developed a stochastic method for applying FT-KS-DFT, that overcomes the bottleneck of calculating the occupied KS orbitals by directly obtaining the density from the KS Hamiltonian. The proposed algorithm scales as O (" close=")N3T3)">N T-1 and is compared with the high-temperature limit scaling O density approximation (LDA); we demonstrate its efficiency, statistical errors, and bias in the estimation of the free energy per electron for a diamond structure silicon. The bias is small compared to the fluctuations and is independent of system size. In addition to calculating the free energy itself, one can also use the method to calculate its derivatives and obtain the equations of state.

  12. Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

    Science.gov (United States)

    Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

    2018-03-01

    We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

  13. Defining the contributions of permanent electrostatics, Pauli repulsion, and dispersion in density functional theory calculations of intermolecular interaction energies

    Energy Technology Data Exchange (ETDEWEB)

    Horn, Paul R., E-mail: prhorn@berkeley.edu; Mao, Yuezhi; Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu [Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California, Berkeley, California 94720, USA and Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley, California 94720 (United States)

    2016-03-21

    In energy decomposition analysis of Kohn-Sham density functional theory calculations, the so-called frozen (or pre-polarization) interaction energy contains contributions from permanent electrostatics, dispersion, and Pauli repulsion. The standard classical approach to separate them suffers from several well-known limitations. We introduce an alternative scheme that employs valid antisymmetric electronic wavefunctions throughout and is based on the identification of individual fragment contributions to the initial supersystem wavefunction as determined by an energetic optimality criterion. The density deformations identified with individual fragments upon formation of the initial supersystem wavefunction are analyzed along with the distance dependence of the new and classical terms for test cases that include the neon dimer, ammonia borane, water-Na{sup +}, water-Cl{sup −}, and the naphthalene dimer.

  14. A Comparative Density Functional Theory and Density Functional Tight Binding Study of Phases of Nitrogen Including a High Energy Density Material N8

    Directory of Open Access Journals (Sweden)

    Nicholas Capel

    2015-11-01

    Full Text Available We present a comparative dispersion-corrected Density Functional Theory (DFT and Density Functional Tight Binding (DFTB-D study of several phases of nitrogen, including the well-known alpha, beta, and gamma phases as well as recently discovered highly energetic phases: covalently bound cubic gauche (cg nitrogen and molecular (vdW-bound N8 crystals. Among several tested parametrizations of N–N interactions for DFTB, we identify only one that is suitable for modeling of all these phases. This work therefore establishes the applicability of DFTB-D to studies of phases, including highly metastable phases, of nitrogen, which will be of great use for modelling of dynamics of reactions involving these phases, which may not be practical with DFT due to large required space and time scales. We also derive a dispersion-corrected DFT (DFT-D setup (atom-centered basis parameters and Grimme dispersion parameters tuned for accurate description simultaneously of several nitrogen allotropes including covalently and vdW-bound crystals and including high-energy phases.

  15. Nonlocal exchange and kinetic-energy density functionals for electronic systems

    International Nuclear Information System (INIS)

    Glossman, M.D.; Rubio, A.; Balbas, L.C.; Alonso, J.A.

    1992-01-01

    The nonlocal weighted density approximation (WDA) to the exchange and kinetic-energy functionals of many electron systems proposed several years ago by Alonso and Girifalco is used to compute, within the framework of density functional theory, the ground-state electronic density and total energy of noble gas atoms and of neutral jellium-like sodium clusters containing up to 500 atoms. These results are compared with analogous calculations using the well known Thomas-Fermi-Weizsacker-Dirac (TFWD) approximations for the kinetic (TFW) and exchange (D) energy density functionals. An outstanding improvement of the total and exchange energies, of the density at the nucleus and of the expectation values is obtained for atoms within the WDA scheme. For sodium clusters the authors notice a sizeable contribution of the nonlocal effects to the total energy and to the density profiles. In the limit of very large clusters these effects should affect the surface energy of the bulk metal

  16. Site-occupation embedding theory using Bethe ansatz local density approximations

    Science.gov (United States)

    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.

  17. Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error.

    Science.gov (United States)

    Bao, Junwei Lucas; Wang, Ying; He, Xiao; Gagliardi, Laura; Truhlar, Donald G

    2017-11-16

    Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.

  18. Microscopically based energy density functionals for nuclei using the density matrix expansion. II. Full optimization and validation

    Science.gov (United States)

    Navarro Pérez, R.; Schunck, N.; Dyhdalo, A.; Furnstahl, R. J.; Bogner, S. K.

    2018-05-01

    Background: Energy density functional methods provide a generic framework to compute properties of atomic nuclei starting from models of nuclear potentials and the rules of quantum mechanics. Until now, the overwhelming majority of functionals have been constructed either from empirical nuclear potentials such as the Skyrme or Gogny forces, or from systematic gradient-like expansions in the spirit of the density functional theory for atoms. Purpose: We seek to obtain a usable form of the nuclear energy density functional that is rooted in the modern theory of nuclear forces. We thus consider a functional obtained from the density matrix expansion of local nuclear potentials from chiral effective field theory. We propose a parametrization of this functional carefully calibrated and validated on selected ground-state properties that is suitable for large-scale calculations of nuclear properties. Methods: Our energy functional comprises two main components. The first component is a non-local functional of the density and corresponds to the direct part (Hartree term) of the expectation value of local chiral potentials on a Slater determinant. Contributions to the mean field and the energy of this term are computed by expanding the spatial, finite-range components of the chiral potential onto Gaussian functions. The second component is a local functional of the density and is obtained by applying the density matrix expansion to the exchange part (Fock term) of the expectation value of the local chiral potential. We apply the UNEDF2 optimization protocol to determine the coupling constants of this energy functional. Results: We obtain a set of microscopically constrained functionals for local chiral potentials from leading order up to next-to-next-to-leading order with and without three-body forces and contributions from Δ excitations. These functionals are validated on the calculation of nuclear and neutron matter, nuclear mass tables, single-particle shell structure

  19. Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections.

    Science.gov (United States)

    Sergiievskyi, Volodymyr P; Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel

    2014-06-05

    Molecular density functional theory (MDFT) offers an efficient implicit-solvent method to estimate molecule solvation free-energies, whereas conserving a fully molecular representation of the solvent. Even within a second-order approximation for the free-energy functional, the so-called homogeneous reference fluid approximation, we show that the hydration free-energies computed for a data set of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by 2-3 orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canonical to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justification to empirical partial molar volume corrections that have been proposed recently.

  20. Multicomponent density functional theory embedding formulation

    Energy Technology Data Exchange (ETDEWEB)

    Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.; Hammes-Schiffer, Sharon, E-mail: shs3@illinois.edu [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Ave, Urbana, Illinois 61801 (United States)

    2016-07-28

    Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

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

    Science.gov (United States)

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

    2011-05-06

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

  2. Wavelet-based linear-response time-dependent density-functional theory

    Science.gov (United States)

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.; Philouze, Christian; Balakirev, Maxim Y.

    2012-06-01

    Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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. 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.

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

    Science.gov (United States)

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

    2017-03-01

    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.

  5. Condensation energy density in Bi-2212 superconductors

    International Nuclear Information System (INIS)

    Matsushita, Teruo; Kiuchi, Masaru; Haraguchi, Teruhisa; Imada, Takeki; Okamura, Kazunori; Okayasu, Satoru; Uchida, Satoshi; Shimoyama, Jun-ichi; Kishio, Kohji

    2006-01-01

    The relationship between the condensation energy density and the anisotropy parameter, γ a , has been derived for Bi-2212 superconductors in various anisotropic states by analysing the critical current density due to columnar defects introduced by heavy ion irradiation. The critical current density depended on the size of the defects, determined by the kind and irradiation energy of the ions. A significantly large critical current density of 17.0 MA cm -2 was obtained at 5 K and 0.1 T even for the defect density of a matching field of 1 T in a specimen irradiated with iodine ions. The dependence of the critical current density on the size of the defects agreed well with the prediction from the summation theory of pinning forces, and the condensation energy density could be obtained consistently from specimens irradiated with different ions. The condensation energy density obtained increased with decreasing γ a over the entire range of measurement temperature, and reached about 60% of the value for the most three-dimensional Y-123 observed by Civale et al at 5 K. This gives the reason for the very strong pinning in Bi-2212 superconductors at low temperatures. The thermodynamic critical field obtained decreased linearly with increasing temperature and extrapolated to zero at a certain characteristic temperature, T * , lower than the critical temperature, T c . T * , which seems to be associated with the superconductivity in the block layers, was highest for the optimally doped specimen. This shows that the superconductivity becomes more inhomogeneous as the doped state of a superconductor deviates from the optimum condition

  6. Joint density-functional theory and its application to systems in solution

    Science.gov (United States)

    Petrosyan, Sahak A.

    The physics of solvation, the interaction of water with solutes, plays a central role in chemistry and biochemistry, and it is essential for the very existence of life. Despite the central importance of water and the advent of the quantum theory early in the twentieth century, the link between the fundamental laws of physics and the observable properties of water remain poorly understood to this day. The central goal of this thesis is to develop a new formalism and framework to make the study of systems (solutes or surfaces) in contact with liquid water as practical and accurate as standard electronic structure calculations without the need for explicit averaging over large ensembles of configurations of water molecules. The thesis introduces a new form of density functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment. This theory rigorously joins an electron density-functional for the electrons of a solute with a classical density-functional theory for the liquid into a single variational principle for the free energy of the combined system. Using the new form of density-functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment, the thesis then presents the first detailed study of the impact of a solvent on the surface chemistry of Cr2O3, the passivating layer of stainless steel alloys. In comparison to a vacuum, we predict that the presence of water has little impact on the adsorption of chloride ions to the oxygen-terminated surface but has a dramatic effect on the binding of hydrogen to that surface. A key ingredient of a successful joint density functional theory is a good approximate functional for describing the solvent. We explore how the simplest examples of the best known class of approximate forms for the classical density functional fail when applied directly to water. The thesis then presents a computationally efficient density

  7. Excitation energies from Görling-Levy perturbation theory along the range-separated adiabatic connection

    Science.gov (United States)

    Rebolini, Elisa; Teale, Andrew M.; Helgaker, Trygve; Savin, Andreas; Toulouse, Julien

    2018-06-01

    A Görling-Levy (GL)-based perturbation theory along the range-separated adiabatic connection is assessed for the calculation of electronic excitation energies. In comparison with the Rayleigh-Schrödinger (RS)-based perturbation theory this GL-based perturbation theory keeps the ground-state density constant at each order and thus gives the correct ionisation energy at each order. Excitation energies up to first order in the perturbation have been calculated numerically for the helium and beryllium atoms and the hydrogen molecule without introducing any density-functional approximations. In comparison with the RS-based perturbation theory, the present GL-based perturbation theory gives much more accurate excitation energies for Rydberg states but similar excitation energies for valence states.

  8. Source-Free Exchange-Correlation Magnetic Fields in Density Functional Theory.

    Science.gov (United States)

    Sharma, S; Gross, E K U; Sanna, A; Dewhurst, J K

    2018-03-13

    Spin-dependent exchange-correlation energy functionals in use today depend on the charge density and the magnetization density: E xc [ρ, m]. However, it is also correct to define the functional in terms of the curl of m for physical external fields: E xc [ρ,∇ × m]. The exchange-correlation magnetic field, B xc , then becomes source-free. We study this variation of the theory by uniquely removing the source term from local and generalized gradient approximations to the functional. By doing so, the total Kohn-Sham moments are improved for a wide range of materials for both functionals. Significantly, the moments for the pnictides are now in good agreement with experiment. This source-free method is simple to implement in all existing density functional theory codes.

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

    Science.gov (United States)

    Kvaal, Simen; Helgaker, Trygve

    2015-11-14

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

  10. Fission fragment charge and mass distributions in 239Pu(n ,f ) in the adiabatic nuclear energy density functional theory

    Science.gov (United States)

    Regnier, D.; Dubray, N.; Schunck, N.; Verrière, M.

    2016-05-01

    Background: Accurate knowledge of fission fragment yields is an essential ingredient of numerous applications ranging from the formation of elements in the r process to fuel cycle optimization for nuclear energy. The need for a predictive theory applicable where no data are available, together with the variety of potential applications, is an incentive to develop a fully microscopic approach to fission dynamics. Purpose: In this work, we calculate the pre-neutron emission charge and mass distributions of the fission fragments formed in the neutron-induced fission of 239Pu using a microscopic method based on nuclear density functional theory (DFT). Methods: Our theoretical framework is the nuclear energy density functional (EDF) method, where large-amplitude collective motion is treated adiabatically by using the time-dependent generator coordinate method (TDGCM) under the Gaussian overlap approximation (GOA). In practice, the TDGCM is implemented in two steps. First, a series of constrained EDF calculations map the configuration and potential-energy landscape of the fissioning system for a small set of collective variables (in this work, the axial quadrupole and octupole moments of the nucleus). Then, nuclear dynamics is modeled by propagating a collective wave packet on the potential-energy surface. Fission fragment distributions are extracted from the flux of the collective wave packet through the scission line. Results: We find that the main characteristics of the fission charge and mass distributions can be well reproduced by existing energy functionals even in two-dimensional collective spaces. Theory and experiment agree typically within two mass units for the position of the asymmetric peak. As expected, calculations are sensitive to the structure of the initial state and the prescription for the collective inertia. We emphasize that results are also sensitive to the continuity of the collective landscape near scission. Conclusions: Our analysis confirms

  11. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems

    International Nuclear Information System (INIS)

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

    2014-01-01

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ω α and oscillator strengths f α for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ω α (R) curves along the bond dissociation coordinate R for the molecules LiH, Li 2 , and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate

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

    Science.gov (United States)

    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.

  13. Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

    Science.gov (United States)

    Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

    2017-10-01

    Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

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

    Science.gov (United States)

    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

  15. Density Profiles, Energy, and Oscillation Strength of a Quantum Dot in Two Dimensions with a Harmonic Oscillator External Potential using an Orbital-free Energy Functional Based on Thomas–Fermi Theory

    Directory of Open Access Journals (Sweden)

    Suhufa Alfarisa

    2016-03-01

    Full Text Available This research aims i to determine the density profile and calculate the ground state energy of a quantum dot in two dimensions (2D with a harmonic oscillator potential using orbital-free density functional theory, and ii to understand the effect of the harmonic oscillator potential strength on the electron density profiles in the quantum dot. This study determines the total energy functional of the quantum dot that is a functional of the density that depends only on spatial variables. The total energy functional consists of three terms. The first term is the kinetic energy functional, which is the Thomas–Fermi approximation in this case. The second term is the external potential. The harmonic oscillator potential is used in this study. The last term is the electron–electron interactions described by the Coulomb interaction. The functional is formally solved to obtain the electron density as a function of spatial variables. This equation cannot be solved analytically, and thus a numerical method is used to determine the profile of the electron density. Using the electron density profiles, the ground state energy of the quantum dot in 2D can be calculated. The ground state energies obtained are 2.464, 22.26, 90.1957, 252.437, and 496.658 au for 2, 6, 12, 20, and 56 electrons, respectively. The highest electron density is localized close to the middle of the quantum dot. The density profiles decrease with the increasing distance, and the lowest density is at the edge of the quantum dot. Generally, increasing the harmonic oscillator potential strength reduces the density profiles around the center of the quantum dot.

  16. Trivial constraints on orbital-free kinetic energy density functionals

    Science.gov (United States)

    Luo, Kai; Trickey, S. B.

    2018-03-01

    Approximate kinetic energy density functionals (KEDFs) are central to orbital-free density functional theory. Limitations on the spatial derivative dependencies of KEDFs have been claimed from differential virial theorems. We identify a central defect in the argument: the relationships are not true for an arbitrary density but hold only for the minimizing density and corresponding chemical potential. Contrary to the claims therefore, the relationships are not constraints and provide no independent information about the spatial derivative dependencies of approximate KEDFs. A simple argument also shows that validity for arbitrary v-representable densities is not restored by appeal to the density-potential bijection.

  17. Many-body theory and Energy Density Functionals

    Energy Technology Data Exchange (ETDEWEB)

    Baldo, M. [INFN, Catania (Italy)

    2016-07-15

    In this paper a method is first presented to construct an Energy Density Functional on a microscopic basis. The approach is based on the Kohn-Sham method, where one introduces explicitly the Nuclear Matter Equation of State, which can be obtained by an accurate many-body calculation. In this way it connects the functional to the bare nucleon-nucleon interaction. It is shown that the resulting functional can be performing as the best Gogny force functional. In the second part of the paper it is shown how one can go beyond the mean-field level and the difficulty that can appear. The method is based on the particle-vibration coupling scheme and a formalism is presented that can handle the correct use of the vibrational degrees of freedom within a microscopic approach. (orig.)

  18. Radical scavenging activity of some natural tropolones by density functional theory

    Directory of Open Access Journals (Sweden)

    A. G. Al-Sehemi

    2017-07-01

    Full Text Available The ground state neutral geometries of some natural tropolones, i.e. stipitatonic acid (AF1, stipitalide (AF2, stipitaldehydic acid (AF3 and methyl stipitate (AF4 have been optimized by using Density Functional Theory (DFT at B3LYP/6-31G*, B3LYP/6-31G**, B3LYP/6-31+G* and B3LYP/6-31+G** levels of theory. The excited state geometries of AF1-AF4 were optimized by adopting the Time Dependent Density Functional Theory (TDDFT at the same levels of theory. The frequencies and cation species of AF1-AF4 were also computed at all the above mentioned levels of theory. We shed light on the electro-optical and molecular properties, e.g. energy gaps, highest occupied molecular orbitals, lowest unoccupied molecular orbitals, absorption wavelengths, electronegativity (χ, hardness (η, electrophilicity (ω, softness (S, electrophilicity index (ωi and the radical scavenging activity (RSA. Hydrogen atom transfer (HAT and one-electron transfer mechanisms have been discussed to shed light on the RSA. The smallest ionization potential and bond dissociation energy of AF4 are revealing that this compound would have more RSA than those of other counterparts.

  19. Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals.

    Science.gov (United States)

    Śmiga, Szymon; Fabiano, Eduardo; Laricchia, Savio; Constantin, Lucian A; Della Sala, Fabio

    2015-04-21

    We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded molecular systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes this limitation and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method.

  20. Monte Carlo Simulations of Electron Energy-Loss Spectra with the Addition of Fine Structure from Density Functional Theory Calculations.

    Science.gov (United States)

    Attarian Shandiz, Mohammad; Guinel, Maxime J-F; Ahmadi, Majid; Gauvin, Raynald

    2016-02-01

    A new approach is presented to introduce the fine structure of core-loss excitations into the electron energy-loss spectra of ionization edges by Monte Carlo simulations based on an optical oscillator model. The optical oscillator strength is refined using the calculated electron energy-loss near-edge structure by density functional theory calculations. This approach can predict the effects of multiple scattering and thickness on the fine structure of ionization edges. In addition, effects of the fitting range for background removal and the integration range under the ionization edge on signal-to-noise ratio are investigated.

  1. Studying the varied shapes of gold clusters by an elegant optimization algorithm that hybridizes the density functional tight-binding theory and the density functional theory

    Science.gov (United States)

    Yen, Tsung-Wen; Lim, Thong-Leng; Yoon, Tiem-Leong; Lai, S. K.

    2017-11-01

    We combined a new parametrized density functional tight-binding (DFTB) theory (Fihey et al. 2015) with an unbiased modified basin hopping (MBH) optimization algorithm (Yen and Lai 2015) and applied it to calculate the lowest energy structures of Au clusters. From the calculated topologies and their conformational changes, we find that this DFTB/MBH method is a necessary procedure for a systematic study of the structural development of Au clusters but is somewhat insufficient for a quantitative study. As a result, we propose an extended hybridized algorithm. This improved algorithm proceeds in two steps. In the first step, the DFTB theory is employed to calculate the total energy of the cluster and this step (through running DFTB/MBH optimization for given Monte-Carlo steps) is meant to efficiently bring the Au cluster near to the region of the lowest energy minimum since the cluster as a whole has explicitly considered the interactions of valence electrons with ions, albeit semi-quantitatively. Then, in the second succeeding step, the energy-minimum searching process will continue with a skilledly replacement of the energy function calculated by the DFTB theory in the first step by one calculated in the full density functional theory (DFT). In these subsequent calculations, we couple the DFT energy also with the MBH strategy and proceed with the DFT/MBH optimization until the lowest energy value is found. We checked that this extended hybridized algorithm successfully predicts the twisted pyramidal structure for the Au40 cluster and correctly confirms also the linear shape of C8 which our previous DFTB/MBH method failed to do so. Perhaps more remarkable is the topological growth of Aun: it changes from a planar (n =3-11) → an oblate-like cage (n =12-15) → a hollow-shape cage (n =16-18) and finally a pyramidal-like cage (n =19, 20). These varied forms of the cluster's shapes are consistent with those reported in the literature.

  2. Density functional and theoretical study of the temperature and pressure dependency of the plasmon energy of solids

    International Nuclear Information System (INIS)

    Attarian Shandiz, M.; Gauvin, R.

    2014-01-01

    The temperature and pressure dependency of the volume plasmon energy of solids was investigated by density functional theory calculations. The volume change of crystal is the major factor responsible for the variation of valence electron density and plasmon energy in the free electron model. Hence, to introduce the effect of temperature and pressure for the density functional theory calculations of plasmon energy, the temperature and pressure dependency of lattice parameter was used. Also, by combination of the free electron model and the equation of state based on the pseudo-spinodal approach, the temperature and pressure dependency of the plasmon energy was modeled. The suggested model is in good agreement with the results of density functional theory calculations and available experimental data for elements with the free electron behavior.

  3. The energy-momentum problem and gravitation theory

    International Nuclear Information System (INIS)

    Logunov, A.A.; Folomeshkin, V.N.

    1977-01-01

    General properties of geometrized gravitation theories are considered. A covariant formulation of conservation laws in an arbitrary Riemann space-time is presented. In the Einstein theory both symmetric and canonical energy-momentum tensors of the matter and gravitational field system and, in particular, energy-momentum of free gravitational waves prove to be equal to zero. Since gravitational waves carry the curvature and, consequently, affect the detector, this bears witness to an intrinsic contradiction of the Einstein theory. To realize the sources of difficulties concerning energy-momentum in the Einstein theory the gravitational field is treated in the same way as all the other physical fields, i.e. in terms of usual Lorentz-invariant field theory. Unification of this approach with the Einstein idea of geometrization enables to construct the geometrized theory, which is free from contradictions, has clearly defined the notions of gravitation field energy-momentum and satisfactorily describes all known experimental facts. To construct a logically consistent theory one should geometrize only the density of the matter Lagrangian. The gravitation field equations are formulated in terms of the Euclidean space-time with a metric tensor γsub(ik), while the matter motion may be completely described in terms of the non-Euclidean space-time with a metric tensor gsub(ik). For strong gravitational fields the predictions of the quasi-linear theory under consideration appriciably differ from those of the Einstein formulation of the gravitation theory. No black holes are present in the theory. The results of the calculation for the energy flow of gravitational waves are rigorously unambiguous and show that gravitational waves carry positively definite energy

  4. Minimal nuclear energy density functional

    Science.gov (United States)

    Bulgac, Aurel; Forbes, Michael McNeil; Jin, Shi; Perez, Rodrigo Navarro; Schunck, Nicolas

    2018-04-01

    We present a minimal nuclear energy density functional (NEDF) called "SeaLL1" that has the smallest number of possible phenomenological parameters to date. SeaLL1 is defined by seven significant phenomenological parameters, each related to a specific nuclear property. It describes the nuclear masses of even-even nuclei with a mean energy error of 0.97 MeV and a standard deviation of 1.46 MeV , two-neutron and two-proton separation energies with rms errors of 0.69 MeV and 0.59 MeV respectively, and the charge radii of 345 even-even nuclei with a mean error ɛr=0.022 fm and a standard deviation σr=0.025 fm . SeaLL1 incorporates constraints on the equation of state (EoS) of pure neutron matter from quantum Monte Carlo calculations with chiral effective field theory two-body (NN ) interactions at the next-to-next-to-next-to leading order (N3LO) level and three-body (NNN ) interactions at the next-to-next-to leading order (N2LO) level. Two of the seven parameters are related to the saturation density and the energy per particle of the homogeneous symmetric nuclear matter, one is related to the nuclear surface tension, two are related to the symmetry energy and its density dependence, one is related to the strength of the spin-orbit interaction, and one is the coupling constant of the pairing interaction. We identify additional phenomenological parameters that have little effect on ground-state properties but can be used to fine-tune features such as the Thomas-Reiche-Kuhn sum rule, the excitation energy of the giant dipole and Gamow-Teller resonances, the static dipole electric polarizability, and the neutron skin thickness.

  5. Vacuum stress energy density and its gravitational implications

    Science.gov (United States)

    Estrada, Ricardo; Fulling, Stephen A.; Kaplan, Lev; Kirsten, Klaus; Liu, Zhonghai; Milton, Kimball A.

    2008-04-01

    In nongravitational physics the local density of energy is often regarded as merely a bookkeeping device; only total energy has an experimental meaning—and it is only modulo a constant term. But in general relativity the local stress-energy tensor is the source term in Einstein's equation. In closed universes, and those with Kaluza-Klein dimensions, theoretical consistency demands that quantum vacuum energy should exist and have gravitational effects, although there are no boundary materials giving rise to that energy by van der Waals interactions. In the lab there are boundaries, and in general the energy density has a nonintegrable singularity as a boundary is approached (for idealized boundary conditions). As pointed out long ago by Candelas and Deutsch, in this situation there is doubt about the viability of the semiclassical Einstein equation. Our goal is to show that the divergences in the linearized Einstein equation can be renormalized to yield a plausible approximation to the finite theory that presumably exists for realistic boundary conditions. For a scalar field with Dirichlet or Neumann boundary conditions inside a rectangular parallelepiped, we have calculated by the method of images all components of the stress tensor, for all values of the conformal coupling parameter and an exponential ultraviolet cutoff parameter. The qualitative features of contributions from various classes of closed classical paths are noted. Then the Estrada-Kanwal distributional theory of asymptotics, particularly the moment expansion, is used to show that the linearized Einstein equation with the stress-energy near a plane boundary as source converges to a consistent theory when the cutoff is removed. This paper reports work in progress on a project combining researchers in Texas, Louisiana and Oklahoma. It is supported by NSF Grants PHY-0554849 and PHY-0554926.

  6. Solvation in atomic liquids: connection between Gaussian field theory and density functional theory

    Directory of Open Access Journals (Sweden)

    V. Sergiievskyi

    2017-12-01

    Full Text Available For the problem of molecular solvation, formulated as a liquid submitted to the external potential field created by a molecular solute of arbitrary shape dissolved in that solvent, we draw a connection between the Gaussian field theory derived by David Chandler [Phys. Rev. E, 1993, 48, 2898] and classical density functional theory. We show that Chandler's results concerning the solvation of a hard core of arbitrary shape can be recovered by either minimising a linearised HNC functional using an auxiliary Lagrange multiplier field to impose a vanishing density inside the core, or by minimising this functional directly outside the core — indeed a simpler procedure. Those equivalent approaches are compared to two other variants of DFT, either in the HNC, or partially linearised HNC approximation, for the solvation of a Lennard-Jones solute of increasing size in a Lennard-Jones solvent. Compared to Monte-Carlo simulations, all those theories give acceptable results for the inhomogeneous solvent structure, but are completely out-of-range for the solvation free-energies. This can be fixed in DFT by adding a hard-sphere bridge correction to the HNC functional.

  7. FDE-vdW: A van der Waals inclusive subsystem density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu [Department of Chemistry, Rutgers University, Newark, New Jersey 07102 (United States); Eshuis, Henk [Department of Chemistry and Biochemistry, Montclair State University, Montclair, New Jersey 07043 (United States)

    2014-07-28

    We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

  8. New theory of radiative energy transfer in free electromagnetic fields

    International Nuclear Information System (INIS)

    Wolf, E.

    1976-01-01

    A new theory of radiative energy transfer in free, statistically stationary electromagnetic fields is presented. It provides a model for energy transport that is rigorous both within the framework of the stochastic theory of the classical field as well as within the framework of the theory of the quantized field. Unlike the usual phenomenological model of radiative energy transfer that centers around a single scalar quantity (the specific intensity of radiation), our theory brings into evidence the need for characterizing the energy transport by means of two (related) quantities: a scalar and a vector that may be identified, in a well-defined sense, with ''angular components'' of the average electromagnetic energy density and of the average Poynting vector, respectively. Both of them are defined in terms of invariants of certain new electromagnetic correlation tensors. In the special case when the field is statistically homogeneous, our model reduces to the usual one and our angular component of the average electromagnetic energy density, when multiplied by the vacuum speed of light, then acquires all the properties of the specific intensity of radiation. When the field is not statistically homogeneous our model approximates to the usual phenomenological one, provided that the angular correlations between plane wave modes of the field extend over a sufficiently small solid angle of directions about the direction of propagation of each mode. It is tentatively suggested that, when suitably normalized, our angular component of the average electromagnetic energy density may be interpreted as a quasi-probability (general quantum-mechancial phase-space distribution function, such as Wigner's) for the position and the momentum of a photon

  9. Covariant density functional theory for nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Badarch, U.

    2007-07-01

    The present thesis is organized as follows. In Chapter 2 we study the Nucleon-Nucleon (NN) interaction in Dirac-Brueckner (DB) approach. We start by considering the NN interaction in free-space in terms of the Bethe-Salpeter (BS) equation to the meson exchange potential model. Then we present the DB approach for nuclear matter by extending the BS equation for the in-medium NN interaction. From the solution of the three-dimensional in-medium BS equation, we derive the DB self-energies and total binding energy which are the main results of the DB approach, which we later incorporate in the field theoretical calculation of the nuclear equation of state. In Chapter 3, we introduce the basic concepts of density functional theory in the context of Quantum Hadrodynamics (QHD-I). We reach the main point of this work in Chapter 4 where we introduce the DDRH approach. In the DDRH theory, the medium dependence of the meson-nucleon vertices is expressed as functionals of the baryon field operators. Because of the complexities of the operator-valued functionals we decide to use the mean-field approximation. In Chapter 5, we contrast microscopic and phenomenological approaches to extracting density dependent meson-baryon vertices. Chapter 6 gives the results of our studies of the EOS of infinite nuclear matter in detail. Using formulas derived in Chapters 4 and 5 we calculate the properties of symmetric and asymmetric nuclear matter and pure neutron matter. (orig.)

  10. Covariant density functional theory for nuclear matter

    International Nuclear Information System (INIS)

    Badarch, U.

    2007-01-01

    The present thesis is organized as follows. In Chapter 2 we study the Nucleon-Nucleon (NN) interaction in Dirac-Brueckner (DB) approach. We start by considering the NN interaction in free-space in terms of the Bethe-Salpeter (BS) equation to the meson exchange potential model. Then we present the DB approach for nuclear matter by extending the BS equation for the in-medium NN interaction. From the solution of the three-dimensional in-medium BS equation, we derive the DB self-energies and total binding energy which are the main results of the DB approach, which we later incorporate in the field theoretical calculation of the nuclear equation of state. In Chapter 3, we introduce the basic concepts of density functional theory in the context of Quantum Hadrodynamics (QHD-I). We reach the main point of this work in Chapter 4 where we introduce the DDRH approach. In the DDRH theory, the medium dependence of the meson-nucleon vertices is expressed as functionals of the baryon field operators. Because of the complexities of the operator-valued functionals we decide to use the mean-field approximation. In Chapter 5, we contrast microscopic and phenomenological approaches to extracting density dependent meson-baryon vertices. Chapter 6 gives the results of our studies of the EOS of infinite nuclear matter in detail. Using formulas derived in Chapters 4 and 5 we calculate the properties of symmetric and asymmetric nuclear matter and pure neutron matter. (orig.)

  11. Reduced-density-matrix theory and algebraic structures

    International Nuclear Information System (INIS)

    Kryachko, E.S.

    1978-01-01

    A survey of recent work on algebraic structures and reduced-density-matrix theory is presented. The approach leads to a method of classifying reduced density matrices and generalizes the notion of open and closed shells in many-body theory. 6 references

  12. Formation energies of rutile metal dioxides using density functional theory

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; Hansen, Heine Anton; Rossmeisl, Jan

    2009-01-01

    We apply standard density functional theory at the generalized gradient approximation (GGA) level to study the stability of rutile metal oxides. It is well known that standard GGA exchange and correlation in some cases is not sufficient to address reduction and oxidation reactions. Especially...... and due to a more accurate description of exchange for this particular GGA functional compared to PBE. Furthermore, we would expect the self-interaction problem to be largest for the most localized d orbitals; that means the late 3d metals and since Co, Fe, Ni, and Cu do not form rutile oxides...

  13. Comments on the locality in density-functional theory

    International Nuclear Information System (INIS)

    Lindgren, Ingvar; Salomonson, Sten

    2003-01-01

    The 'locality hypothesis' in density-functional theory (DFT), implying that the functional derivative is equivalent to a multiplicative local function, forms the basis of models of Kohn-Sham type. This has been generally accepted by the community since the advent of the model, and has later been formally proved for a large class of functionals. The hypothesis has recently been questioned by Nesbet [Phys. Rev. A 58, R12 (1998) and Phys. Rev. A 65, 010502 (2001)], who claims that it fails for the kinetic-energy functional for a system with more than two noninteracting electrons with a nondegenerate ground state. This conclusion has been questioned by Gal [Phys. Rev. A 62, 044501 (2000)] and by Holas and March [Phys. Rev. A 64, 016501 (2001)]. We claim that the arguments of Nesbet are incorrect, since the orbital functional used for the kinetic energy is not a unique functional of the total density in the domain of unnormalized orbitals. We have demonstrated that with a proper definition of the kinetic energy, which is a unique density functional also in the unnormalized region, the derivative can be represented by a single local multiplicative function for all v-representable densities. Therefore, we consider the controversy connected with the issue raised by Nesbet as resolved. We believe that the proof of the differentiability given here can be extended to larger groups of DFT functionals, and works along these lines are in progress

  14. Energy effects on the structure and thermodynamic properties of nanoconfined fluids (a density functional theory study).

    Science.gov (United States)

    Keshavarzi, Ezat; Kamalvand, Mohammad

    2009-04-23

    The structure and properties of fluids confined in nanopores may show a dramatic departure from macroscopic bulk fluids. The main reason for this difference lies in the influence of system walls. In addition to the entropic wall effect, system walls can significantly change the energy of the confined fluid compared to macroscopic bulk fluids. The energy effect of the walls on a nanoconfined fluid appears in two forms. The first effect is the cutting off of the intermolecular interactions by the walls, which appears for example in the integrals for calculation of the thermodynamic properties. The second wall effect involves the wall-molecule interactions. In such confined fluids, the introduction of wall forces and the competition between fluid-wall and fluid-fluid forces could lead to interesting thermodynamic properties, including new kinds of phase transitions not observed in the macroscopic fluid systems. In this article, we use the perturbative fundamental measure density functional theory to study energy effects on the structure and properties of a hard core two-Yukawa fluid confined in a nanoslit. Our results show the changes undergone by the structure and phase transition of the nanoconfined fluids as a result of energy effects.

  15. Excitation energy and angular momentum dependence of the nuclear level densities

    International Nuclear Information System (INIS)

    Razavi, R.; Kakavand, T.; Behkami, A. N.

    2007-01-01

    We have investigated the excitation energy (E) dependence of nuclear level density for Bethe formula and constant temperature model. The level density parameter aa nd the back shifted energy from the Bethe formula are obtained by fitting the complete level schemes. Also the level density parameters from the constant temperature model have been determined for several nuclei. we have shown that the microscopic theory provides more precise information on the nuclear level densities. On the other hand, the spin cut-off parameter and effective moment of inertia are determined by studying of the angular momentum (J) dependence of the nuclear level density, and effective moment of inertia is compared with rigid body value.

  16. Simple descriptors for proton-conducting perovskites from density functional theory

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan

    2010-01-01

    series of (pseudo)cubic perovskites, ABO3, have been investigated using density functional theory calculations. The structures have been optimized and thermodynamic properties and activation energies for the relevant steps of the hydrogen/proton diffusion mechanism have been calculated using...... the nudged elastic band path technique. We find a strong correlation between the O-H binding energy for hydrogen/proton uptake in perovskites and the energy barriers involved in the observed Grotthuss-type diffusion process. We demonstrate the possibility of estimating diffusion rates based on O-H binding...

  17. Discontinuities of Green functions in field theory at finite temperature and density

    International Nuclear Information System (INIS)

    Kobes, R.L.; Semenoff, G.W.

    1985-01-01

    We derive systematic rules for calculating the imaginary parts of Minkowski space Green functions in quantum field theory at finite temperature and density. Self-energy corrections are used as an example of the application of these rules. (orig.)

  18. General framework for fluctuating dynamic density functional theory

    Science.gov (United States)

    Durán-Olivencia, Miguel A.; Yatsyshin, Peter; Goddard, Benjamin D.; Kalliadasis, Serafim

    2017-12-01

    We introduce a versatile bottom-up derivation of a formal theoretical framework to describe (passive) soft-matter systems out of equilibrium subject to fluctuations. We provide a unique connection between the constituent-particle dynamics of real systems and the time evolution equation of their measurable (coarse-grained) quantities, such as local density and velocity. The starting point is the full Hamiltonian description of a system of colloidal particles immersed in a fluid of identical bath particles. Then, we average out the bath via Zwanzig’s projection-operator techniques and obtain the stochastic Langevin equations governing the colloidal-particle dynamics. Introducing the appropriate definition of the local number and momentum density fields yields a generalisation of the Dean-Kawasaki (DK) model, which resembles the stochastic Navier-Stokes description of a fluid. Nevertheless, the DK equation still contains all the microscopic information and, for that reason, does not represent the dynamical law of observable quantities. We address this controversial feature of the DK description by carrying out a nonequilibrium ensemble average. Adopting a natural decomposition into local-equilibrium and nonequilibrium contribution, where the former is related to a generalised version of the canonical distribution, we finally obtain the fluctuating-hydrodynamic equation governing the time-evolution of the mesoscopic density and momentum fields. Along the way, we outline the connection between the ad hoc energy functional introduced in previous DK derivations and the free-energy functional from classical density-functional theory. The resultant equation has the structure of a dynamical density-functional theory (DDFT) with an additional fluctuating force coming from the random interactions with the bath. We show that our fluctuating DDFT formalism corresponds to a particular version of the fluctuating Navier-Stokes equations, originally derived by Landau and Lifshitz

  19. Density functional theory investigation of two-dimensional dipolar fermions in a harmonic trap

    International Nuclear Information System (INIS)

    Ustunel, Hande; Abedinpour, Saeed H; Tanatar, B

    2014-01-01

    We investigate the behavior of polarized dipolar fermions in a two-dimensional harmonic trap in the framework of the density functional theory (DFT) formalism using the local density approximation. We treat only a few particles interacting moderately. Important results were deduced concerning key characteristics of the system such as total energy and particle density. Our results indicate that, at variance with Coulombic systems, the exchange- correlation component was found to provide a large contribution to the total energy for a large range of interaction strengths and particle numbers. In addition, the density profiles of the dipoles are shown to display important features around the origin that is not possible to capture by earlier, simpler treatments of such systems

  20. [Ionization energies and infrared spectra studies of histidine using density functional theory].

    Science.gov (United States)

    Hu, Qiong; Wang, Guo-Ying; Liu, Gang; Ou, Jia-Ming; Wang, Rui-Li

    2010-05-01

    Histidines provide axial ligands to the primary electron donors in photosynthetic reaction centers (RCs) and play an important role in the protein environments of these donors. In this paper the authors present a systematic study of ionization energies and vibrational properties of histidine using hybrid density functional theory (DFT). All calculations were undertaken by using B3LYP method in combination with four basis sets: 6-31G(d), 6-31G(df, p), 6-31+G(d) and 6-311+G(2d, 2p) with the aim to investigate how the basis sets influence the calculation results. To investigate solvent effects and gain a detailed understanding of marker bands of histidine, the ionization energies of histidine and the vibrational frequencies of histidine which are unlabeled and 13C, 15N, and 2H labeled in the gas phase, CCl4, protein environment, THF and water solution, which span a wide range of dielectric constant, were also calculated. Our results showed that: (1) The main geometry parameters of histidine were impacted by basis sets and mediums, and C2-N3 and N3-C4 bond of imidazole ring of histidine side chain display the maximum bond lengths in the gas phase; (2) single point energies and frequencies calculated were decreased while ionization energies increased with the increasing level of basis sets and diffuse function applied in the same solvent; (3) with the same computational method, the higher the dielectric constant of the solvent used, the lower the ionization energy and vibrational frequency and the higher the intensity obtained. In addition, calculated ionization energy in the gas phase and marker bands of histidine as well as frequency shift upon 13C and 15N labeling at the computationally more expensive 6-311+G(2d, 2p) level are in good agreement with experimental observations available in literatures. All calculations indicated that the results calculated by using higher level basis set with diffuse function were more accurate and closer to the experimental value. In

  1. Multicomponent density-functional theory for time-dependent systems

    NARCIS (Netherlands)

    Butriy, O.; Ebadi, H.; de Boeij, P. L.; van Leeuwen, R.; Gross, E. K. U.

    2007-01-01

    We derive the basic formalism of density functional theory for time-dependent electron-nuclear systems. The basic variables of this theory are the electron density in body-fixed frame coordinates and the diagonal of the nuclear N-body density matrix. The body-fixed frame transformation is carried

  2. Thermodynamics as a Foundation for Density Functional Theory

    International Nuclear Information System (INIS)

    Argaman, Nathan

    2014-01-01

    Density Functional Theory (DFT) is the method of choice for an ever increasing number of electronic structure computations (recently reaching 30,000 publications per year). It was founded in the sixties on the basis of the Hohenberg-Kohn theorem and the Kohn-Sham equations, which were originally proved and derived for electronic ground states. Alternatively, one may use thermodynamics to derive DFT for finite-temperature ensembles, with the ground-state theory recovered in the zero temperature limit. Specifically, the transformation from chemical potential µ to electron number N as a free variable may be directly generalized to clarify how DFT uses the density distribution n(r), rather than the external potential v(r), to specify a particular inhomogeneous electronic system. Relating interacting and non-interacting systems with the same n(r) distribution, one recovers not only the Kohn-Sham formulation, but also the so-called adiabatic connection theorem, which gives an explicit expression for the exchange-correlation energy in terms of the 'exchangecorrelation hole.' This derivation has the advantage of being constructive, rather than being based on a reductio ad absurdum argument. It thus serves as an excellent basis for a discussion of the approximations which are inevitably introduced, including the Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA)

  3. Local energy equation for two-electron atoms and relation between kinetic energy and electron densities

    International Nuclear Information System (INIS)

    March, N.H.

    2002-08-01

    In early work, Dawson and March [J. Chem. Phys. 81, 5850 (1984)] proposed a local energy method for treating both Hartree-Fock and correlated electron theory. Here, an exactly solvable model two-electron atom with pure harmonic interactions is treated in its ground state in the above context. A functional relation between the kinetic energy density t(r) at the origin r=0 and the electron density p(r) at the same point then emerges. The same approach is applied to the Hookean atom; in which the two electrons repel with Coulombic energy e 2 /r 12 , with r 12 the interelectronic separation, but are still harmonically confined. Again the kinetic energy density t(r) is the focal point, but now generalization away from r=0 is also effected. Finally, brief comments are added about He-like atomic ions in the limit of large atomic number. (author)

  4. Non-local energy density functionals: models plus some exact general results

    International Nuclear Information System (INIS)

    March, N.H.

    2001-02-01

    Holas and March (Phys. Rev. A51, 2040, 1995) gave a formally exact expression for the force - δV xc (r-tilde)/δr-tilde associated with the exchange-correlation potential V xc (r-tilde) of density functional theory. This forged a precise link between first- and second-order density matrices and V xc (r-tilde). Here models are presented in which these low-order matrices can be related to the ground-state electron density. This allows non-local energy density functionals to be constructed within the framework of such models. Finally, results emerging from these models have led to the derivation of some exact 'nuclear cusp' relations for exchange and correlation energy densities in molecules, clusters and condensed phases. (author)

  5. Density-functional theory simulation of large quantum dots

    Science.gov (United States)

    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.

  6. Magnetic energy density and plasma energy density in the Venus wake

    Science.gov (United States)

    Perez De Tejada, H. A.; Durand-Manterola, H. J.; Lundin, R.; Barabash, S.; Zhang, T.; Reyes-Ruiz, M.; Sauvaud, J.

    2013-05-01

    Magnetic energy density and plasma energy density in the Venus wake H. Pérez-de-Tejada1, H. Durand-Manterola1, R. Lundin2, S. Barabash2, T. L. Zhang3, A. Sauvaud4, M. Reyes-Ruiz5. 1 - Institute of Geophysics, UNAM, México, D. F. 2 - Swedish Institute of Space Physics, Umea, Sweden 3 - Space Research Institute, Graz, Austria 4 - CESR, Toulouse, France 5 - Institute of Astronomy, UNAM, Ensenada, México Measurements conducted in the Venus wake with the magnetometer and the Aspera-4 plasma instrument of the Venus Express spacecraft show that average values of the kinetic energy density of the plasma in that region are comparable to average local values of the magnetic energy density. Observations were carried out in several orbits of the Venus Express near the midnight plane and suggest that the total energy content in the Venus wake is distributed with nearly comparable values between the plasma and the magnetic field. Processes associated with the solar wind erosion of planetary ions from the polar magnetic regions of the ionosphere are involved in the comparable distribution of both energy components.

  7. Rapidity-density patterns for events in a stochastic-field multiparticle theory

    International Nuclear Information System (INIS)

    Arnold, R.C.

    1976-02-01

    Typical-event rapidity distributions expected at energies of a few TeV are calculated in a stochastic-field multiparticle production theory. Short range rapidity correlations with characteristics of a Van der Waals fluid give rise to ''domain'' patterns in rapidity density, which have the appearance of clusters separated by rapidity gaps

  8. Density functional and many-body theories of Hydrogen plasmas

    International Nuclear Information System (INIS)

    Perrot, F.; Dharma-Wardana, M.W.C.

    1983-11-01

    This work is an attempt to go beyond the standard description of hot condensed matter using the well-known ''average atom model''. The first part describes a static model using ''Density functional theory'' to calculate self-consistent coupled electron and ion density profiles of the plasma not restricted to a single average atomic sphere. In a second part, the results are used as ingredients for a many-body approach to electronic properties: the one-particle Green-function self-energy is calculated, from which shifted levels, populations and level-widths are deduced. Results for the Hydrogen plasma are reported, with emphasis on the 1s bound state

  9. Covariant density functional theory beyond mean field and applications for nuclei far from stability

    International Nuclear Information System (INIS)

    Ring, P

    2010-01-01

    Density functional theory provides a very powerful tool for a unified microscopic description of nuclei all over the periodic table. It is not only successful in reproducing bulk properties of nuclear ground states such as binding energies, radii, or deformation parameters, but it also allows the investigation of collective phenomena, such as giant resonances and rotational excitations. However, it is based on the mean field concept and therefore it has its limits. We discuss here two methods based based on covariant density functional theory going beyond the mean field concept, (i) models with an energy dependent self energy allowing the coupling to complex configurations and a quantitative description of the width of giant resonances and (ii) methods of configuration mixing between Slater determinants with different deformation and orientation providing are very successful description of transitional nuclei and quantum phase transitions.

  10. Density functional theory calculations of magnetocrystalline anisotropy energies for (Fe(1-x)Co(x))(2)B.

    Science.gov (United States)

    Däne, Markus; Kim, Soo Kyung; Surh, Michael P; Åberg, Daniel; Benedict, Lorin X

    2015-07-08

    We present and discuss density functional theory calculations of magnetic properties of the family of ferromagnetic compounds, (Fe(1-x)Co(x))(2)B, focusing specifically on the magnetocrystalline anisotropy energy (MAE). Using periodic supercells of various sizes (up to 96 atoms), it is shown that the general qualitative features of the composition dependence of the MAE is in agreement with experimental findings, while our predicted magnitudes are larger than those of experiment. We find that the use of small supercells (6 and 12-atom) favors larger MAE values relative to a statistical sample of configurations constructed with 96-atom supercells. The effect of lattice relaxations is shown to be small. Calculations of the Curie temperature for this alloy are also presented.

  11. Density measurement using gamma radiation - theory and application

    International Nuclear Information System (INIS)

    Springer, E.K.

    1979-01-01

    There are still widespread uncertainties about the use and safety of gamma radiation in industries. This paper describes, by the example of radiometric density measurement, the theory of gamma radiation. The differences and advantages of both types of detectors, the ionization chamber and the scintillation counter, are discussed. The degree of accuracy which can be expected from the radiometric density meter will be defined, and the inter-relationship: source strength - measuring range - measuring length(normally the pipe diameter) in relation to the measuring accuracy required will be explained in detail. The use of radioactive material requires the permission of the Atomic Energy Board. The formalities involved to receive a user's licence and the implementations of safety standards set by the local authorities are discussed in depth [af

  12. Microhartree precision in density functional theory calculations

    Science.gov (United States)

    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.

  13. Efficient molecular density functional theory using generalized spherical harmonics expansions.

    Science.gov (United States)

    Ding, Lu; Levesque, Maximilien; Borgis, Daniel; Belloni, Luc

    2017-09-07

    We show that generalized spherical harmonics are well suited for representing the space and orientation molecular density in the resolution of the molecular density functional theory. We consider the common system made of a rigid solute of arbitrary complexity immersed in a molecular solvent, both represented by molecules with interacting atomic sites and classical force fields. The molecular solvent density ρ(r,Ω) around the solute is a function of the position r≡(x,y,z) and of the three Euler angles Ω≡(θ,ϕ,ψ) describing the solvent orientation. The standard density functional, equivalent to the hypernetted-chain closure for the solute-solvent correlations in the liquid theory, is minimized with respect to ρ(r,Ω). The up-to-now very expensive angular convolution products are advantageously replaced by simple products between projections onto generalized spherical harmonics. The dramatic gain in speed of resolution enables to explore in a systematic way molecular solutes of up to nanometric sizes in arbitrary solvents and to calculate their solvation free energy and associated microscopic solvent structure in at most a few minutes. We finally illustrate the formalism by tackling the solvation of molecules of various complexities in water.

  14. Plato: A localised orbital based density functional theory code

    Science.gov (United States)

    Kenny, S. D.; Horsfield, A. P.

    2009-12-01

    The Plato package allows both orthogonal and non-orthogonal tight-binding as well as density functional theory (DFT) calculations to be performed within a single framework. The package also provides extensive tools for analysing the results of simulations as well as a number of tools for creating input files. The code is based upon the ideas first discussed in Sankey and Niklewski (1989) [1] with extensions to allow high-quality DFT calculations to be performed. DFT calculations can utilise either the local density approximation or the generalised gradient approximation. Basis sets from minimal basis through to ones containing multiple radial functions per angular momenta and polarisation functions can be used. Illustrations of how the package has been employed are given along with instructions for its utilisation. Program summaryProgram title: Plato Catalogue identifier: AEFC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 219 974 No. of bytes in distributed program, including test data, etc.: 1 821 493 Distribution format: tar.gz Programming language: C/MPI and PERL Computer: Apple Macintosh, PC, Unix machines Operating system: Unix, Linux and Mac OS X Has the code been vectorised or parallelised?: Yes, up to 256 processors tested RAM: Up to 2 Gbytes per processor Classification: 7.3 External routines: LAPACK, BLAS and optionally ScaLAPACK, BLACS, PBLAS, FFTW Nature of problem: Density functional theory study of electronic structure and total energies of molecules, crystals and surfaces. Solution method: Localised orbital based density functional theory. Restrictions: Tight-binding and density functional theory only, no exact exchange. Unusual features: Both atom centred and uniform meshes available

  15. Magnetic fields and density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Salsbury Jr., Freddie [Univ. of California, Berkeley, CA (United States)

    1999-02-01

    A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.

  16. Magnetic fields and density functional theory

    International Nuclear Information System (INIS)

    Salsbury, Freddie Jr.

    1999-01-01

    A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules

  17. Quantum Crystallography: Density Matrix-Density Functional Theory and the X-Ray Diffraction Experiment

    Science.gov (United States)

    Soirat, Arnaud J. A.

    Density Matrix Theory is a Quantum Mechanical formalism in which the wavefunction is eliminated and its role taken over by reduced density matrices. The interest of this is that, it allows one, in principle, to calculate any electronic property of a physical system, without having to solve the Schrodinger equation, using only two entities much simpler than an N-body wavefunction: first and second -order reduced density matrices. In practice, though, this very promising possibility faces the tremendous theoretical problem of N-representability, which has been solved for the former, but, until now, voids any hope of theoretically determining the latter. However, it has been shown that single determinant reduced density matrices of any order may be recovered from coherent X-ray diffraction data, if one provides a proper Quantum Mechanical description of the Crystallography experiment. A deeper investigation of this method is the purpose of this work, where we, first, further study the calculation of X-ray reduced density matrices N-representable by a single Slater determinant. In this context, we independently derive necessary and sufficient conditions for the uniqueness of the method. We then show how to account for electron correlation in this model. For the first time, indeed, we derive highly accurate, yet practical, density matrices approximately N-representable by correlated-determinant wavefunctions. The interest of such a result lies in the Quantum Mechanical validity of these density matrices, their property of being entirely obtainable from X-ray coherent diffraction data, their very high accuracy conferred by this known property of the N-representing wavefunction, as well as their definition as explicit functionals of the density. All of these properties are finally used in both a theoretical and a numerical application: in the former, we show that these density matrices may be used in the context of Density Functional Theory to highly accurately determine

  18. density functional theory approach

    Indian Academy of Sciences (India)

    YOGESH ERANDE

    2017-07-27

    Jul 27, 2017 ... a key role in all optical switching devices, since their optical properties can be .... optimized in the gas phase using Density Functional Theory. (DFT).39 The ...... The Mediation of Electrostatic Effects by Sol- vents J. Am. Chem.

  19. Molecular Excitation Energies from Time-Dependent Density Functional Theory Employing Random-Phase Approximation Hessians with Exact Exchange.

    Science.gov (United States)

    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.

  20. Neutron stars as probes of extreme energy density matter

    Indian Academy of Sciences (India)

    2015-05-07

    May 7, 2015 ... Neutron stars have long been regarded as extraterrestrial laboratories from which we can learn about extreme energy density matter at low temperatures. In this article, some of the recent advances made in astrophysical observations and related theory are highlighted. Although the focus is on the much ...

  1. Density functional theory for polymeric systems in 2D

    International Nuclear Information System (INIS)

    Słyk, Edyta; Bryk, Paweł; Roth, Roland

    2016-01-01

    We propose density functional theory for polymeric fluids in two dimensions. The approach is based on Wertheim’s first order thermodynamic perturbation theory (TPT) and closely follows density functional theory for polymers proposed by Yu and Wu (2002 J. Chem. Phys . 117 2368). As a simple application we evaluate the density profiles of tangent hard-disk polymers at hard walls. The theoretical predictions are compared against the results of the Monte Carlo simulations. We find that for short chain lengths the theoretical density profiles are in an excellent agreement with the Monte Carlo data. The agreement is less satisfactory for longer chains. The performance of the theory can be improved by recasting the approach using the self-consistent field theory formalism. When the self-avoiding chain statistics is used, the theory yields a marked improvement in the low density limit. Further improvements for long chains could be reached by going beyond the first order of TPT. (paper)

  2. G-centers in irradiated silicon revisited: A screened hybrid density functional theory approach

    KAUST Repository

    Wang, H.

    2014-05-13

    Electronic structure calculations employing screened hybrid density functional theory are used to gain fundamental insight into the interaction of carbon interstitial (Ci) and substitutional (Cs) atoms forming the CiCs defect known as G-center in silicon (Si). The G-center is one of the most important radiation related defects in Czochralski grown Si. We systematically investigate the density of states and formation energy for different types of CiCs defects with respect to the Fermi energy for all possible charge states. Prevalence of the neutral state for the C-type defect is established.

  3. A multiconfigurational hybrid density-functional theory

    DEFF Research Database (Denmark)

    Sharkas, Kamal; Savin, Andreas; Jensen, Hans Jørgen Aagaard

    2012-01-01

    We propose a multiconfigurational hybrid density-functional theory which rigorously combines a multiconfiguration self-consistent-field calculation with a density-functional approximation based on a linear decomposition of the electron-electron interaction. This gives a straightforward extension ...

  4. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

    Science.gov (United States)

    Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

    2015-02-24

    Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

  5. A thermodynamic perturbation theory for the surface tension and ion density profile of a liquid metal

    International Nuclear Information System (INIS)

    Evans, R.; Kumaravadivel, R.

    1976-01-01

    A simple scheme for determining the ion density profile and the surface tension of a liquid metal is described. Assuming that the interaction between metallic pseudo-ions is of the form introduced by Evans, an approximate expression for the excess free energy of the system is derived using the thermodynamic perturbation theory of Weeks, Chandler and Anderson. This excess free energy is then minimized with respect to a parameter which specifies the ion density profile, and the surface tension is given directly. From a consideration of the dependence of the interionic forces on the electron density it is predicted that the ions should take up a very steep density profile at the liquid metal surface. This behaviour is contrasted with that to be expected for rare-gas fluids in which the interatomic forces are density-independent. The values of the surface tension calculated for liquid Na, K and Al from a simplified version of the theory are in reasonable agreement with experiment. (author)

  6. Building a universal nuclear energy density functional (UNEDF)

    Energy Technology Data Exchange (ETDEWEB)

    Nazarewicz, Witold [Univ. of Tennessee, Knoxville, TN (United States)

    2012-07-01

    The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: First, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties. Second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data. Third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.

  7. Buckled graphene: A model study based on density functional theory

    KAUST Repository

    Khan, Yasser

    2010-09-01

    We make use of ab initio calculations within density functional theory to investigate the influence of buckling on the electronic structure of single layer graphene. Our systematic study addresses a wide range of bond length and bond angle variations in order to obtain insights into the energy scale associated with the formation of ripples in a graphene sheet. © 2010 Elsevier B.V. All rights reserved.

  8. Buckled graphene: A model study based on density functional theory

    KAUST Repository

    Khan, Yasser; Mukaddam, Mohsin Ahmed; Schwingenschlö gl, Udo

    2010-01-01

    We make use of ab initio calculations within density functional theory to investigate the influence of buckling on the electronic structure of single layer graphene. Our systematic study addresses a wide range of bond length and bond angle variations in order to obtain insights into the energy scale associated with the formation of ripples in a graphene sheet. © 2010 Elsevier B.V. All rights reserved.

  9. Open-system Kohn-Sham density functional theory.

    Science.gov (United States)

    Zhou, Yongxi; Ernzerhof, Matthias

    2012-03-07

    A simple model for electron transport through molecules is provided by the source-sink potential (SSP) method [F. Goyer, M. Ernzerhof, and M. Zhuang, J. Chem. Phys. 126, 144104 (2007)]. In SSP, the boundary conditions of having an incoming and outgoing electron current are enforced through complex potentials that are added to the Hamiltonian. Depending on the sign of the imaginary part of the potentials, current density is generated or absorbed. In this way, a finite system can be used to model infinite molecular electronic devices. The SSP has originally been developed for the Hückel method and subsequently it has been extended [F. Goyer and M. Ernzerhof, J. Chem. Phys. 134, 174101 (2011)] to the Hubbard model. Here we present a step towards its generalization for first-principles electronic structure theory methods. In particular, drawing on our earlier work, we discuss a new generalized density functional theory for complex non-Hermitian Hamiltonians. This theory enables us to combine SSP and Kohn-Sham theory to obtain a method for the description of open systems that exchange current density with their environment. Similarly, the Hartree-Fock method is extended to the realm of non-Hermitian, SSP containing Hamiltonians. As a proof of principle, we present the first applications of complex-density functional theory (CODFT) as well as non-Hermitian Hartree-Fock theory to electron transport through molecules. © 2012 American Institute of Physics

  10. Reduced density matrix functional theory at finite temperature

    Energy Technology Data Exchange (ETDEWEB)

    Baldsiefen, Tim

    2012-10-15

    Density functional theory (DFT) is highly successful in many fields of research. There are, however, areas in which its performance is rather limited. An important example is the description of thermodynamical variables of a quantum system in thermodynamical equilibrium. Although the finite-temperature version of DFT (FT-DFT) rests on a firm theoretical basis and is only one year younger than its brother, groundstate DFT, it has been successfully applied to only a few problems. Because FT-DFT, like DFT, is in principle exact, these shortcomings can be attributed to the difficulties of deriving valuable functionals for FT-DFT. In this thesis, we are going to present an alternative theoretical description of quantum systems in thermal equilibrium. It is based on the 1-reduced density matrix (1RDM) of the system, rather than on its density and will rather cumbersomly be called finite-temperature reduced density matrix functional theory (FT-RDMFT). Its zero-temperature counterpart (RDMFT) proved to be successful in several fields, formerly difficult to address via DFT. These fields include, for example, the calculation of dissociation energies or the calculation of the fundamental gap, also for Mott insulators. This success is mainly due to the fact that the 1RDM carries more directly accessible ''manybody'' information than the density alone, leading for example to an exact description of the kinetic energy functional. This sparks the hope that a description of thermodynamical systems employing the 1RDM via FT-RDMFT can yield an improvement over FT-DFT. Giving a short review of RDMFT and pointing out difficulties when describing spin-polarized systems initiates our work. We then lay the theoretical framework for FT-RDMFT by proving the required Hohenberg-Kohn-like theorems, investigating and determining the domain of FT-RDMFT functionals and by deriving several properties of the exact functional. Subsequently, we present a perturbative method to

  11. Reduced density matrix functional theory at finite temperature

    International Nuclear Information System (INIS)

    Baldsiefen, Tim

    2012-10-01

    Density functional theory (DFT) is highly successful in many fields of research. There are, however, areas in which its performance is rather limited. An important example is the description of thermodynamical variables of a quantum system in thermodynamical equilibrium. Although the finite-temperature version of DFT (FT-DFT) rests on a firm theoretical basis and is only one year younger than its brother, groundstate DFT, it has been successfully applied to only a few problems. Because FT-DFT, like DFT, is in principle exact, these shortcomings can be attributed to the difficulties of deriving valuable functionals for FT-DFT. In this thesis, we are going to present an alternative theoretical description of quantum systems in thermal equilibrium. It is based on the 1-reduced density matrix (1RDM) of the system, rather than on its density and will rather cumbersomly be called finite-temperature reduced density matrix functional theory (FT-RDMFT). Its zero-temperature counterpart (RDMFT) proved to be successful in several fields, formerly difficult to address via DFT. These fields include, for example, the calculation of dissociation energies or the calculation of the fundamental gap, also for Mott insulators. This success is mainly due to the fact that the 1RDM carries more directly accessible ''manybody'' information than the density alone, leading for example to an exact description of the kinetic energy functional. This sparks the hope that a description of thermodynamical systems employing the 1RDM via FT-RDMFT can yield an improvement over FT-DFT. Giving a short review of RDMFT and pointing out difficulties when describing spin-polarized systems initiates our work. We then lay the theoretical framework for FT-RDMFT by proving the required Hohenberg-Kohn-like theorems, investigating and determining the domain of FT-RDMFT functionals and by deriving several properties of the exact functional. Subsequently, we present a perturbative method to iteratively construct

  12. Time-dependent density-functional theory concepts and applications

    CERN Document Server

    Ullrich, Carsten A

    2011-01-01

    Time-dependent density-functional theory (TDDFT) describes the quantum dynamics of interacting electronic many-body systems formally exactly and in a practical and efficient manner. TDDFT has become the leading method for calculating excitation energies and optical properties of large molecules, with accuracies that rival traditional wave-function based methods, but at a fraction of the computational cost.This book is the first graduate-level text on the concepts and applications of TDDFT, including many examples and exercises, and extensive coverage of the literature. The book begins with a s

  13. Quantal density functional theory. 2. ed.

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2016-01-01

    This book is on quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The time-independent QDFT constitutes a special case. The 2 nd edition describes the further development of the theory, and extends it to include the presence of an external magnetostatic field. The theory is based on the 'quantal Newtonian' second and first laws for the individual electron. These laws are in terms of 'classical' fields that pervade all space, and their quantal sources. The fields are separately representative of the electron correlations that must be accounted for in local potential theory. Recent developments show that irrespective of the type of external field the electrons are subject to, the only correlations beyond those due to the Pauli exclusion principle and Coulomb repulsion that need be considered are solely of the correlation-kinetic effects. Foundational to QDFT, the book describes Schroedinger theory from the new perspective of the single electron in terms of the 'quantal Newtonian' laws. Hohenberg-Kohn density functional theory (DFT), new understandings of the theory and its extension to the presence of an external uniform magnetostatic field are described. The physical interpretation via QDFT, in terms of electron correlations, of Kohn-Sham DFT, approximations to it and Slater theory are provided.

  14. Quantal density functional theory. 2. ed.

    Energy Technology Data Exchange (ETDEWEB)

    Sahni, Viraht

    2016-07-01

    This book is on quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The time-independent QDFT constitutes a special case. The 2{sup nd} edition describes the further development of the theory, and extends it to include the presence of an external magnetostatic field. The theory is based on the 'quantal Newtonian' second and first laws for the individual electron. These laws are in terms of 'classical' fields that pervade all space, and their quantal sources. The fields are separately representative of the electron correlations that must be accounted for in local potential theory. Recent developments show that irrespective of the type of external field the electrons are subject to, the only correlations beyond those due to the Pauli exclusion principle and Coulomb repulsion that need be considered are solely of the correlation-kinetic effects. Foundational to QDFT, the book describes Schroedinger theory from the new perspective of the single electron in terms of the 'quantal Newtonian' laws. Hohenberg-Kohn density functional theory (DFT), new understandings of the theory and its extension to the presence of an external uniform magnetostatic field are described. The physical interpretation via QDFT, in terms of electron correlations, of Kohn-Sham DFT, approximations to it and Slater theory are provided.

  15. Approximate self-consistent potentials for density-functional-theory exchange-correlation functionals

    International Nuclear Information System (INIS)

    Cafiero, Mauricio; Gonzalez, Carlos

    2005-01-01

    We show that potentials for exchange-correlation functionals within the Kohn-Sham density-functional-theory framework may be written as potentials for simpler functionals multiplied by a factor close to unity, and in a self-consistent field calculation, these effective potentials find the correct self-consistent solutions. This simple theory is demonstrated with self-consistent exchange-only calculations of the atomization energies of some small molecules using the Perdew-Kurth-Zupan-Blaha (PKZB) meta-generalized-gradient-approximation (meta-GGA) exchange functional. The atomization energies obtained with our method agree with or surpass previous meta-GGA calculations performed in a non-self-consistent manner. The results of this work suggest the utility of this simple theory to approximate exchange-correlation potentials corresponding to energy functionals too complicated to generate closed forms for their potentials. We hope that this method will encourage the development of complex functionals which have correct boundary conditions and are free of self-interaction errors without the worry that the functionals are too complex to differentiate to obtain potentials

  16. Wavelet-based linear-response time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.

    2012-01-01

    Highlights: ► We has been implemented LR-TD-DFT in the pseudopotential wavelet-based program. ► We have compared the results against all-electron Gaussian-type program. ► Orbital energies converges significantly faster for BigDFT than for DEMON2K. ► We report the X-ray crystal structure of the small organic molecule flugi6. ► Measured and calculated absorption spectrum of flugi6 is also reported. - Abstract: Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N 2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

  17. Comment on 'Kinetic energy as a density functional'

    International Nuclear Information System (INIS)

    Holas, A.; March, N.H.

    2002-01-01

    In a recent paper, Nesbet [Phys. Rev. A 65, 010502(R) (2001)] has proposed dropping ''the widespread but unjustified assumption that the existence of a ground-state density functional for the kinetic energy, T s [ρ], of an N-electron system implies the existence of a density-functional derivative, δT s [ρ]/δρ(r), equivalent to a local potential function,'' because, according to his arguments, this derivative 'has the mathematical character of a linear operator that acts on orbital wave functions'. Our Comment demonstrates that the statement called by Nesbet an 'unjustified assumption' happens, in fact, to be a rigorously proven theorem. Therefore, his previous conclusions stemming from his different view of this derivative, which undermined the foundations of density-functional theory, can be discounted

  18. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    Density functional theory, natural bond orbital and quantum theory of atoms in molecule analyses on the hydrogen bonding interactions in tryptophan-water complexes. XIQIAN NIU, ZHENGGUO HUANG. ∗. , LINGLING MA, TINGTING SHEN and LINGFEI GUO. Tianjin Key Laboratory of Structure and Performance for ...

  19. A density gradient theory based method for surface tension calculations

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Michelsen, Michael Locht; Kontogeorgis, Georgios

    2016-01-01

    The density gradient theory has been becoming a widely used framework for calculating surface tension, within which the same equation of state is used for the interface and bulk phases, because it is a theoretically sound, consistent and computationally affordable approach. Based on the observation...... that the optimal density path from the geometric mean density gradient theory passes the saddle point of the tangent plane distance to the bulk phases, we propose to estimate surface tension with an approximate density path profile that goes through this saddle point. The linear density gradient theory, which...... assumes linearly distributed densities between the two bulk phases, has also been investigated. Numerical problems do not occur with these density path profiles. These two approximation methods together with the full density gradient theory have been used to calculate the surface tension of various...

  20. Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

    Science.gov (United States)

    Husowitz, B; Talanquer, V

    2007-02-07

    Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

  1. What Density Functional Theory could do for Quantum Information

    Science.gov (United States)

    Mattsson, Ann

    2015-03-01

    The Hohenberg-Kohn theorem of Density Functional Theory (DFT), and extensions thereof, tells us that all properties of a system of electrons can be determined through their density, which uniquely determines the many-body wave-function. Given access to the appropriate, universal, functionals of the density we would, in theory, be able to determine all observables of any electronic system, without explicit reference to the wave-function. On the other hand, the wave-function is at the core of Quantum Information (QI), with the wave-function of a set of qubits being the central computational resource in a quantum computer. While there is seemingly little overlap between DFT and QI, reliance upon observables form a key connection. Though the time-evolution of the wave-function and associated phase information is fundamental to quantum computation, the initial and final states of a quantum computer are characterized by observables of the system. While observables can be extracted directly from a system's wave-function, DFT tells us that we may be able to intuit a method for extracting them from its density. In this talk, I will review the fundamentals of DFT and how these principles connect to the world of QI. This will range from DFT's utility in the engineering of physical qubits, to the possibility of using it to efficiently (but approximately) simulate Hamiltonians at the logical level. The apparent paradox of describing algorithms based on the quantum mechanical many-body wave-function with a DFT-like theory based on observables will remain a focus throughout. The ultimate goal of this talk is to initiate a dialog about what DFT could do for QI, in theory and in practice. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  2. Strain Energy Density in the Elastodynamics of the Spacetime Continuum and the Electromagnetic Field

    Directory of Open Access Journals (Sweden)

    Millette P. A.

    2013-04-01

    Full Text Available We investigate the strain energy density of the spacetime continuum in the Elasto- dynamics of the Spacetime Continuum by applying continuum m echanical results to strained spacetime. The strain energy density is a scalar. W e find that it is separated into two terms: the first one expresses the dilatation energy density (the “mass” longitu- dinal term while the second one expresses the distortion en ergy density (the “massless” transverse term. The quadratic structure of the energy rel ation of Special Relativity is found to be present in the theory. In addition, we find that the kinetic energy pc is car- ried by the distortion part of the deformation, while the dil atation part carries only the rest-mass energy. The strain energy density of the electrom agnetic energy-momentum stress tensor is calculated. The dilatation energy density (the rest-mass energy density of the photon is found to be 0 as expected. The transverse dis tortion energy density is found to include a longitudinal electromagnetic energy fl ux term, from the Poynting vector, that is massless as it is due to distortion, not dilatation, of the spacetime con- tinuum. However, because this energy flux is along the direct ion of propagation (i.e. longitudinal, it gives rise to the particle aspect of the el ectromagnetic field, the photon.

  3. ONETEP: linear-scaling density-functional theory with plane-waves

    International Nuclear Information System (INIS)

    Haynes, P D; Mostof, A A; Skylaris, C-K; Payne, M C

    2006-01-01

    This paper provides a general overview of the methodology implemented in onetep (Order-N Electronic Total Energy Package), a parallel density-functional theory code for largescale first-principles quantum-mechanical calculations. The distinctive features of onetep are linear-scaling in both computational effort and resources, obtained by making well-controlled approximations which enable simulations to be performed with plane-wave accuracy. Titanium dioxide clusters of increasing size designed to mimic surfaces are studied to demonstrate the accuracy and scaling of onetep

  4. An exposition on Friedmann cosmology with negative energy densities

    International Nuclear Information System (INIS)

    Nemiroff, Robert J.; Joshi, Ravi; Patla, Bijunath R.

    2015-01-01

    How would negative energy density affect a classic Friedmann cosmology? Although never measured and possibly unphysical, certain realizations of quantum field theories leaves the door open for such a possibility. In this paper we analyze the evolution of a universe comprising varying amounts of negative energy forms. Negative energy components have negative normalized energy densities, Ω < 0. They include negative phantom energy with an equation of state parameter w < −1, negative cosmological constant: w=−1, negative domain walls: w = −2/3, negative cosmic strings: w=−1/3, negative mass: w = 0, negative radiation: w = 1/3 and negative ultralight: w > 1/3. Assuming that such energy forms generate pressure like perfect fluids, the attractive or repulsive nature of negative energy components are reviewed. The Friedmann equation is satisfied only when negative energy forms are coupled to a greater magnitude of positive energy forms or positive curvature. We show that the solutions exhibit cyclic evolution with bounces and turnovers.The future and fate of such universes in terms of curvature, temperature, acceleration, and energy density are reviewed. The end states are dubbed ''big crunch,' '' big void,' or ''big rip' and further qualified as ''warped',''curved', or ''flat',''hot' versus ''cold', ''accelerating' versus ''decelerating' versus ''coasting'. A universe that ends by contracting to zero energy density is termed ''big poof.' Which contracting universes ''bounce' in expansion and which expanding universes ''turnover' into contraction are also reviewed

  5. Perturbation theory of the quark-gluon plasma at finite temperature and baryon number density

    International Nuclear Information System (INIS)

    Anon.

    1984-01-01

    At very high energy densities, hadronic matter becomes an almost ideal gas of quarks and gluons. In these circumstances, the effects of particle interactions are small, and to some order in perturbation theory are computable by methods involving weak coupling expansions. To illustrate the perturbative methods which may be used to compute the thermodynamic potential, the results and methods which are employed to compute to first order in α/sub s/ are reviewed. The problem of the plasmon effect, and the necessity of using non-perturbative methods when going beyond first order in α/sub s/ in evaluating the thermodynamic potential are discussed. The results at zero temperature and finite baryon number density to second order in α/sub s/ are also reviewed. The method of renormalization group improving the weak coupling expansions by replacing the expansion by an expansion in a temperature and baryon number density dependent coupling which approaches zero at high energy densities is discussed. Non-perturbative effects such as instantons are briefly mentioned and the breakdown of perturbation theory for the thermodynamical at order α/sub s/ 3 for finite temperature is presented

  6. Hot-electron-assisted femtochemistry at surfaces: A time-dependent density functional theory approach

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Rubio, Angel; Olsen, Thomas

    2009-01-01

    Using time-evolution time-dependent density functional theory (TDDFT) within the adiabatic local-density approximation, we study the interactions between single electrons and molecular resonances at surfaces. Our system is a nitrogen molecule adsorbed on a ruthenium surface. The surface is modele...... resonance and the lowering of the resonance energy due to an image charge effect. Finally we apply the TDDFT procedure to only consider the decay of molecular excitations and find that it agrees quite well with the width of the projected density of Kohn-Sham states....

  7. Accurate core-electron binding energy shifts from density functional theory

    International Nuclear Information System (INIS)

    Takahata, Yuji; Marques, Alberto Dos Santos

    2010-01-01

    Current review covers description of density functional methods of calculation of accurate core-electron binding energy (CEBE) of second and third row atoms; applications of calculated CEBEs and CEBE shifts (ΔCEBEs) in elucidation of topics such as: hydrogen-bonding, peptide bond, polymers, DNA bases, Hammett substituent (σ) constants, inductive and resonance effects, quantitative structure activity relationship (QSAR), and solid state effect (WD). This review limits itself to works of mainly Chong and his coworkers for the period post-2002. It is not a fully comprehensive account of the current state of the art.

  8. Time-dependent quantum fluid density functional theory of hydrogen ...

    Indian Academy of Sciences (India)

    WINTEC

    density functional theory; quantum fluid dynamics. 1. Introduction ... dynamics of strongly non-linear interaction of atoms with intense ... theory and quantum fluid dynamics in real space. .... clear evidence of bond softening since density in the.

  9. Spin theory of the density functional: reduced matrices and density functions

    International Nuclear Information System (INIS)

    Pavlov, R.; Delchev, Y.; Pavlova, K.; Maruani, J.

    1993-01-01

    Expressions for the reduced matrices and density functions of N-fermion systems of arbitrary order s (1<=s<=N) are derived within the frame of rigorous spin approach to the density functional theory (DFT). Using the local-scale transformation method and taking into account the particle spin it is shown that the reduced matrices and density functions are functionals of the total one-fermion density. Similar dependence is found for the distribution density of s-particle aggregates. Generalization and applicability of DFT to the case of s-particle ensembles and aggregates is discussed. 14 refs

  10. Spin-Density Functionals from Current-Density Functional Theory and Vice Versa: A Road towards New Approximations

    International Nuclear Information System (INIS)

    Capelle, K.; Gross, E.

    1997-01-01

    It is shown that the exchange-correlation functional of spin-density functional theory is identical, on a certain set of densities, with the exchange-correlation functional of current-density functional theory. This rigorous connection is used to construct new approximations of the exchange-correlation functionals. These include a conceptually new generalized-gradient spin-density functional and a nonlocal current-density functional. copyright 1997 The American Physical Society

  11. Electronic zero-point oscillations in the strong-interaction limit of density functional theory

    NARCIS (Netherlands)

    Gori Giorgi, P.; Vignale, G.; Seidl, M.

    2009-01-01

    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

  12. Validation of missed space-group symmetry in X-ray powder diffraction structures with dispersion-corrected density functional theory

    DEFF Research Database (Denmark)

    Hempler, Daniela; Schmidt, Martin U.; Van De Streek, Jacco

    2017-01-01

    More than 600 molecular crystal structures with correct, incorrect and uncertain space-group symmetry were energy-minimized with dispersion-corrected density functional theory (DFT-D, PBE-D3). For the purpose of determining the correct space-group symmetry the required tolerance on the atomic...... with missed symmetry were investigated by dispersion-corrected density functional theory. In 98.5% of the cases the correct space group is found....

  13. Foundations of high-energy-density physics physical processes of matter at extreme conditions

    CERN Document Server

    Larsen, Jon

    2017-01-01

    High-energy-density physics explores the dynamics of matter at extreme conditions. This encompasses temperatures and densities far greater than we experience on Earth. It applies to normal stars, exploding stars, active galaxies, and planetary interiors. High-energy-density matter is found on Earth in the explosion of nuclear weapons and in laboratories with high-powered lasers or pulsed-power machines. The physics explored in this book is the basis for large-scale simulation codes needed to interpret experimental results whether from astrophysical observations or laboratory-scale experiments. The key elements of high-energy-density physics covered are gas dynamics, ionization, thermal energy transport, and radiation transfer, intense electromagnetic waves, and their dynamical coupling. Implicit in this is a fundamental understanding of hydrodynamics, plasma physics, atomic physics, quantum mechanics, and electromagnetic theory. Beginning with a summary of the topics and exploring the major ones in depth, thi...

  14. Fitting theories of nuclear binding energies

    International Nuclear Information System (INIS)

    Bertsch, G.F.; Sabbey, B.; Uusnaekki, M.

    2005-01-01

    In developing theories of nuclear binding energy such as density-functional theory, the effort required to make a fit can be daunting because of the large number of parameters that may be in the theory and the large number of nuclei in the mass table. For theories based on the Skyrme interaction, the effort can be reduced considerably by using the singular value decomposition to reduce the size of the parameter space. We find that the sensitive parameters define a space of dimension four or so, and within this space a linear refit is adequate for a number of Skyrme parameters sets from the literature. We find no marked differences in the quality of the fit among the SLy4, the BSk4, and SkP parameter sets. The root-mean-square residual error in even-even nuclei is about 1.5 MeV, half the value of the liquid drop model. We also discuss an alternative norm for evaluating mass fits, the Chebyshev norm. It focuses attention on the cases with the largest discrepancies between theory and experiment. We show how it works with the liquid drop model and make some applications to models based on Skyrme energy functionals. The Chebyshev norm seems to be more sensitive to new experimental data than the root-mean-square norm. The method also has the advantage that candidate improvements to the theories can be assessed with computations on smaller sets of nuclei

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

    Science.gov (United States)

    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.

  16. Alternative separation of exchange and correlation energies in range-separated density-functional perturbation theory

    DEFF Research Database (Denmark)

    Cornaton, Y.; Stoyanova, A.; Jensen, Hans Jørgen Aagaard

    2013-01-01

    of the noninteracting Kohn-Sham one. When second-order corrections to the density are neglected, the energy expression reduces to a range-separated double-hybrid (RSDH) type of functional, RSDHf, where "f" stands for "full-range integrals" as the regular full-range interaction appears explicitly in the energy...

  17. Multireference quantum chemistry through a joint density matrix renormalization group and canonical transformation theory.

    Science.gov (United States)

    Yanai, Takeshi; Kurashige, Yuki; Neuscamman, Eric; Chan, Garnet Kin-Lic

    2010-01-14

    We describe the joint application of the density matrix renormalization group and canonical transformation theory to multireference quantum chemistry. The density matrix renormalization group provides the ability to describe static correlation in large active spaces, while the canonical transformation theory provides a high-order description of the dynamic correlation effects. We demonstrate the joint theory in two benchmark systems designed to test the dynamic and static correlation capabilities of the methods, namely, (i) total correlation energies in long polyenes and (ii) the isomerization curve of the [Cu(2)O(2)](2+) core. The largest complete active spaces and atomic orbital basis sets treated by the joint DMRG-CT theory in these systems correspond to a (24e,24o) active space and 268 atomic orbitals in the polyenes and a (28e,32o) active space and 278 atomic orbitals in [Cu(2)O(2)](2+).

  18. High-density fluid-perturbation theory based on an inverse 12th-power hard-sphere reference system

    International Nuclear Information System (INIS)

    Ross, M.

    1979-01-01

    A variational theory is developed that is accurate at normal liquid densities and densities up to 4 times that of the argon triple point. This theory uses the inverse 12th-power potential as a reference system. The properties of this reference system are expressed in terms of hard-sphere packing fractions by using a modified form of hard-space variational theory. As a result of this ''bootstrapping,'' a variational procedure may be followed that employs the inverse 12th-power system as a reference but uses the hard-sphere packing fraction as the scaling parameter with which to minimize the Helmholtz free energy

  19. Teaching Density Functional Theory Through Experiential Learning

    International Nuclear Information System (INIS)

    Narasimhan, Shobhana

    2015-01-01

    Today, quantum mechanical density functional theory is often the method of choice for performing accurate calculations on atomic, molecular and condensed matter systems. Here, I share some of my experiences in teaching the necessary basics of solid state physics, as well as the theory and practice of density functional theory, in a number of workshops held in developing countries over the past two decades. I discuss the advantages of supplementing the usual mathematically formal teaching methods, characteristic of graduate courses, with the use of visual imagery and analogies. I also describe a successful experiment we carried out, which resulted in a joint publication co-authored by 67 lecturers and students participating in a summer school. (paper)

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

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Yifan; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu [Quantum Theory Project and Departments of Chemistry and Physics, University of Florida, Gainesville, Florida 32611 (United States)

    2016-07-21

    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 properties such as geometries, reaction barrier heights, and atomization energies.

  1. Use of density functional theory in drug metabolism studies

    DEFF Research Database (Denmark)

    Rydberg, Patrik; Jørgensen, Flemming Steen; Olsen, Lars

    2014-01-01

    INTRODUCTION: The cytochrome P450 enzymes (CYPs) metabolize many drug compounds. They catalyze a wide variety of reactions, and potentially, a large number of different metabolites can be generated. Density functional theory (DFT) has, over the past decade, been shown to be a powerful tool...... isoforms. This is probably due to the fact that the binding of the substrates is not the major determinant. When binding of the substrate plays a significant role, the well-known issue of determining the free energy of binding is the challenge. How approaches taking the protein environment into account...

  2. Magnetic behavior study of samarium nitride using density functional theory

    Science.gov (United States)

    Som, Narayan N.; Mankad, Venu H.; Dabhi, Shweta D.; Patel, Anjali; Jha, Prafulla K.

    2018-02-01

    In this work, the state-of-art density functional theory is employed to study the structural, electronic and magnetic properties of samarium nitride (SmN). We have performed calculation for both ferromagnetic and antiferromagnetic states in rock-salt phase. The calculated results of optimized lattice parameter and magnetic moment agree well with the available experimental and theoretical values. From energy band diagram and electronic density of states, we observe a half-metallic behaviour in FM phase of rock salt SmN in while metallicity in AFM I and AFM III phases. We present and discuss our current understanding of the possible half-metallicity together with the magnetic ordering in SmN. The calculated phonon dispersion curves shows dynamical stability of the considered structures. The phonon density of states and Eliashberg functional have also been analysed to understand the superconductivity in SmN.

  3. Nitrotyrosine adsorption on carbon nanotube: a density functional theory study

    Science.gov (United States)

    Majidi, R.; Karami, A. R.

    2014-05-01

    We have studied the effect of nitrotyrosine on electronic properties of different single-wall carbon nanotubes by density functional theory. Optimal adsorption configurations of nitrotyrosine adsorbed on carbon nanotube have been determined by calculation of adsorption energy. Adsorption energies indicate that nitrotyrosine is chemisorbed on carbon nanotubes. It is found that the nitrotyrosine adsorption modifies the electronic properties of the semiconducting carbon nanotubes significantly and these nanotubes become n-type semiconductors, while the effect of nitrotyrosine on metallic carbon nanotubes is not considerable and these nanotubes remain metallic. Results clarify sensitivity of carbon nanotubes to nitrotyrosine adsorption and suggest the possibility of using carbon nanotubes as biosensor for nitrotyrosine detection.

  4. Density functional theory: Foundations reviewed

    Energy Technology Data Exchange (ETDEWEB)

    Kryachko, Eugene S., E-mail: eugene.kryachko@ulg.ac.be [Bogolyubov Institute for Theoretical Physics, Kiev, 03680 (Ukraine); Ludeña, Eduardo V., E-mail: popluabe@yahoo.es [Centro de Química, Instituto Venezolano de Investigaciones Científicas, IVIC, Apartado 21827, Caracas 1020-A (Venezuela, Bolivarian Republic of); Prometheus Program, Senescyt (Ecuador); Grupo Ecuatoriano para el Estudio Experimental y Teórico de Nanosistemas, GETNano, USFQ, N104-E, Quito (Ecuador); Escuela Politécnica Superior del Litoral, ESPOL, Guayaquil (Ecuador)

    2014-11-10

    Guided by the above motto (quotation), we review a broad range of issues lying at the foundations of Density Functional Theory, DFT, a theory which is currently omnipresent in our everyday computational study of atoms and molecules, solids and nano-materials, and which lies at the heart of modern many-body computational technologies. The key goal is to demonstrate that there are definitely the ways to improve DFT. We start by considering DFT in the larger context provided by reduced density matrix theory (RDMT) and natural orbital functional theory (NOFT), and examine the implications that N-representability conditions on the second-order reduced density matrix (2-RDM) have not only on RDMT and NOFT but, also, by extension, on the functionals of DFT. This examination is timely in view of the fact that necessary and sufficient N-representability conditions on the 2-RDM have recently been attained. In the second place, we review some problems appearing in the original formulation of the first Hohenberg–Kohn theorem which is still a subject of some controversy. In this vein we recall Lieb’s comment on this proof and the extension to this proof given by Pino et al. (2009), and in this context examine the conditions that must be met in order that the one-to-one correspondence between ground-state densities and external potentials remains valid for finite subspaces (namely, the subspaces where all Kohn–Sham solutions are obtained in practical applications). We also consider the issue of whether the Kohn–Sham equations can be derived from basic principles or whether they are postulated. We examine this problem in relation to ab initio DFT. The possibility of postulating arbitrary Kohn–Sham-type equations, where the effective potential is by definition some arbitrary mixture of local and non-local terms, is discussed. We also deal with the issue of whether there exists a universal functional, or whether one should advocate instead the construction of problem

  5. Dynamical corrections to density-functional theory for quasiparticles in ferromagnetic 4f systems. I. T = 0 results for EuO

    International Nuclear Information System (INIS)

    Nolting, W.; Borstel, G.; Borgiel, W.

    1987-01-01

    A theory for the electronic quasiparticle spectrum of ferromagnetic 4f systems is presented and applied to the semiconductor EuO. The starting point is a d-f exchange model, which we solve exactly for T = 0. One of the results is a simple relationship between the spin-up quasiparticle energies and the ''free'' Bloch energies epsilon-c/sub m/(k), which we use to fix the epsilon-c/sub m/(k) in a highly realistic manner by performing a new self-consistent spin-polarized band-structure calculation based on density-functional theory. With the so-determined Bloch energies we investigate the spin-down quasiparticle spectrum, which exhibits even at T = 0 strong many-body effects as a consequence of spin-exchange processes between localized magnetic 4f moments and itinerant conduction electrons. We discuss in detail the spin-down quasiparticle spectral density for the ΓL direction, which should be observable in an inverse photoemission experiment. The shape of this function is strongly k dependent, revealing different types of quasiparticles. The prominent quasiparticle peaks in the spin-down quasiparticle spectral density are used to construct a quasiparticle band structure, which shows some striking deviations from the one-particle solution of the density-functional theory. Furthermore, results for the electronic self-energy and the quasiparticle density of states are presented

  6. A physically motivated sparse cubature scheme with applications to molecular density-functional theory

    International Nuclear Information System (INIS)

    Rodriguez, Juan I; Thompson, David C; Anderson, James S M; Thomson, Jordan W; Ayers, Paul W

    2008-01-01

    We present a novel approach for performing multi-dimensional integration of arbitrary functions. The method starts with Smolyak-type sparse grids as cubature formulae on the unit cube and uses a transformation of coordinates based on the conditional distribution method to adapt those formulae to real space. Our method is tested on integrals in one, two, three and six dimensions. The three dimensional integration formulae are used to evaluate atomic interaction energies via the Gordon-Kim model. The six dimensional integration formulae are tested in conjunction with the nonlocal exchange-correlation energy functional proposed by Lee and Parr. This methodology is versatile and powerful; we contemplate application to frozen-density embedding, next-generation molecular-mechanics force fields, 'kernel-type' exchange-correlation energy functionals and pair-density functional theory

  7. Pressure and surface tension of soild-liquid interface using Tarazona density functional theory

    Directory of Open Access Journals (Sweden)

    M. M.

    2000-12-01

    Full Text Available   The weighted density functional theory proposed by Tarazona is applied to study the solid-liquid interface. In the last two decades the weighted density functional became a useful tool to consider the properties of inhomogeneous liquids. In this theory, the role of the size of molecules or the particles of which the matter is composed, was found to be important. In this resarch we study a hard sphere fluid beside a hard wall. For this study the liquid is an inhomogeneous system. We use the definition of the direct correlation function as a second derivative of free energy with respect to the density. We use this definition and the definition of the weighting function, then we minimize the grand potential with respect to the density to get the Euler Lagrange equation and we obtain an integral equation to find the inhomogeneous density profile. The obtained density profile as a function of the distance from the wall, for different bulk density is plotted in three dimensions. We also calculate the pressure and compare it with the Carnahan-starling results, and finally we obtained the surface tension at liquid-solid interface and compared it with the results of Monte Carlo simulation.

  8. Holographic Bound in Quantum Field Energy Density and Cosmological Constant

    OpenAIRE

    Castorina, Paolo

    2012-01-01

    The cosmological constant problem is reanalyzed by imposing the limitation of the number of degrees of freedom (d.o.f.) due to entropy bounds directly in the calculation of the energy density of a field theory. It is shown that if a quantum field theory has to be consistent with gravity and holography, i.e. with an upper limit of storing information in a given area, the ultraviolet momentum cut-off is not the Planck mass, M_p, as naively expected, but M_p/N_U^(1/4) where N_U is the number of ...

  9. Constructive definition of functional derivatives in density-functional theory

    International Nuclear Information System (INIS)

    Luo Ji

    2006-01-01

    It is shown that the functional derivatives in density-functional theory (DFT) can be explicitly defined within the domain of electron densities restricted by the electron number, and a constructive definition of such restricted derivatives is suggested. With this definition, Kohn-Sham (KS) equations can be established for an N-electron system without extending the functional domain and introducing a Lagrange multiplier. This may clarify some of the fundamental questions raised by Nesbet (1998 Phys. Rev. A 58 R12). The definition naturally leads to the fact that the KS effective potential is determined only to within an additive constant, thus the KS levels can shift freely and the relation between the highest occupied molecular orbital (HOMO) energy and the ionization potential of the system depends on the choice of the constant. On the other hand, if the domain of functionals is indeed extended beyond the electron number restriction, conclusions depend on whether the extended functionals have unrestricted derivatives or not. It is shown that the ensemble extension of DFT to open systems of mixed states (Perdew et al 1982 Phys. Rev. Lett. 49 1691) leads to an energy functional which has no unrestricted derivative at integer electron numbers. Hence after this extension, the relation between the HOMO energy and the ionization potential for an N-electron system is still uncertain. Besides, there are different extensions of the energy functional to a domain of densities unrestricted by the integer electron number, resulting in different unrestricted derivatives and electron systems with different chemical potentials. Even for the exact exchange-correlation potential, there is still an undetermined constant, whether it is a restricted or unrestricted derivative

  10. Extended screened exchange functional derived from transcorrelated density functional theory.

    Science.gov (United States)

    Umezawa, Naoto

    2017-09-14

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

  11. Reduced density-matrix functional theory: Correlation and spectroscopy.

    Science.gov (United States)

    Di Sabatino, S; Berger, J A; Reining, L; Romaniello, P

    2015-07-14

    In this work, we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the calculation of total energies, occupation numbers, removal/addition energies, and spectral functions. We use the exactly solvable Hubbard dimer at 1/4 and 1/2 fillings as test systems. This allows us to analyze the underlying physics and to elucidate the origin of the observed trends. For comparison, we also report the results of the GW approximation, where the self-energy functional is approximated, but no further hypothesis is made concerning the approximations of the observables. In particular, we focus on the atomic limit, where the two sites of the dimer are pulled apart and electrons localize on either site with equal probability, unless a small perturbation is present: this is the regime of strong electron correlation. In this limit, using the Hubbard dimer at 1/2 filling with or without a spin-symmetry-broken ground state allows us to explore how degeneracies and spin-symmetry breaking are treated in RDMFT. We find that, within the used approximations, neither in RDMFT nor in GW, the signature of strong correlation is present, when looking at the removal/addition energies and spectral function from the spin-singlet ground state, whereas both give the exact result for the spin-symmetry broken case. Moreover, we show how the spectroscopic properties change from one spin structure to the other.

  12. Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.

    Science.gov (United States)

    Ren, Hai-Sheng; Ming, Mei-Jun; Ma, Jian-Yi; Li, Xiang-Yuan

    2013-08-22

    Within the framework of constrained density functional theory (CDFT), the diabatic or charge localized states of electron transfer (ET) have been constructed. Based on the diabatic states, inner reorganization energy λin has been directly calculated. For solvent reorganization energy λs, a novel and reasonable nonequilibrium solvation model is established by introducing a constrained equilibrium manipulation, and a new expression of λs has been formulated. It is found that λs is actually the cost of maintaining the residual polarization, which equilibrates with the extra electric field. On the basis of diabatic states constructed by CDFT, a numerical algorithm using the new formulations with the dielectric polarizable continuum model (D-PCM) has been implemented. As typical test cases, self-exchange ET reactions between tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) and their corresponding ionic radicals in acetonitrile are investigated. The calculated reorganization energies λ are 7293 cm(-1) for TCNE/TCNE(-) and 5939 cm(-1) for TTF/TTF(+) reactions, agreeing well with available experimental results of 7250 cm(-1) and 5810 cm(-1), respectively.

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

    Science.gov (United States)

    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.

  14. Time-Dependent Density Functional Theory for Open Systems and Its Applications.

    Science.gov (United States)

    Chen, Shuguang; Kwok, YanHo; Chen, GuanHua

    2018-02-20

    Photovoltaic devices, electrochemical cells, catalysis processes, light emitting diodes, scanning tunneling microscopes, molecular electronics, and related devices have one thing in common: open quantum systems where energy and matter are not conserved. Traditionally quantum chemistry is confined to isolated and closed systems, while quantum dissipation theory studies open quantum systems. The key quantity in quantum dissipation theory is the reduced system density matrix. As the reduced system density matrix is an O(M! × M!) matrix, where M is the number of the particles of the system of interest, quantum dissipation theory can only be employed to simulate systems of a few particles or degrees of freedom. It is thus important to combine quantum chemistry and quantum dissipation theory so that realistic open quantum systems can be simulated from first-principles. We have developed a first-principles method to simulate the dynamics of open electronic systems, the time-dependent density functional theory for open systems (TDDFT-OS). Instead of the reduced system density matrix, the key quantity is the reduced single-electron density matrix, which is an N × N matrix where N is the number of the atomic bases of the system of interest. As the dimension of the key quantity is drastically reduced, the TDDFT-OS can thus be used to simulate the dynamics of realistic open electronic systems and efficient numerical algorithms have been developed. As an application, we apply the method to study how quantum interference develops in a molecular transistor in time domain. We include electron-phonon interaction in our simulation and show that quantum interference in the given system is robust against nuclear vibration not only in the steady state but also in the transient dynamics. As another application, by combining TDDFT-OS with Ehrenfest dynamics, we study current-induced dissociation of water molecules under scanning tunneling microscopy and follow its time dependent

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

    OpenAIRE

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

    2005-01-01

    We propose an alternative formulation of Many-Body Perturbation Theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, that leads to excellent optical absorption and energy loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-depend...

  16. Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

    Science.gov (United States)

    Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

    2015-01-01

    Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Density Functional Theory and Materials Modeling at Atomistic Length Scales

    Directory of Open Access Journals (Sweden)

    Swapan K. Ghosh

    2002-04-01

    Full Text Available Abstract: We discuss the basic concepts of density functional theory (DFT as applied to materials modeling in the microscopic, mesoscopic and macroscopic length scales. The picture that emerges is that of a single unified framework for the study of both quantum and classical systems. While for quantum DFT, the central equation is a one-particle Schrodinger-like Kohn-Sham equation, the classical DFT consists of Boltzmann type distributions, both corresponding to a system of noninteracting particles in the field of a density-dependent effective potential, the exact functional form of which is unknown. One therefore approximates the exchange-correlation potential for quantum systems and the excess free energy density functional or the direct correlation functions for classical systems. Illustrative applications of quantum DFT to microscopic modeling of molecular interaction and that of classical DFT to a mesoscopic modeling of soft condensed matter systems are highlighted.

  18. Density functional theory for adsorption of gas mixtures in metal-organic frameworks.

    Science.gov (United States)

    Liu, Yu; Liu, Honglai; Hu, Ying; Jiang, Jianwen

    2010-03-04

    In this work, a recently developed density functional theory in three-dimensional space was extended to the adsorption of gas mixtures. Weighted density approximations to the excess free energy with different weighting functions were adopted for both repulsive and attractive contributions. An equation of state for hard-sphere mixtures and a modified Benedict-Webb-Rubin equation for Lennard-Jones mixtures were used to estimate the excess free energy of a uniform fluid. The theory was applied to the adsorption of CO(2)/CH(4) and CO(2)/N(2) mixtures in two metal-organic frameworks: ZIF-8 and Zn(2)(BDC)(2)(ted). To validate the theoretical predictions, grand canonical Monte Carlo simulations were also conducted. The predicted adsorption and selectivity from DFT were found to agree well with the simulation results. CO(2) has stronger adsorption than CH(4) and N(2), particularly in Zn(2)(BDC)(2)(ted). The selectivity of CO(2) over CH(4) or N(2) increases with increasing pressure as attributed to the cooperative interactions of adsorbed CO(2) molecules. The composition of the gas mixture exhibits a significant effect on adsorption but not on selectivity.

  19. Numerical analysis of energy density and particle density in high energy heavy-ion collisions

    International Nuclear Information System (INIS)

    Fu Yuanyong; Lu Zhongdao

    2004-01-01

    Energy density and particle density in high energy heavy-ion collisions are calculated with infinite series expansion method and Gauss-Laguerre formulas in numerical integration separately, and the results of these two methods are compared, the higher terms and linear terms in series expansion are also compared. The results show that Gauss-Laguerre formulas is a good method in calculations of high energy heavy-ion collisions. (author)

  20. Exact-exchange time-dependent density-functional theory for static and dynamic polarizabilities

    International Nuclear Information System (INIS)

    Hirata, So; Ivanov, Stanislav; Bartlett, Rodney J.; Grabowski, Ireneusz

    2005-01-01

    Time-dependent density-functional theory (TDDFT) employing the exact-exchange functional has been formulated on the basis of the optimized-effective-potential (OEP) method of Talman and Shadwick for second-order molecular properties and implemented into a Gaussian-basis-set, trial-vector algorithm. The only approximation involved, apart from the lack of correlation effects and the use of Gaussian-type basis functions, was the consistent use of the adiabatic approximation in the exchange kernel and in the linear response function. The static and dynamic polarizabilities and their anisotropy predicted by the TDDFT with exact exchange (TDOEP) agree accurately with the corresponding values from time-dependent Hartree-Fock theory, the exact-exchange counterpart in the wave function theory. The TDOEP is free from the nonphysical asymptotic decay of the exchange potential of most conventional density functionals or from any other manifestations of the incomplete cancellation of the self-interaction energy. The systematic overestimation of the absolute values and dispersion of polarizabilities that plagues most conventional TDDFT cannot be seen in the TDOEP

  1. Equilibrium structure and Ti-catalyzed H-2 desorption in NaAlH4 nanoparticles from density functional theory

    DEFF Research Database (Denmark)

    Vegge, T.

    2006-01-01

    the kinetics significantly, the physical understanding remains elusive. Density functional theory is used to calculate the energy of the potential low energy surfaces of NaAlH4 to establish the equilibrium particle shape, and furthermore to determine the deposition energy of Ti/TiH2 and the substitutional...

  2. Bond breaking and bond formation: how electron correlation is captured in many-body perturbation theory and density-functional theory.

    Science.gov (United States)

    Caruso, Fabio; Rohr, Daniel R; Hellgren, Maria; Ren, Xinguo; Rinke, Patrick; Rubio, Angel; Scheffler, Matthias

    2013-04-05

    For the paradigmatic case of H(2) dissociation, we compare state-of-the-art many-body perturbation theory in the GW approximation and density-functional theory in the exact-exchange plus random-phase approximation (RPA) for the correlation energy. For an unbiased comparison and to prevent spurious starting point effects, both approaches are iterated to full self-consistency (i.e., sc-RPA and sc-GW). The exchange-correlation diagrams in both approaches are topologically identical, but in sc-RPA they are evaluated with noninteracting and in sc-GW with interacting Green functions. This has a profound consequence for the dissociation region, where sc-RPA is superior to sc-GW. We argue that for a given diagrammatic expansion, sc-RPA outperforms sc-GW when it comes to bond breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

  3. Self-Interaction Error in Density Functional Theory: An Appraisal.

    Science.gov (United States)

    Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G

    2018-05-03

    Self-interaction error (SIE) is considered to be one of the major sources of error in most approximate exchange-correlation functionals for Kohn-Sham density-functional theory (KS-DFT), and it is large with all local exchange-correlation functionals and with some hybrid functionals. In this work, we consider systems conventionally considered to be dominated by SIE. For these systems, we demonstrate that by using multiconfiguration pair-density functional theory (MC-PDFT), the error of a translated local density-functional approximation is significantly reduced (by a factor of 3) when using an MCSCF density and on-top density, as compared to using KS-DFT with the parent functional; the error in MC-PDFT with local on-top functionals is even lower than the error in some popular KS-DFT hybrid functionals. Density-functional theory, either in MC-PDFT form with local on-top functionals or in KS-DFT form with some functionals having 50% or more nonlocal exchange, has smaller errors for SIE-prone systems than does CASSCF, which has no SIE.

  4. Extension of the self-consistent-charge density-functional tight-binding method: third-order expansion of the density functional theory total energy and introduction of a modified effective coulomb interaction.

    Science.gov (United States)

    Yang, Yang; Yu, Haibo; York, Darrin; Cui, Qiang; Elstner, Marcus

    2007-10-25

    The standard self-consistent-charge density-functional-tight-binding (SCC-DFTB) method (Phys. Rev. B 1998, 58, 7260) is derived by a second-order expansion of the density functional theory total energy expression, followed by an approximation of the charge density fluctuations by charge monopoles and an effective damped Coulomb interaction between the atomic net charges. The central assumptions behind this effective charge-charge interaction are the inverse relation of atomic size and chemical hardness and the use of a fixed chemical hardness parameter independent of the atomic charge state. While these approximations seem to be unproblematic for many covalently bound systems, they are quantitatively insufficient for hydrogen-bonding interactions and (anionic) molecules with localized net charges. Here, we present an extension of the SCC-DFTB method to incorporate third-order terms in the charge density fluctuations, leading to chemical hardness parameters that are dependent on the atomic charge state and a modification of the Coulomb scaling to improve the electrostatic treatment within the second-order terms. These modifications lead to a significant improvement in the description of hydrogen-bonding interactions and proton affinities of biologically relevant molecules.

  5. Building a Universal Nuclear Energy Density Functional

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, Joe A. [Michigan State Univ., East Lansing, MI (United States); Furnstahl, Dick; Horoi, Mihai; Lust, Rusty; Nazaewicc, Witek; Ng, Esmond; Thompson, Ian; Vary, James

    2012-12-30

    During the period of Dec. 1 2006 – Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: First, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; Second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; Third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.

  6. Influence of Exchange-Correlation Functional in the Calculations of Vertical Excitation Energies of Halogenated Copper Phthalocyanines using Time-Dependent Density Functional Theory (TD-DFT)

    International Nuclear Information System (INIS)

    Lee, Sang Uck

    2013-01-01

    The accurate prediction of vertical excitation energies is very important for the development of new materials in the dye and pigment industry. A time-dependent density functional theory (TD-DFT) approach coupled with 22 different exchange-correlation functionals was used for the prediction of vertical excitation energies in the halogenated copper phthalocyanine molecules in order to find the most appropriate functional and to determine the accuracy of the prediction of the absorption wavelength and observed spectral shifts. Among the tested functional, B3LYP functional provides much more accurate vertical excitation energies and UV-vis spectra. Our results clearly provide a benchmark calibration of the TD-DFT method for phthalocyanine based dyes and pigments used in industry

  7. Hydrogen plasmas beyond density-functional theory: dynamic correlations and the onset of localization

    International Nuclear Information System (INIS)

    Perrot, F.; Dharma-Wardana, M.W.C.

    1984-01-01

    The density-functional theory (DFT) equations - previously considered in their application to the study of a system of ions and electrons in thermodynamic equilibrium at arbitrary temperatures and pressure - are reviewed with attention given to extending their validity in obtaining the one-electron excitation spectrum. The DFT model developed here provides structure factors and Kohn-Sham eigenstates which are then used to calculate the self-energy of the one-electron Green function, thus transcending the local-density approximations and the well-known limitations of DFT, especially with regard to the excitation spectrum. The one-particle formalism used makes contact with the multiple-scattering theories of disordered materials, liquid metals, etc., and is a necessary first step to a future calculation of two-particle propagators and related properties. 28 references

  8. Analytic derivatives for perturbatively corrected ''double hybrid'' density functionals: Theory, implementation, and applications

    International Nuclear Information System (INIS)

    Neese, Frank; Schwabe, Tobias; Grimme, Stefan

    2007-01-01

    A recently proposed new family of density functionals [S. Grimme, J. Chem. Phys. 124, 34108 (2006)] adds a fraction of nonlocal correlation as a new ingredient to density functional theory (DFT). This fractional correlation energy is calculated at the level of second-order many-body perturbation theory (PT2) and replaces some of the semilocal DFT correlation of standard hybrid DFT methods. The new ''double hybrid'' functionals (termed, e.g., B2-PLYP) contain only two empirical parameters that have been adjusted in thermochemical calculations on parts of the G2/3 benchmark set. The methods have provided the lowest errors ever obtained by any DFT method for the full G3 set of molecules. In this work, the applicability of the new functionals is extended to the exploration of potential energy surfaces with analytic gradients. The theory of the analytic gradient largely follows the standard theory of PT2 gradients with some additional subtleties due to the presence of the exchange-correlation terms in the self-consistent field operator. An implementation is reported for closed-shell as well as spin-unrestricted reference determinants. Furthermore, the implementation includes external point charge fields and also accommodates continuum solvation models at the level of the conductor like screening model. The density fitting resolution of the identity (RI) approximation can be applied to the evaluation of the PT2 part with large gains in computational efficiency. For systems with ∼500-600 basis functions the evaluation of the double hybrid gradient is approximately four times more expensive than the calculation of the standard hybrid DFT gradient. Extensive test calculations are provided for main group elements and transition metal containing species. The results reveal that the B2-PLYP functional provides excellent molecular geometries that are superior compared to those from standard DFT and MP2

  9. Revisiting the density scaling of the non-interacting kinetic energy.

    Science.gov (United States)

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

    2014-07-28

    Scaling relations play an important role in the understanding and development of approximate functionals in density functional theory. Recently, a number of these relationships have been redefined in terms of the Kohn-Sham orbitals [Calderín, Phys. Rev. A: At., Mol., Opt. Phys., 2013, 86, 032510]. For density scaling the author proposed a procedure involving a multiplicative scaling of the Kohn-Sham orbitals whilst keeping their occupation numbers fixed. In the present work, the differences between this scaling with fixed occupation numbers and that of previous studies, where the particle number change implied by the scaling was accommodated through the use of the grand canonical ensemble, are examined. We introduce the terms orbital and ensemble density scaling for these approaches, respectively. The natural ambiguity of the density scaling of the non-interacting kinetic energy functional is examined and the ancillary definitions implicit in each approach are highlighted and compared. As a consequence of these differences, Calderín recovered a homogeneity of degree 1 for the non-interacting kinetic energy functional under orbital scaling, contrasting recent work by the present authors [J. Chem. Phys., 2012, 136, 034101] where the functional was found to be inhomogeneous under ensemble density scaling. Furthermore, we show that the orbital scaling result follows directly from the linearity and the single-particle nature of the kinetic energy operator. The inhomogeneity of the non-interacting kinetic energy functional under ensemble density scaling can be quantified by defining an effective homogeneity. This quantity is shown to recover the homogeneity values for important approximate forms that are exact for limiting cases such as the uniform electron gas and one-electron systems. We argue that the ensemble density scaling provides more insight into the development of new functional forms.

  10. A Safari Through Density Functional Theory

    Science.gov (United States)

    Dreizler, Reiner M.; Lüdde, Cora S.

    Density functional theory is widely used to treat quantum many body problems in many areas of physics and related fields. A brief survey of this method covering foundations, functionals and applications is presented here.

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

    Science.gov (United States)

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

    2018-01-01

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

  12. Predicting Multicomponent Adsorption Isotherms in Open-Metal Site Materials Using Force Field Calculations Based on Energy Decomposed Density Functional Theory.

    Science.gov (United States)

    Heinen, Jurn; Burtch, Nicholas C; Walton, Krista S; Fonseca Guerra, Célia; Dubbeldam, David

    2016-12-12

    For the design of adsorptive-separation units, knowledge is required of the multicomponent adsorption behavior. Ideal adsorbed solution theory (IAST) breaks down for olefin adsorption in open-metal site (OMS) materials due to non-ideal donor-acceptor interactions. Using a density-function-theory-based energy decomposition scheme, we develop a physically justifiable classical force field that incorporates the missing orbital interactions using an appropriate functional form. Our first-principles derived force field shows greatly improved quantitative agreement with the inflection points, initial uptake, saturation capacity, and enthalpies of adsorption obtained from our in-house adsorption experiments. While IAST fails to make accurate predictions, our improved force field model is able to correctly predict the multicomponent behavior. Our approach is also transferable to other OMS structures, allowing the accurate study of their separation performances for olefins/paraffins and further mixtures involving complex donor-acceptor interactions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Density functional theory in quantum chemistry

    CERN Document Server

    Tsuneda, Takao

    2014-01-01

    This book examines density functional theory based on the foundation of quantum chemistry. Unconventional in approach, it reviews basic concepts, then describes the physical meanings of state-of-the-art exchange-correlation functionals and their corrections.

  14. Pressure and surface tension of solid-liquid interface using Tara zona density functional theory

    International Nuclear Information System (INIS)

    Moradi, M.; Kavosh Tehrani, M.

    2001-01-01

    The weighted density functional theory proposed by Tara zona is applied to study the solid-liquid interface. In the last two decades the weighted density functional became a useful tool to consider the properties of inhomogeneous liquids. In this theory, the role of the size of molecules or the particles of which the matter is composed, was found to be important. In this research we study a hard sphere fluid beside a hard wall. For this study the liquid is an inhomogeneous system. We use the definition of the direct correlation function as a second derivative of free energy with respect to the density. We use this definition and the definition of the weighting function, then we minimize the grand potential with respect to the density to get the Euler Lagrange equation and we obtain an integral equation to find the inhomogeneous density profile. The obtained density profile as a function of the distance from the wall, for different bulk density is pitted in three dimensions. We also calculate the pressure and compare it with the Carnahan-Starling results, and finally we obtained the surface tension at liquid-solid interface and compared it with the results of Monte Carlo simulation

  15. Correlated density matrix theory of spatially inhomogeneous Bose fluids

    International Nuclear Information System (INIS)

    Gernoth, K.A.; Clark, J.W.; Ristig, M.L.

    1994-06-01

    In this paper, the variational Hartree-Jastrow theory of the ground state of spatially inhomogeneous Bose systems is extended to finite temperatures. The theory presented here is a generalization also in the sense that it extends the correlated density matrix approach, formulated previously for uniform Bose fluids, to systems with nonuniform density profiles. The method provides a framework in which the effects of thermal excitations on the spatial structure of a Bose fluid, as represented by the density profile and the two-body distribution functions, may be discussed on the basis on an ab initio microscopic description of the system. Thermal excitations make their appearance through self-consistently determined one-body and two-body potentials which enter the nonlinear, coupled Euler-Lagrange equations for the one-body density and for the pair distribution function. Since back-flow correlations are neglected, the excitations are described by a Feynman eigenvalue equation, suitably generalized to nonzero temperatures. The only external quantities entering the correlated density matrix theory elaborated here are the bare two-body interaction potential and, in actual applications, the boundary conditions to be imposed on the one-body density. 30 refs

  16. Exchange-Correlation Effects for Noncovalent Interactions in Density Functional Theory.

    Science.gov (United States)

    Otero-de-la-Roza, A; DiLabio, Gino A; Johnson, Erin R

    2016-07-12

    In this article, we develop an understanding of how errors from exchange-correlation functionals affect the modeling of noncovalent interactions in dispersion-corrected density-functional theory. Computed CCSD(T) reference binding energies for a collection of small-molecule clusters are decomposed via a molecular many-body expansion and are used to benchmark density-functional approximations, including the effect of semilocal approximation, exact-exchange admixture, and range separation. Three sources of error are identified. Repulsion error arises from the choice of semilocal functional approximation. This error affects intermolecular repulsions and is present in all n-body exchange-repulsion energies with a sign that alternates with the order n of the interaction. Delocalization error is independent of the choice of semilocal functional but does depend on the exact exchange fraction. Delocalization error misrepresents the induction energies, leading to overbinding in all induction n-body terms, and underestimates the electrostatic contribution to the 2-body energies. Deformation error affects only monomer relaxation (deformation) energies and behaves similarly to bond-dissociation energy errors. Delocalization and deformation errors affect systems with significant intermolecular orbital interactions (e.g., hydrogen- and halogen-bonded systems), whereas repulsion error is ubiquitous. Many-body errors from the underlying exchange-correlation functional greatly exceed in general the magnitude of the many-body dispersion energy term. A functional built to accurately model noncovalent interactions must contain a dispersion correction, semilocal exchange, and correlation components that minimize the repulsion error independently and must also incorporate exact exchange in such a way that delocalization error is absent.

  17. Accurate Ground-State Energies of Solids and Molecules from Time-Dependent Density-Functional Theory

    DEFF Research Database (Denmark)

    Olsen, Thomas; Thygesen, Kristian Sommer

    2014-01-01

    We demonstrate that ground-state energies approaching chemical accuracy can be obtained by combining the adiabatic-connection fluctuation-dissipation theorem with time-dependent densityfunctional theory. The key ingredient is a renormalization scheme, which eliminates the divergence...

  18. Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT and Time-Dependent Density Functional Theory (TD-DFT Study

    Directory of Open Access Journals (Sweden)

    Guo-Jun Kang

    2016-11-01

    Full Text Available The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH3-YD2 and TPhe-YD were systematically investigated by density functional theory (DFT and time-dependent density functional theory (TD-DFT to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO2 cluster were fully investigated. From the analyses of natural bond orbital (NBO, extended charge decomposition analysis (ECDA, and electron density variations (Δρ between the excited state and ground state, it was found that the introduction of N(CH32 and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH32 and 1,1,2-triphenylethene groups. NCH3-YD2 with N(CH32 groups in the donor part is an effective way to improve the interactions between the dyes and TiO2 surface, light having efficiency (LHE, and free energy change (ΔGinject, which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs.

  19. Central depression in nucleonic densities: Trend analysis in the nuclear density functional theory approach

    Science.gov (United States)

    Schuetrumpf, B.; Nazarewicz, W.; Reinhard, P.-G.

    2017-08-01

    Background: The central depression of nucleonic density, i.e., a reduction of density in the nuclear interior, has been attributed to many factors. For instance, bubble structures in superheavy nuclei are believed to be due to the electrostatic repulsion. In light nuclei, the mechanism behind the density reduction in the interior has been discussed in terms of shell effects associated with occupations of s orbits. Purpose: The main objective of this work is to reveal mechanisms behind the formation of central depression in nucleonic densities in light and heavy nuclei. To this end, we introduce several measures of the internal nucleonic density. Through the statistical analysis, we study the information content of these measures with respect to nuclear matter properties. Method: We apply nuclear density functional theory with Skyrme functionals. Using the statistical tools of linear least square regression, we inspect correlations between various measures of central depression and model parameters, including nuclear matter properties. We study bivariate correlations with selected quantities as well as multiple correlations with groups of parameters. Detailed correlation analysis is carried out for 34Si for which a bubble structure has been reported recently, 48Ca, and N =82 , 126, and 184 isotonic chains. Results: We show that the central depression in medium-mass nuclei is very sensitive to shell effects, whereas for superheavy systems it is firmly driven by the electrostatic repulsion. An appreciable semibubble structure in proton density is predicted for 294Og, which is currently the heaviest nucleus known experimentally. Conclusion: Our correlation analysis reveals that the central density indicators in nuclei below 208Pb carry little information on parameters of nuclear matter; they are predominantly driven by shell structure. On the other hand, in the superheavy nuclei there exists a clear relationship between the central nucleonic density and symmetry energy.

  20. Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

    Science.gov (United States)

    Soniat, Marielle; Rogers, David M; Rempe, Susan B

    2015-07-14

    A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

  1. JDFTx: Software for joint density-functional theory

    Directory of Open Access Journals (Sweden)

    Ravishankar Sundararaman

    2017-01-01

    Full Text Available Density-functional theory (DFT has revolutionized computational prediction of atomic-scale properties from first principles in physics, chemistry and materials science. Continuing development of new methods is necessary for accurate predictions of new classes of materials and properties, and for connecting to nano- and mesoscale properties using coarse-grained theories. JDFTx is a fully-featured open-source electronic DFT software designed specifically to facilitate rapid development of new theories, models and algorithms. Using an algebraic formulation as an abstraction layer, compact C++11 code automatically performs well on diverse hardware including GPUs (Graphics Processing Units. This code hosts the development of joint density-functional theory (JDFT that combines electronic DFT with classical DFT and continuum models of liquids for first-principles calculations of solvated and electrochemical systems. In addition, the modular nature of the code makes it easy to extend and interface with, facilitating the development of multi-scale toolkits that connect to ab initio calculations, e.g. photo-excited carrier dynamics combining electron and phonon calculations with electromagnetic simulations.

  2. Shannon Entropy in Atoms: A Test for the Assessment of Density Functionals in Kohn-Sham Theory

    Directory of Open Access Journals (Sweden)

    Claudio Amovilli

    2018-05-01

    Full Text Available Electron density is used to compute Shannon entropy. The deviation from the Hartree–Fock (HF of this quantity has been observed to be related to correlation energy. Thus, Shannon entropy is here proposed as a valid quantity to assess the quality of an energy density functional developed within Kohn–Sham theory. To this purpose, results from eight different functionals, representative of Jacob’s ladder, are compared with accurate results obtained from diffusion quantum Monte Carlo (DMC computations. For three series of atomic ions, our results show that the revTPSS and the PBE0 functionals are the best, whereas those based on local density approximation give the largest discrepancy from DMC Shannon entropy.

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

    Science.gov (United States)

    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.

  4. Studies on density dependence of charge separation in a direct energy converter using slanted Cusp magnetic field

    International Nuclear Information System (INIS)

    Munakata, Yoshiro; Kawaguchi, Takashi; Takeno, Hiromasa; Yasaka, Yasuyoshi; Ichimura, Kazuya; Nakashima, Yousuke

    2012-01-01

    In an advanced fusion, fusion-produced charged particles must be separated from each other for efficient energy conversion to electricity. The CuspDEC performs this function of separation and direct energy conversion. Analysis of working characteristics of CuspDEC on plasma density is an important subject. This paper summarizes and discusses experimental and theoretical works for high density plasma by using a small scale experimental device employing a slanted cusp magnetic field. When the incident plasma is low-density, good separation of the charged particles can be accomplished and this is explained by the theory based on a single particle motion. In high density plasma, however, this theory cannot be always applied due to space charge effects. In the experiment, as gradient of the field line increases, separation capability of the charged particles becomes higher. As plasma density becomes higher, however, separation capability becomes lower. This can be qualitatively explained by using calculations of the modified Störmer potential including space charge potential. (author)

  5. Differentiability in density-functional theory: Further study of the locality theorem

    International Nuclear Information System (INIS)

    Lindgren, Ingvar; Salomonson, Sten

    2004-01-01

    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 arguments [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 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

  6. A density functional theory study of arsenic immobilization by the Al(III)-modified zeolite clinoptilolite

    NARCIS (Netherlands)

    Awuah, Joel B.; Dzade, N.Y.; Tia, Richard; Adei, Evans; Kwakye-Awuah, Bright; Catlow, C. Richard A.; de Leeuw, Nora H.

    2016-01-01

    We present density functional theory calculations of the adsorption of arsenic acid (AsO(OH)3) and arsenous acid (As(OH)3) on the Al(III)-modified natural zeolite clinoptilolite under anhydrous and hydrated conditions. From our calculated adsorption energies, we show that adsorption of both arsenic

  7. Density functional theory calculations of energy-loss carbon near-edge spectra of small diameter armchair and zigzag nanotubes: Core-hole, curvature, and momentum-transfer orientation effects

    International Nuclear Information System (INIS)

    Titantah, J.T.; Lamoen, D.; Jorissen, K.

    2004-01-01

    We perform density functional theory calculations on a series of armchair and zigzag nanotubes of diameters less than 1 nm using the all-electron full-potential(-linearized)-augmented-plane-wave method. Emphasis is laid on the effects of curvature, the electron-beam orientation, and the inclusion of the core hole on the carbon electron-energy-loss K edge. The electron-energy-loss near-edge spectra of all the studied tubes show strong curvature effects compared to that of flat graphene. The curvature-induced π-σ hybridization is shown to have a more drastic effect on the electronic properties of zigzag tubes than on those of armchair tubes. We show that the core-hole effect must be accounted for in order to correctly reproduce electron-energy-loss measurements. We also find that the energy-loss near-edge spectra of these carbon systems are dominantly dipole selected and that they can be expressed simply as a proportionality with the local momentum projected density of states, thus portraying the weak energy dependence of the transition matrix elements. Compared to graphite, we report a reduction in the anisotropy as seen on the energy-loss near-edge spectra of carbon nanotubes

  8. Total binding energy of heavy positive ions including density treatment of Darwin and Breit corrections

    International Nuclear Information System (INIS)

    Hill, S.H.; Grout, P.J.; March, N.H.

    1987-01-01

    Previous work on the relativistic Thomas-Fermi treatment of total energies of neutral atoms is first generalised to heavy positive ions. To facilitate quantitative contact with the numerical predictions of Dirac-Fock theory, Darwin and Breit corrections are expressed in terms of electron density, and computed using input again from relativistic Thomas-Fermi theory. These corrections significantly improve the agreement between the two seemingly very different theories. (author)

  9. Effects of pairing correlation on nuclear level density parameter and nucleon separation energy

    International Nuclear Information System (INIS)

    Rajesekaran, T.R.; Selvaraj, S.

    2002-01-01

    A systematic study of effects of pairing correlations on nuclear level density parameter 'a' and neutron separation energy S N is presented for 152 Gd using statistical theory of nuclei with deformation, collective and noncollective rotational degrees of freedom, shell effects, and pairing correlations

  10. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry

    OpenAIRE

    Luis R. Domingo

    2016-01-01

    A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through ...

  11. Range-separated time-dependent density-functional theory with a frequency-dependent second-order Bethe-Salpeter correlation kernel

    Energy Technology Data Exchange (ETDEWEB)

    Rebolini, Elisa, E-mail: elisa.rebolini@kjemi.uio.no; Toulouse, Julien, E-mail: julien.toulouse@upmc.fr [Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Univ Paris 06, CNRS, 4 place Jussieu, F-75005 Paris (France)

    2016-03-07

    We present a range-separated linear-response time-dependent density-functional theory (TDDFT) which combines a density-functional approximation for the short-range response kernel and a frequency-dependent second-order Bethe-Salpeter approximation for the long-range response kernel. This approach goes beyond the adiabatic approximation usually used in linear-response TDDFT and aims at improving the accuracy of calculations of electronic excitation energies of molecular systems. A detailed derivation of the frequency-dependent second-order Bethe-Salpeter correlation kernel is given using many-body Green-function theory. Preliminary tests of this range-separated TDDFT method are presented for the calculation of excitation energies of the He and Be atoms and small molecules (H{sub 2}, N{sub 2}, CO{sub 2}, H{sub 2}CO, and C{sub 2}H{sub 4}). The results suggest that the addition of the long-range second-order Bethe-Salpeter correlation kernel overall slightly improves the excitation energies.

  12. Restoring the consistency with the contact density theorem of a classical density functional theory of ions at a planar electrical double layer.

    Science.gov (United States)

    Gillespie, Dirk

    2014-11-01

    Classical density functional theory (DFT) of fluids is a fast and efficient theory to compute the structure of the electrical double layer in the primitive model of ions where ions are modeled as charged, hard spheres in a background dielectric. While the hard-core repulsive component of this ion-ion interaction can be accurately computed using well-established DFTs, the electrostatic component is less accurate. Moreover, many electrostatic functionals fail to satisfy a basic theorem, the contact density theorem, that relates the bulk pressure, surface charge, and ion densities at their distances of closest approach for ions in equilibrium at a smooth, hard, planar wall. One popular electrostatic functional that fails to satisfy the contact density theorem is a perturbation approach developed by Kierlik and Rosinberg [Phys. Rev. A 44, 5025 (1991)PLRAAN1050-294710.1103/PhysRevA.44.5025] and Rosenfeld [J. Chem. Phys. 98, 8126 (1993)JCPSA60021-960610.1063/1.464569], where the full free-energy functional is Taylor-expanded around a bulk (homogeneous) reference fluid. Here, it is shown that this functional fails to satisfy the contact density theorem because it also fails to satisfy the known low-density limit. When the functional is corrected to satisfy this limit, a corrected bulk pressure is derived and it is shown that with this pressure both the contact density theorem and the Gibbs adsorption theorem are satisfied.

  13. Accurate and systematically improvable density functional theory embedding for correlated wavefunctions

    International Nuclear Information System (INIS)

    Goodpaster, Jason D.; Barnes, Taylor A.; Miller, Thomas F.; Manby, Frederick R.

    2014-01-01

    We analyze the sources of error in quantum embedding calculations in which an active subsystem is treated using wavefunction methods, and the remainder using density functional theory. We show that the embedding potential felt by the electrons in the active subsystem makes only a small contribution to the error of the method, whereas the error in the nonadditive exchange-correlation energy dominates. We test an MP2 correction for this term and demonstrate that the corrected embedding scheme accurately reproduces wavefunction calculations for a series of chemical reactions. Our projector-based embedding method uses localized occupied orbitals to partition the system; as with other local correlation methods, abrupt changes in the character of the localized orbitals along a reaction coordinate can lead to discontinuities in the embedded energy, but we show that these discontinuities are small and can be systematically reduced by increasing the size of the active region. Convergence of reaction energies with respect to the size of the active subsystem is shown to be rapid for all cases where the density functional treatment is able to capture the polarization of the environment, even in conjugated systems, and even when the partition cuts across a double bond

  14. VV and VO2 defects in silicon studied with hybrid density functional theory

    KAUST Repository

    Christopoulos, Stavros Richard G

    2014-12-07

    The formation of VO (A-center), VV and VO2 defects in irradiated Czochralski-grown silicon (Si) is of technological importance. Recent theoretical studies have examined the formation and charge states of the A-center in detail. Here we use density functional theory employing hybrid functionals to analyze the formation of VV and VO2 defects. The formation energy as a function of the Fermi energy is calculated for all possible charge states. For the VV and VO2 defects double negatively charged and neutral states dominate, respectively.

  15. Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals.

    Science.gov (United States)

    Furness, James W; Verbeke, Joachim; Tellgren, Erik I; Stopkowicz, Stella; Ekström, Ulf; Helgaker, Trygve; Teale, Andrew M

    2015-09-08

    We present the self-consistent implementation of current-dependent (hybrid) meta-generalized gradient approximation (mGGA) density functionals using London atomic orbitals. A previously proposed generalized kinetic energy density is utilized to implement mGGAs in the framework of Kohn-Sham current density functional theory (KS-CDFT). A unique feature of the nonperturbative implementation of these functionals is the ability to seamlessly explore a wide range of magnetic fields up to 1 au (∼235 kT) in strength. CDFT functionals based on the TPSS and B98 forms are investigated, and their performance is assessed by comparison with accurate coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) data. In the weak field regime, magnetic properties such as magnetizabilities and nuclear magnetic resonance shielding constants show modest but systematic improvements over generalized gradient approximations (GGA). However, in the strong field regime, the mGGA-based forms lead to a significantly improved description of the recently proposed perpendicular paramagnetic bonding mechanism, comparing well with CCSD(T) data. In contrast to functionals based on the vorticity, these forms are found to be numerically stable, and their accuracy at high field suggests that the extension of mGGAs to CDFT via the generalized kinetic energy density should provide a useful starting point for further development of CDFT approximations.

  16. A general range-separated double-hybrid density-functional theory.

    Science.gov (United States)

    Kalai, Cairedine; Toulouse, Julien

    2018-04-28

    A range-separated double-hybrid (RSDH) scheme which generalizes the usual range-separated hybrids and double hybrids is developed. This scheme consistently uses a two-parameter Coulomb-attenuating-method (CAM)-like decomposition of the electron-electron interaction for both exchange and correlation in order to combine Hartree-Fock exchange and second-order Møller-Plesset (MP2) correlation with a density functional. The RSDH scheme relies on an exact theory which is presented in some detail. Several semi-local approximations are developed for the short-range exchange-correlation density functional involved in this scheme. After finding optimal values for the two parameters of the CAM-like decomposition, the RSDH scheme is shown to have a relatively small basis dependence and to provide atomization energies, reaction barrier heights, and weak intermolecular interactions globally more accurate or comparable to range-separated MP2 or standard MP2. The RSDH scheme represents a new family of double hybrids with minimal empiricism which could be useful for general chemical applications.

  17. Density functional theory a practical introduction

    CERN Document Server

    Sholl, David

    2009-01-01

    Demonstrates how anyone in math, science, and engineering can master DFT calculations Density functional theory (DFT) is one of the most frequently used computational tools for studying and predicting the properties of isolated molecules, bulk solids, and material interfaces, including surfaces. Although the theoretical underpinnings of DFT are quite complicated, this book demonstrates that the basic concepts underlying the calculations are simple enough to be understood by anyone with a background in chemistry, physics, engineering, or mathematics. The authors show how the widespread availability of powerful DFT codes makes it possible for students and researchers to apply this important computational technique to a broad range of fundamental and applied problems. Density Functional Theory: A Practical Introduction offers a concise, easy-to-follow introduction to the key concepts and practical applications of DFT, focusing on plane-wave DFT. The authors have many years of experience introducing DFT to studen...

  18. Role of physisorption states in molecular scattering: a semilocal density-functional theory study on O2/Ag(111).

    Science.gov (United States)

    Goikoetxea, I; Meyer, J; Juaristi, J I; Alducin, M; Reuter, K

    2014-04-18

    We simulate the scattering of O2 from Ag(111) with classical dynamics simulations performed on a six-dimensional potential energy surface calculated within semilocal density-functional theory. The enigmatic experimental trends that originally required the conjecture of two types of repulsive walls, arising from a physisorption and chemisorption part of the interaction potential, are fully reproduced. Given the inadequate description of the physisorption properties in semilocal density-functional theory, our work casts severe doubts on the prevalent notion to use molecular scattering data as indirect evidence for the existence of such states.

  19. Density Functional Theory versus the Hartree-Fock Method: Comparative Assessment

    International Nuclear Information System (INIS)

    Amusia, M.Ya.; Shaginyan, V.R.; Msezane, A.Z.

    2003-01-01

    We compare two different approaches to investigations of many-electron systems. The first is the Hartree-Fock (HF) method and the second is the Density Functional Theory (DFT). Overview of the main features and peculiar properties of the HF method are presented. A way to realize the HF method within the Kohn-Sham (KS) approach of the DFT is discussed. We show that this is impossible without including a specific correlation energy, which is defined by the difference between the sum of the kinetic and exchange energies of a system considered within KS and HF, respectively. It is the nonlocal exchange potential entering the HF equations that generates this correlation energy. We show that the total correlation energy of a finite electron system, which has to include this correlation energy, cannot be obtained from considerations of uniform electron systems. The single-particle excitation spectrum of many-electron systems is related to the eigenvalues of the corresponding KS equations. We demonstrate that this spectrum does not coincide in general with the eigenvalues of KS or HF equations

  20. Density Functional Theory versus the Hartree-Fock Method: Comparative Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Amusia, M.Ya.; Shaginyan, V.R. [The Hebrew University, Jerusalem (Israel); Msezane, A.Z. [Clark Atlanta Univ., Atlanta, GA (United States). Center for Theoretical Studies of Physical Systems

    2003-12-01

    We compare two different approaches to investigations of many-electron systems. The first is the Hartree-Fock (HF) method and the second is the Density Functional Theory (DFT). Overview of the main features and peculiar properties of the HF method are presented. A way to realize the HF method within the Kohn-Sham (KS) approach of the DFT is discussed. We show that this is impossible without including a specific correlation energy, which is defined by the difference between the sum of the kinetic and exchange energies of a system considered within KS and HF, respectively. It is the nonlocal exchange potential entering the HF equations that generates this correlation energy. We show that the total correlation energy of a finite electron system, which has to include this correlation energy, cannot be obtained from considerations of uniform electron systems. The single-particle excitation spectrum of many-electron systems is related to the eigenvalues of the corresponding KS equations. We demonstrate that this spectrum does not coincide in general with the eigenvalues of KS or HF equations.

  1. Coulomb displacement energies and neutron density distributions

    International Nuclear Information System (INIS)

    Shlomo, S.

    1979-01-01

    We present a short review of the present status of the theory of Coulomb displacement energies, ΔEsub(c), discussing the Okamoto-Nolem-Schiffer anomaly and its solution. We emphasize, in particular, that contrary to previous hopes, ΔEsub(c) does not determine rsub(ex), the root-mean square (rms) radius of the excess (valence) neutron density distribution. Instead, ΔEsub(c) is very sensitive to the value of Δr = rsub(n) - rsub(p), the difference between the rms radii of the density distributions of all neutrons and all protons. For neutron rich nuclei, such as 48 Ca and 208 Pb, a value of Δr = 0.1 fm is found to be consistent with ΔEsub(c). This value of Δr, which is considerably smaller than that (of 0.2 - 0.3 fm) predicted by some common Hartree-Fock calculations, seems to be confirmed by very recent experimental results. (orig.)

  2. Locality of correlation in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Burke, Kieron [Department of Chemistry, University of California, Irvine, California 92697 (United States); Cancio, Antonio [Department of Physics and Astronomy, Ball State University, Muncie, Indiana 47306 (United States); Gould, Tim [Qld Micro- and Nanotechnology Centre, Griffith University, Nathan, Qld 4111 (Australia); Pittalis, Stefano [CNR-Istituto di Nanoscienze, Via Campi 213A, I-41125 Modena (Italy)

    2016-08-07

    The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that E{sub C} → −A{sub C} ZlnZ + B{sub C}Z as Z → ∞, where Z is the atomic number, A{sub C} is known, and we estimate B{sub C} to be about 37 mhartree. The local density approximation yields A{sub C} exactly, but a very incorrect value for B{sub C}, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with B{sub C} a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.

  3. Combining extrapolation with ghost interaction correction in range-separated ensemble density functional theory for excited states

    Science.gov (United States)

    Alam, Md. Mehboob; Deur, Killian; Knecht, Stefan; Fromager, Emmanuel

    2017-11-01

    The extrapolation technique of Savin [J. Chem. Phys. 140, 18A509 (2014)], which was initially applied to range-separated ground-state-density-functional Hamiltonians, is adapted in this work to ghost-interaction-corrected (GIC) range-separated ensemble density-functional theory (eDFT) for excited states. While standard extrapolations rely on energies that decay as μ-2 in the large range-separation-parameter μ limit, we show analytically that (approximate) range-separated GIC ensemble energies converge more rapidly (as μ-3) towards their pure wavefunction theory values (μ → +∞ limit), thus requiring a different extrapolation correction. The purpose of such a correction is to further improve on the convergence and, consequently, to obtain more accurate excitation energies for a finite (and, in practice, relatively small) μ value. As a proof of concept, we apply the extrapolation method to He and small molecular systems (viz., H2, HeH+, and LiH), thus considering different types of excitations such as Rydberg, charge transfer, and double excitations. Potential energy profiles of the first three and four singlet Σ+ excitation energies in HeH+ and H2, respectively, are studied with a particular focus on avoided crossings for the latter. Finally, the extraction of individual state energies from the ensemble energy is discussed in the context of range-separated eDFT, as a perspective.

  4. Density functional theory

    International Nuclear Information System (INIS)

    Freyss, M.

    2015-01-01

    This chapter gives an introduction to first-principles electronic structure calculations based on the density functional theory (DFT). Electronic structure calculations have a crucial importance in the multi-scale modelling scheme of materials: not only do they enable one to accurately determine physical and chemical properties of materials, they also provide data for the adjustment of parameters (or potentials) in higher-scale methods such as classical molecular dynamics, kinetic Monte Carlo, cluster dynamics, etc. Most of the properties of a solid depend on the behaviour of its electrons, and in order to model or predict them it is necessary to have an accurate method to compute the electronic structure. DFT is based on quantum theory and does not make use of any adjustable or empirical parameter: the only input data are the atomic number of the constituent atoms and some initial structural information. The complicated many-body problem of interacting electrons is replaced by an equivalent single electron problem, in which each electron is moving in an effective potential. DFT has been successfully applied to the determination of structural or dynamical properties (lattice structure, charge density, magnetisation, phonon spectra, etc.) of a wide variety of solids. Its efficiency was acknowledged by the attribution of the Nobel Prize in Chemistry in 1998 to one of its authors, Walter Kohn. A particular attention is given in this chapter to the ability of DFT to model the physical properties of nuclear materials such as actinide compounds. The specificities of the 5f electrons of actinides will be presented, i.e., their more or less high degree of localisation around the nuclei and correlations. The limitations of the DFT to treat the strong 5f correlations are one of the main issues for the DFT modelling of nuclear fuels. Various methods that exist to better treat strongly correlated materials will finally be presented. (author)

  5. Time dependent density functional theory of light absorption in dense plasmas: application to iron-plasma

    International Nuclear Information System (INIS)

    Grimaldi, F.; Grimaldi-Lecourt, A.; Dharma-Wardana, M.W.C.

    1986-10-01

    The objective of this paper is to present a simple time-dependent calculation of the light absorption cross section for a strongly coupled partially degenerate plasma so as to transcend the usual single-particle picture. This is achieved within the density functional theory (DFT) of plasmas by generalizing the method given by Zangwill and Soven for atomic calculations at zero temperature. The essential feature of the time dependent DFT is the correct treatment of the relaxation of the system under the external field. Exploratory calculations for a Fe-plasma at 100 eV show new features in the absorption cross section which are absent in the usual single particle theory. These arise from inter-shell correlations, channel mixing and self-energy effects. These many-body effects introduce significant modifications to the radiative properties of plasmas and are shown to be efficiently calculable by time dependent density functional theory (TD-DFT)

  6. Time dependent density functional theory of light absorption in dense plasmas: application to iron-plasma

    International Nuclear Information System (INIS)

    Grimaldi, F.; Grimaldi-Lecourt, A.; Dharma-Wardana, M.W.C.

    1985-02-01

    The objective of this paper is to present a simple time-dependent calculation of the light absorption cross section for a strongly coupled partially degenerate plasma so as to transcend the usual single-particle picture. This is achieved within the density functional theory (DFT) of plasmas by generalizing the method given by Zangwill and Soven for atomic calculations at zero temperature. The essential feature of the time dependent DFT is the correct treatment of the relaxation of the system under the external field. Exploratory calculations for an Fe-plasma at 100 eV show new features in the absorption cross section which are absent in the usual single particle theory. These arise from inter-shell correlations, channel mixing and self-energy effects. These many-body effects introduce significant modifications to the radiative properties of plasma and are shown to be efficiently calculable by time dependent density functional theory (TD-DFT)

  7. A Density Functional Theory Study

    KAUST Repository

    Lim, XiaoZhi

    2011-12-11

    Complexes with pincer ligand moieties have garnered much attention in the past few decades. They have been shown to be highly active catalysts in several known transition metal-catalyzed organic reactions as well as some unprecedented organic transformations. At the same time, the use of computational organometallic chemistry to aid in the understanding of the mechanisms in organometallic catalysis for the development of improved catalysts is on the rise. While it was common in earlier studies to reduce computational cost by truncating donor group substituents on complexes such as tertbutyl or isopropyl groups to hydrogen or methyl groups, recent advancements in the processing capabilities of computer clusters and codes have streamlined the time required for calculations. As the full modeling of complexes become increasingly popular, a commonly overlooked aspect, especially in the case of complexes bearing isopropyl substituents, is the conformational analysis of complexes. Isopropyl groups generate a different conformer with each 120 ° rotation (rotamer), and it has been found that each rotamer typically resides in its own potential energy well in density functional theory studies. As a result, it can be challenging to select the most appropriate structure for a theoretical study, as the adjustment of isopropyl substituents from a higher-energy rotamer to the lowest-energy rotamer usually does not occur during structure optimization. In this report, the influence of the arrangement of isopropyl substituents in pincer complexes on calculated complex structure energies as well as a case study on the mechanism of the isomerization of an iPrPCP-Fe complex is covered. It was found that as many as 324 rotamers can be generated for a single complex, as in the case of an iPrPCP-Ni formato complex, with the energy difference between the global minimum and the highest local minimum being as large as 16.5 kcalmol-1. In the isomerization of a iPrPCP-Fe complex, it was found

  8. Structure of single-particle nuclear densities from Hartree-Fock theory and model independent analysis

    International Nuclear Information System (INIS)

    Starodubskij, V.E.; Shaginyan, V.R.

    1979-01-01

    Friar-Negele method is applied to determine the static densities of neutrons and nuclear matter from the fast proton-nuclei elastic scattering data. This model-independent analysis (MIA) has been carried out for 28 Si, sup(32,34)S, sup(40,42,44,48)Ca, 48 Ti, sup(58,60)Ni, 90 Zr, 208 Pb nuclei. The binding energies, rms radii, densities and scattering cross sections of 1 GeV-proton are calculated in the framework of the Hartree-Fock theory (HF) with Skyrme's interaction. The HF and MIA densities and cross sections have been compared to draw a conclusion on the quality of the HF densities. Calculation of the cross sections has included the spin-orbit interaction with parameters taken from the polarization data

  9. Chemical hardness and density functional theory

    Indian Academy of Sciences (India)

    Unknown

    RALPH G PEARSON. Chemistry Department, University of California, Santa Barbara, CA 93106, USA. Abstract. The concept of chemical hardness is reviewed from a personal point of view. Keywords. Hardness; softness; hard & soft acids bases (HSAB); principle of maximum hardness. (PMH) density functional theory (DFT) ...

  10. Nuclear symmetry energy in density dependent hadronic models

    International Nuclear Information System (INIS)

    Haddad, S.

    2008-12-01

    The density dependence of the symmetry energy and the correlation between parameters of the symmetry energy and the neutron skin thickness in the nucleus 208 Pb are investigated in relativistic Hadronic models. The dependency of the symmetry energy on density is linear around saturation density. Correlation exists between the neutron skin thickness in the nucleus 208 Pb and the value of the nuclear symmetry energy at saturation density, but not with the slope of the symmetry energy at saturation density. (author)

  11. Batteries. Higher energy density than gasoline?

    International Nuclear Information System (INIS)

    Fischer, Michael; Werber, Mathew; Schwartz, Peter V.

    2009-01-01

    The energy density of batteries is two orders of magnitude below that of liquid fuels. However, this information alone cannot be used to compare batteries to liquid fuels for automobile energy storage media. Because electric motors have a higher energy conversion efficiency and lower mass than combustion engines, they can provide a higher deliverable mechanical energy density than internal combustion for most transportation applications. (author)

  12. On exact and approximate exchange-energy densities

    DEFF Research Database (Denmark)

    Springborg, Michael; Dahl, Jens Peder

    1999-01-01

    Based on correspondence rules between quantum-mechanical operators and classical functions in phase space we construct exchange-energy densities in position space. Whereas these are not unique but depend on the chosen correspondence rule, the exchange potential is unique. We calculate this exchange......-energy density for 15 closed-shell atoms, and compare it with kinetic- and Coulomb-energy densities. It is found that it has a dominating local-density character, but electron-shell effects are recognizable. The approximate exchange-energy functionals that have been proposed so far are found to account only...

  13. Studies of the energy density functional and its derivatives in atomic and molecular systems

    International Nuclear Information System (INIS)

    Robles, J.

    1986-01-01

    The first chapter is a review of formal density functional theory, (DFT). In the second chapter, approximations to exact DFT are reviewed. In chapter three, the author proposes a modified molecular Thomas-Fermi, (TF) theory. He proceeds by imposing a continuity condition on the density. This avoids the singularities at the nuclei of classical TF. The method is sanctioned by Teller and Balasz theorems. However, it is found that while the classical TF theory is improved, the present method still predicts no-binding. In chapter four, it is suggested that the correlation energy, (E/sub c/), is proportional to the exchange energy, (K), E/sub c/ = cK. This idea is tested with Hartree-Fock (HF) and DFT data. In HF, c = 1/40 for atoms and c = 1/25 for molecules. Furthermore, the method is used to estimate dissociation energies. Thereafter, the author studies the chemical potential, (μ), of atoms (chapter five) and molecules (chapter six). In chapter seven, the concept of local pressure in an inhomogeneous electronic system is studied and extended, within the local thermodynamic formulation of DFT. Finally, appendix A provides the required mathematical framework (basic functional calculus) to understand this work, while appendix B is essentially a summary of the HF method

  14. Current Issues in Finite-T Density-Functional Theory and Warm-Correlated Matter †

    Directory of Open Access Journals (Sweden)

    M. W. C. Dharma-wardana

    2016-03-01

    Full Text Available Finite-temperature density functional theory (DFT has become of topical interest, partly due to the increasing ability to create novel states of warm-correlated matter (WCM.Warm-dense matter (WDM, ultra-fast matter (UFM, and high-energy density matter (HEDM may all be regarded as subclasses of WCM. Strong electron-electron, ion-ion and electron-ion correlation effects and partial degeneracies are found in these systems where the electron temperature Te is comparable to the electron Fermi energy EF. Thus, many electrons are in continuum states which are partially occupied. The ion subsystem may be solid, liquid or plasma, with many states of ionization with ionic charge Zj. Quasi-equilibria with the ion temperature Ti ≠ Te are common. The ion subsystem in WCM can no longer be treated as a passive “external potential”, as is customary in T = 0 DFT dominated by solid-state theory or quantum chemistry. Many basic questions arise in trying to implement DFT for WCM. Hohenberg-Kohn-Mermin theory can be adapted for treating these systems if suitable finite-T exchange-correlation (XC functionals can be constructed. They are functionals of both the one-body electron density ne and the one-body ion densities ρj. Here, j counts many species of nuclei or charge states. A method of approximately but accurately mapping the quantum electrons to a classical Coulomb gas enables one to treat electron-ion systems entirely classically at any temperature and arbitrary spin polarization, using exchange-correlation effects calculated in situ, directly from the pair-distribution functions. This eliminates the need for any XC-functionals. This classical map has been used to calculate the equation of state of WDM systems, and construct a finite-T XC functional that is found to be in close agreement with recent quantum path-integral simulation data. In this review, current developments and concerns in finite-T DFT, especially in the context of non-relativistic warm

  15. Tuning electronic properties in graphene quantum dots by chemical functionalization: Density functional theory calculations

    Science.gov (United States)

    Abdelsalam, Hazem; Elhaes, Hanan; Ibrahim, Medhat A.

    2018-03-01

    The energy gap and dipole moment of chemically functionalized graphene quantum dots are investigated by density functional theory. The energy gap can be tuned through edge passivation by different elements or groups. Edge passivation by oxygen considerably decreases the energy gap in hexagonal nanodots. Edge states in triangular quantum dots can also be manipulated by passivation with fluorine. The dipole moment depends on: (a) shape and edge termination of the quantum dot, (b) attached group, and (c) position to which the groups are attached. Depending on the position of attached groups, the total dipole can be increased, decreased, or eliminated.

  16. Characterization of the nitrogen split interstitial defect in wurtzite aluminum nitride using density functional theory

    International Nuclear Information System (INIS)

    Szállás, A.; Szász, K.; Trinh, X. T.; Son, N. T.; Janzén, E.; Gali, A.

    2014-01-01

    We carried out Heyd-Scuseria-Ernzerhof hybrid density functional theory plane wave supercell calculations in wurtzite aluminum nitride in order to characterize the geometry, formation energies, transition levels, and hyperfine tensors of the nitrogen split interstitial defect. The calculated hyperfine tensors may provide useful fingerprint of this defect for electron paramagnetic resonance measurement.

  17. Characterization of the nitrogen split interstitial defect in wurtzite aluminum nitride using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Szállás, A., E-mail: szallas.attila@wigner.mta.hu [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Szász, K. [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Institute of Physics, Eötvös University, Pázmány Péter sétány 1/A, H-1117 Budapest (Hungary); Trinh, X. T.; Son, N. T.; Janzén, E. [Department of Physics, Chemistry and Biology, Linköping University, SE-581 83 Linköping (Sweden); Gali, A., E-mail: gali.adam@wigner.mta.hu [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Department of Atomic Physics, Budapest University of Technology and Economics, Budafoki út 8, H-1111 Budapest (Hungary)

    2014-09-21

    We carried out Heyd-Scuseria-Ernzerhof hybrid density functional theory plane wave supercell calculations in wurtzite aluminum nitride in order to characterize the geometry, formation energies, transition levels, and hyperfine tensors of the nitrogen split interstitial defect. The calculated hyperfine tensors may provide useful fingerprint of this defect for electron paramagnetic resonance measurement.

  18. A density functional theory-based chemical potential equalisation

    Indian Academy of Sciences (India)

    A chemical potential equalisation scheme is proposed for the calculation of these quantities and hence the dipole polarizability within the framework of density functional theory based linear response theory. The resulting polarizability is expressed in terms of the contributions from individual atoms in the molecule. A few ...

  19. Dual descriptors within the framework of spin-polarized density functional theory.

    Science.gov (United States)

    Chamorro, E; Pérez, P; Duque, M; De Proft, F; Geerlings, P

    2008-08-14

    Spin-polarized density functional theory (SP-DFT) allows both the analysis of charge-transfer (e.g., electrophilic and nucleophilic reactivity) and of spin-polarization processes (e.g., photophysical changes arising from electron transitions). In analogy with the dual descriptor introduced by Morell et al. [J. Phys. Chem. A 109, 205 (2005)], we introduce new dual descriptors intended to simultaneously give information of the molecular regions where the spin-polarization process linking states of different multiplicity will drive electron density and spin density changes. The electronic charge and spin rearrangement in the spin forbidden radiative transitions S(0)-->T(n,pi(*)) and S(0)-->T(pi,pi(*)) in formaldehyde and ethylene, respectively, have been used as benchmark examples illustrating the usefulness of the new spin-polarization dual descriptors. These quantities indicate those regions where spin-orbit coupling effects are at work in such processes. Additionally, the qualitative relationship between the topology of the spin-polarization dual descriptors and the vertical singlet triplet energy gap in simple substituted carbene series has been also discussed. It is shown that the electron density and spin density rearrangements arise in agreement with spectroscopic experimental evidence and other theoretical results on the selected target systems.

  20. Calculations of nuclear energies using the energy density formalism

    International Nuclear Information System (INIS)

    Pu, W.W.T.

    1975-01-01

    The energy density formalism (EDF) is used to investigate two problems. In this formalism the energy of the nucleus is expressed as a functional of its density. The nucleus energy is obtained by minimizing the functional with respect to the density. The first problem has to do with the stability of nuclei having shapes of different degrees of central depression (bubble shapes). It is shown that the bubble shapes are energetically favorable only for unrealistically large nuclei. Particularly, the super heavy nucleus that has been suggested (Z = 114, N = 184) prefers a shape with constant central density. These results are in good agreement with earlier calculations using the liquid drop model. The second problem concerns an anomaly detected experimentally in the isotope shift of mercury. The isotope shifts among a long chain of mercury isotopes show a sudden change as the neutron number is reduced. In particular, the experimental result suggests that the effective size of the charge distributions of 183 Hg and 185 Hg are as large as that of 196 Hg. Such sudden changes in other nuclei have been attributed to a sudden onset of permanent quadruple deformation. In the case of mercury there is no experimental evidence for deformed shapes. It was, therefore, suggested that the proton distribution might develop a central depression in the lighter isotopes. The EDF is used to investigate the mercury isotope shift anomaly following the aforementioned suggestion. Specifically, nucleon densities with different degrees of central depression are generated. Energies corresponding to these densities are obtained. To allow for shell effects, nucleon densities are obtained from single-particle wave functions. Calculations are made for a few mercury isotopes, especially for 184 Hg. The results are that in all cases the energy is lower for densities corresponding to a solid spherical shape

  1. The force distribution probability function for simple fluids by density functional theory.

    Science.gov (United States)

    Rickayzen, G; Heyes, D M

    2013-02-28

    Classical density functional theory (DFT) is used to derive a formula for the probability density distribution function, P(F), and probability distribution function, W(F), for simple fluids, where F is the net force on a particle. The final formula for P(F) ∝ exp(-AF(2)), where A depends on the fluid density, the temperature, and the Fourier transform of the pair potential. The form of the DFT theory used is only applicable to bounded potential fluids. When combined with the hypernetted chain closure of the Ornstein-Zernike equation, the DFT theory for W(F) agrees with molecular dynamics computer simulations for the Gaussian and bounded soft sphere at high density. The Gaussian form for P(F) is still accurate at lower densities (but not too low density) for the two potentials, but with a smaller value for the constant, A, than that predicted by the DFT theory.

  2. Interacting ghost dark energy in Brans-Dicke theory

    International Nuclear Information System (INIS)

    Ebrahimi, Esmaeil; Sheykhi, Ahmad

    2011-01-01

    We investigate the QCD ghost model of dark energy in the framework of Brans-Dicke cosmology. First, we study the non-interacting ghost dark energy in a flat Brans-Dicke theory. In this case we obtain the equation of state and the deceleration parameters and a differential equation governing the evolution of ghost energy density. Interestingly enough, we find that the equation of state parameter of the non-interacting ghost dark energy can cross the phantom line (w D =-1) provided the parameters of the model are chosen suitably. Then, we generalize the study to the interacting ghost dark energy in both flat and non-flat Brans-Dicke framework and find out that the transition of w D to phantom regime can be more easily achieved for than when resort to the Einstein field equations is made.

  3. Quantal density-functional theory in the presence of a magnetic field

    International Nuclear Information System (INIS)

    Yang Tao; Pan Xiaoyin; Sahni, Viraht

    2011-01-01

    We generalize the quantal density-functional theory (QDFT) of electrons in the presence of an external electrostatic field E(r)=-∇v(r) to include an external magnetostatic field B(r)=∇xA(r), where (v(r),A(r)) are the respective scalar and vector potentials. The generalized QDFT, valid for nondegenerate ground and excited states, is the mapping from the interacting system of electrons to a model of noninteracting fermions with the same density ρ(r) and physical current density j(r), and from which the total energy can be obtained. The properties (ρ(r),j(r)) constitute the basic quantum-mechanical variables because, as proved previously, for a nondegenerate ground state they uniquely determine the potentials (v(r),A(r)). The mapping to the noninteracting system is arbitrary in that the model fermions may be either in their ground or excited state. The theory is explicated by application to a ground state of the exactly solvable (two-dimensional) Hooke's atom in a magnetic field, with the mapping being to a model system also in its ground state. The majority of properties of the model are obtained in closed analytical or semianalytical form. A comparison with the corresponding mapping from a ground state of the (three-dimensional) Hooke's atom in the absence of a magnetic field is also made.

  4. A density functional theory-based investigation of adhesion of poly(butylene terephthalate) on aluminum

    International Nuclear Information System (INIS)

    David, Melanie; Roman, Tanglaw; Nakanishi, Hiroshi; Kasai, Hideaki; Ando, Naoki; Naritomi, Masanori

    2006-01-01

    We investigate the adhesion of PBT on aluminum using density functional theory-based calculations. The geometric structure of the PBT monomer is first relaxed then an aluminum atom is connected to the monomer in different orientations. We calculate their total energies and determine the orientation that gives the strongest binding between the monomer and the aluminum atom. Binding is strongest when the Al connects linearly with the carbonyl oxygen in the ester group. We present binding mechanisms and total energy relationships for the different orientations

  5. Local Fitting of the Kohn-Sham Density in a Gaussian and Plane Waves Scheme for Large-Scale Density Functional Theory Simulations.

    Science.gov (United States)

    Golze, Dorothea; Iannuzzi, Marcella; Hutter, Jürg

    2017-05-09

    A local resolution-of-the-identity (LRI) approach is introduced in combination with the Gaussian and plane waves (GPW) scheme to enable large-scale Kohn-Sham density functional theory calculations. In GPW, the computational bottleneck is typically the description of the total charge density on real-space grids. Introducing the LRI approximation, the linear scaling of the GPW approach with respect to system size is retained, while the prefactor for the grid operations is reduced. The density fitting is an O(N) scaling process implemented by approximating the atomic pair densities by an expansion in one-center fit functions. The computational cost for the grid-based operations becomes negligible in LRIGPW. The self-consistent field iteration is up to 30 times faster for periodic systems dependent on the symmetry of the simulation cell and on the density of grid points. However, due to the overhead introduced by the local density fitting, single point calculations and complete molecular dynamics steps, including the calculation of the forces, are effectively accelerated by up to a factor of ∼10. The accuracy of LRIGPW is assessed for different systems and properties, showing that total energies, reaction energies, intramolecular and intermolecular structure parameters are well reproduced. LRIGPW yields also high quality results for extended condensed phase systems such as liquid water, ice XV, and molecular crystals.

  6. Obtaining Hartree-Fock and density functional theory doubly excited states with Car-Parrinello density matrix search

    Science.gov (United States)

    Liang, Wenkel; Isborn, Christine M.; Li, Xiaosong

    2009-11-01

    The calculation of doubly excited states is one of the major problems plaguing the modern day excited state workhorse methodology of linear response time dependent Hartree-Fock (TDHF) and density function theory (TDDFT). We have previously shown that the use of a resonantly tuned field within real-time TDHF and TDDFT is able to simultaneously excite both the α and β electrons to achieve the two-electron excited states of minimal basis H2 and HeH+ [C. M. Isborn and X. Li, J. Chem. Phys. 129, 204107 (2008)]. We now extend this method to many electron systems with the use of our Car-Parrinello density matrix search (CP-DMS) with a first-principles fictitious mass method for wave function optimization [X. Li, C. L. Moss, W. Liang, and Y. Feng, J. Chem. Phys. 130, 234115 (2009)]. Real-time TDHF/TDDFT is used during the application of the laser field perturbation, driving the electron density toward the doubly excited state. The CP-DMS method then converges the density to the nearest stationary state. We present these stationary state doubly excited state energies and properties at the HF and DFT levels for H2, HeH+, lithium hydride, ethylene, and butadiene.

  7. Modeling charged defects inside density functional theory band gaps

    International Nuclear Information System (INIS)

    Schultz, Peter A.; Edwards, Arthur H.

    2014-01-01

    Density functional theory (DFT) has emerged as an important tool to probe microscopic behavior in materials. The fundamental band gap defines the energy scale for charge transition energy levels of point defects in ionic and covalent materials. The eigenvalue gap between occupied and unoccupied states in conventional DFT, the Kohn–Sham gap, is often half or less of the experimental band gap, seemingly precluding quantitative studies of charged defects. Applying explicit and rigorous control of charge boundary conditions in supercells, we find that calculations of defect energy levels derived from total energy differences give accurate predictions of charge transition energy levels in Si and GaAs, unhampered by a band gap problem. The GaAs system provides a good theoretical laboratory for investigating band gap effects in defect level calculations: depending on the functional and pseudopotential, the Kohn–Sham gap can be as large as 1.1 eV or as small as 0.1 eV. We find that the effective defect band gap, the computed range in defect levels, is mostly insensitive to the Kohn–Sham gap, demonstrating it is often possible to use conventional DFT for quantitative studies of defect chemistry governing interesting materials behavior in semiconductors and oxides despite a band gap problem

  8. High Energy Density Laboratory Astrophysics

    CERN Document Server

    Lebedev, Sergey V

    2007-01-01

    During the past decade, research teams around the world have developed astrophysics-relevant research utilizing high energy-density facilities such as intense lasers and z-pinches. Every two years, at the International conference on High Energy Density Laboratory Astrophysics, scientists interested in this emerging field discuss the progress in topics covering: - Stellar evolution, stellar envelopes, opacities, radiation transport - Planetary Interiors, high-pressure EOS, dense plasma atomic physics - Supernovae, gamma-ray bursts, exploding systems, strong shocks, turbulent mixing - Supernova remnants, shock processing, radiative shocks - Astrophysical jets, high-Mach-number flows, magnetized radiative jets, magnetic reconnection - Compact object accretion disks, x-ray photoionized plasmas - Ultrastrong fields, particle acceleration, collisionless shocks. These proceedings cover many of the invited and contributed papers presented at the 6th International Conference on High Energy Density Laboratory Astrophys...

  9. Applications of Density Functional Theory in Soft Condensed Matter

    Science.gov (United States)

    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.

  10. Analytic cubic and quartic force fields using density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ringholm, Magnus; Gao, Bin; Thorvaldsen, Andreas J.; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); Jonsson, Dan [Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); High Performance Computing Group, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); Bast, Radovan [Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, AlbaNova University Center, S-10691 Stockholm, Sweden and PDC Center for High Performance Computing, Royal Institute of Technology, S-10044 Stockholm (Sweden); Ekström, Ulf; Helgaker, Trygve [Center for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)

    2014-01-21

    We present the first analytic implementation of cubic and quartic force constants at the level of Kohn–Sham density-functional theory. The implementation is based on an open-ended formalism for the evaluation of energy derivatives in an atomic-orbital basis. The implementation relies on the availability of open-ended codes for evaluation of one- and two-electron integrals differentiated with respect to nuclear displacements as well as automatic differentiation of the exchange–correlation kernels. We use generalized second-order vibrational perturbation theory to calculate the fundamental frequencies of methane, ethane, benzene, and aniline, comparing B3LYP, BLYP, and Hartree–Fock results. The Hartree–Fock anharmonic corrections agree well with the B3LYP corrections when calculated at the B3LYP geometry and from B3LYP normal coordinates, suggesting that the inclusion of electron correlation is not essential for the reliable calculation of cubic and quartic force constants.

  11. Validation of molecular crystal structures from powder diffraction data with dispersion-corrected density functional theory (DFT-D)

    DEFF Research Database (Denmark)

    van de Streek, Jacco; Neumann, Marcus A

    2014-01-01

    In 2010 we energy-minimized 225 high-quality single-crystal (SX) structures with dispersion-corrected density functional theory (DFT-D) to establish a quantitative benchmark. For the current paper, 215 organic crystal structures determined from X-ray powder diffraction (XRPD) data and published...

  12. Fundamentals of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Marques, Miguel A.L.; Rubio, Angel

    2012-01-01

    There have been many significant advances in time-dependent density functional theory over recent years, both in enlightening the fundamental theoretical basis of the theory, as well as in computational algorithms and applications. This book, as successor to the highly successful volume Time-Dependent Density Functional Theory (Lect. Notes Phys. 706, 2006) brings together for the first time all recent developments in a systematic and coherent way. First, a thorough pedagogical presentation of the fundamental theory is given, clarifying aspects of the original proofs and theorems, as well as presenting fresh developments that extend the theory into new realms such as alternative proofs of the original Runge-Gross theorem, open quantum systems, and dispersion forces to name but a few. Next, all of the basic concepts are introduced sequentially and building in complexity, eventually reaching the level of open problems of interest. Contemporary applications of the theory are discussed, from real-time coupled-electron-ion dynamics, to excited-state dynamics and molecular transport. Last but not least, the authors introduce and review recent advances in computational implementation, including massively parallel architectures and graphical processing units. Special care has been taken in editing this volume as a multi-author textbook, following a coherent line of thought, and making all the relevant connections between chapters and concepts consistent throughout. As such it will prove to be the text of reference in this field, both for beginners as well as expert researchers and lecturers teaching advanced quantum mechanical methods to model complex physical systems, from molecules to nanostructures, from biocomplexes to surfaces, solids and liquids. (orig.)

  13. Density functional theory and evolution algorithm calculations of elastic properties of AlON

    Energy Technology Data Exchange (ETDEWEB)

    Batyrev, I. G.; Taylor, D. E.; Gazonas, G. A.; McCauley, J. W. [U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States)

    2014-01-14

    Different models for aluminum oxynitride (AlON) were calculated using density functional theory and optimized using an evolutionary algorithm. Evolutionary algorithm and density functional theory (DFT) calculations starting from several models of AlON with different Al or O vacancy locations and different positions for the N atoms relative to the vacancy were carried out. The results show that the constant anion model [McCauley et al., J. Eur. Ceram. Soc. 29(2), 223 (2009)] with a random distribution of N atoms not adjacent to the Al vacancy has the lowest energy configuration. The lowest energy structure is in a reasonable agreement with experimental X-ray diffraction spectra. The optimized structure of a 55 atom unit cell was used to construct 220 and 440 atom models for simulation cells using DFT with a Gaussian basis set. Cubic elastic constant predictions were found to approach the experimentally determined AlON single crystal elastic constants as the model size increased from 55 to 440 atoms. The pressure dependence of the elastic constants found from simulated stress-strain relations were in overall agreement with experimental measurements of polycrystalline and single crystal AlON. Calculated IR intensity and Raman spectra are compared with available experimental data.

  14. Strong Correlation in Kohn-Sham Density Functional Theory

    NARCIS (Netherlands)

    Malet, F.; Gori Giorgi, P.

    2012-01-01

    We use the exact strong-interaction limit of the Hohenberg-Kohn energy density functional to approximate the exchange-correlation energy of the restricted Kohn-Sham scheme. Our approximation corresponds to a highly nonlocal density functional whose functional derivative can be easily constructed,

  15. Threshold defect production in silicon determined by density functional theory molecular dynamics simulations

    International Nuclear Information System (INIS)

    Holmstroem, E.; Kuronen, A.; Nordlund, K.

    2008-01-01

    We studied threshold displacement energies for creating stable Frenkel pairs in silicon using density functional theory molecular dynamics simulations. The average threshold energy over all lattice directions was found to be 36±2 STAT ±2 SYST eV, and thresholds in the directions and were found to be 20±2 SYST eV and 12.5±1.5 SYST eV, respectively. Moreover, we found that in most studied lattice directions, a bond defect complex is formed with a lower threshold than a Frenkel pair. The average threshold energy for producing either a bond defect or a Frenkel pair was found to be 24±1 STAT ±2 SYST eV

  16. Ab initio quasi-particle approximation bandgaps of silicon nanowires calculated at density functional theory/local density approximation computational effort

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, M., E-mail: ribeiro.jr@oorbit.com.br [Office of Operational Research for Business Intelligence and Technology, Principal Office, Buffalo, Wyoming 82834 (United States)

    2015-06-21

    Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost.

  17. Ab initio quasi-particle approximation bandgaps of silicon nanowires calculated at density functional theory/local density approximation computational effort

    International Nuclear Information System (INIS)

    Ribeiro, M.

    2015-01-01

    Ab initio calculations of hydrogen-passivated Si nanowires were performed using density functional theory within LDA-1/2, to account for the excited states properties. A range of diameters was calculated to draw conclusions about the ability of the method to correctly describe the main trends of bandgap, quantum confinement, and self-energy corrections versus the diameter of the nanowire. Bandgaps are predicted with excellent accuracy if compared with other theoretical results like GW, and with the experiment as well, but with a low computational cost

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

    Science.gov (United States)

    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.

  19. Perturbation theory corrections to the two-particle reduced density matrix variational method.

    Science.gov (United States)

    Juhasz, Tamas; Mazziotti, David A

    2004-07-15

    In the variational 2-particle-reduced-density-matrix (2-RDM) method, the ground-state energy is minimized with respect to the 2-particle reduced density matrix, constrained by N-representability conditions. Consider the N-electron Hamiltonian H(lambda) as a function of the parameter lambda where we recover the Fock Hamiltonian at lambda=0 and we recover the fully correlated Hamiltonian at lambda=1. We explore using the accuracy of perturbation theory at small lambda to correct the 2-RDM variational energies at lambda=1 where the Hamiltonian represents correlated atoms and molecules. A key assumption in the correction is that the 2-RDM method will capture a fairly constant percentage of the correlation energy for lambda in (0,1] because the nonperturbative 2-RDM approach depends more significantly upon the nature rather than the strength of the two-body Hamiltonian interaction. For a variety of molecules we observe that this correction improves the 2-RDM energies in the equilibrium bonding region, while the 2-RDM energies at stretched or nearly dissociated geometries, already highly accurate, are not significantly changed. At equilibrium geometries the corrected 2-RDM energies are similar in accuracy to those from coupled-cluster singles and doubles (CCSD), but at nonequilibrium geometries the 2-RDM energies are often dramatically more accurate as shown in the bond stretching and dissociation data for water and nitrogen. (c) 2004 American Institute of Physics.

  20. Theory of ultra dense matter and the dynamics of high energy interactions involving nuclei

    International Nuclear Information System (INIS)

    Gyulassy, M.

    1993-01-01

    Progress in the areas of pQCD radiative processes in dense matter, QCD transport theories to describe the evolution of nonequilibrium phenomena in dense matter, and the development and testing of phenomenological models of high-energy nuclear collisions is summarized. The evolution of the total energy density of quarks and gluons with minijet initial conditions at RHIC energy is shown for Au+Au

  1. Are both symmetric and buckled dimers on Si(100) minima? Density functional and multireference perturbation theory calculations

    International Nuclear Information System (INIS)

    Jung, Yousung; Shao, Yihan; Gordon, Mark S.; Doren, Douglas J.; Head-Gordon, Martin

    2003-01-01

    We report a spin-unrestricted density functional theory (DFT) solution at the symmetric dimer structure for cluster models of Si(100). With this solution, it is shown that the symmetric structure is a minimum on the DFT potential energy surface, although higher in energy than the buckled structure. In restricted DFT calculations the symmetric structure is a saddle point connecting the two buckled minima. To further assess the effects of electron correlation on the relative energies of symmetric versus buckled dimers on Si(100), multireference second order perturbation theory (MRMP2) calculations are performed on these DFT optimized minima. The symmetric structure is predicted to be lower in energy than the buckled structure via MRMP2, while the reverse order is found by DFT. The implications for recent experimental interpretations are discussed

  2. Study of chemical bonding in the interhalogen complexes based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. Kh., E-mail: poleshch@tspu.edu.ru [National Research Tomsk Polytechnic University (Russian Federation); Fateev, A. V.; Yarkova, A. G. [Tomsk State Pedagogical University (Russian Federation); Ermakhanov, M. N.; Saidakhmetov, P. A. [M. Auezov South Kazakhstan State University (Kazakhstan)

    2016-12-15

    The density functional theory analysis was used for a number XYL complexes (XY is a dihalogen molecule and L is a Lewis base), formed between molecules I{sub 2}, ICl, IBr and pyridine. The calculated geometrical parameters, IR spectra and nuclear quadrupole interaction constants of iodine are consistent with the data of microwave spectroscopy and nuclear quadrupole resonance. The good correlation between the experimental and calculated binding energies of the inner electrons of iodine, chlorine and nitrogen atoms were found with the calculation using both Gaussian and Slater functions. The comparison of experimental and calculated changes in the electron density on the atoms upon complex formation suggested the choice of scheme for calculating the effective charge on the atoms, which allow us to interpret the experimental spectra. It is shown that the use of both calculated schemes allows us to predict the enthalpy of complex formation in close agreement with the experimental values. The energy analysis shows that in the complexes the electrostatic binding energy dominates that of covalent binding.

  3. Tight-binding approximations to time-dependent density functional theory — A fast approach for the calculation of electronically excited states

    Energy Technology Data Exchange (ETDEWEB)

    Rüger, Robert, E-mail: rueger@scm.com [Scientific Computing & Modelling NV, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Department of Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Linnéstr. 2, 04103 Leipzig (Germany); Lenthe, Erik van [Scientific Computing & Modelling NV, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Heine, Thomas [Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Linnéstr. 2, 04103 Leipzig (Germany); Visscher, Lucas [Department of Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands)

    2016-05-14

    We propose a new method of calculating electronically excited states that combines a density functional theory based ground state calculation with a linear response treatment that employs approximations used in the time-dependent density functional based tight binding (TD-DFTB) approach. The new method termed time-dependent density functional theory TD-DFT+TB does not rely on the DFTB parametrization and is therefore applicable to systems involving all combinations of elements. We show that the new method yields UV/Vis absorption spectra that are in excellent agreement with computationally much more expensive TD-DFT calculations. Errors in vertical excitation energies are reduced by a factor of two compared to TD-DFTB.

  4. Building A Universal Nuclear Energy Density Functional (UNEDF)

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, Joe [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Furnstahl, Dick [The Ohio State Univ., Columbus, OH (United States); Horoi, Mihai [Central Michigan Univ., Mount Pleasant, MI (United States); Lusk, Rusty [Argonne National Lab. (ANL), Argonne, IL (United States); Nazarewicz, Witek [Univ. of Tennessee, Knoxville, TN (United States); Ng, Esmond [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Thompson, Ian [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Vary, James [Iowa State Univ., Ames, IA (United States)

    2012-09-30

    During the period of Dec. 1 2006 - Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei, based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: first, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory. The main physics areas of UNEDF, defined at the beginning of the project, were: ab initio structure; ab initio functionals; DFT applications; DFT extensions; reactions.

  5. Describing a Strongly Correlated Model System with Density Functional Theory.

    Science.gov (United States)

    Kong, Jing; Proynov, Emil; Yu, Jianguo; Pachter, Ruth

    2017-07-06

    The linear chain of hydrogen atoms, a basic prototype for the transition from a metal to Mott insulator, is studied with a recent density functional theory model functional for nondynamic and strong correlation. The computed cohesive energy curve for the transition agrees well with accurate literature results. The variation of the electronic structure in this transition is characterized with a density functional descriptor that yields the atomic population of effectively localized electrons. These new methods are also applied to the study of the Peierls dimerization of the stretched even-spaced Mott insulator to a chain of H 2 molecules, a different insulator. The transitions among the two insulating states and the metallic state of the hydrogen chain system are depicted in a semiquantitative phase diagram. Overall, we demonstrate the capability of studying strongly correlated materials with a mean-field model at the fundamental level, in contrast to the general pessimistic view on such a feasibility.

  6. Mechanical confinement for improved energy storage density in BNT-BT-KNN lead-free ceramic capacitors

    Directory of Open Access Journals (Sweden)

    Aditya Chauhan

    2014-08-01

    Full Text Available With the advent of modern power electronics, embedded circuits and non-conventional energy harvesting, the need for high performance capacitors is bound to become indispensible. The current state-of-art employs ferroelectric ceramics and linear dielectrics for solid state capacitance. However, lead-free ferroelectric ceramics propose to offer significant improvement in the field of electrical energy storage owing to their high discharge efficiency and energy storage density. In this regards, the authors have investigated the effects of compressive stress as a means of improving the energy storage density of lead-free ferroelectric ceramics. The energy storage density of 0.91(Bi0.5Na0.5TiO3-0.07BaTiO3-0.02(K0.5Na0.5NbO3 ferroelectric bulk ceramic was analyzed as a function of varying levels of compressive stress and operational temperature .It was observed that a peak energy density of 387 mJ.cm-3 was obtained at 100 MPa applied stress (25oC. While a maximum energy density of 568 mJ.cm-3 was obtained for the same stress at 80oC. These values are indicative of a significant, 25% and 84%, improvement in the value of stored energy compared to an unloaded material. Additionally, material's discharge efficiency has also been discussed as a function of operational parameters. The observed phenomenon has been explained on the basis of field induced structural transition and competitive domain switching theory.

  7. X-ray spectroscopy for high energy-density X pinch density and temperature measurements (invited)

    International Nuclear Information System (INIS)

    Pikuz, S.A.; Shelkovenko, T.A.; Chandler, K.M.; Mitchell, M.D.; Hammer, D.A.; Skobelev, I.Y.; Shlyaptseva, A.S.; Hansen, S.B.

    2004-01-01

    X pinch plasmas produced from fine metal wires can reach near solid densities and temperatures of 1 keV or even more. Plasma conditions change on time scales as short as 5-10 ps as determined using an x-ray streak camera viewing a focusing crystal spectrograph or directly viewing the plasma through multiple filters on a single test. As a result, it is possible to determine plasma conditions from spectra with ∼10 ps time resolution. Experiments and theory are now coming together to give a consistent picture of the dynamics and kinetics of these high energy density plasmas with very high temporal and spatial precision. A set of diagnostic techniques used in experiments for spectrally, temporally, and spatially resolved measurements of X pinch plasmas is described. Results of plasma parameter determination from these measurements are presented. X ray backlighting of one x-pinch by another with ∼30 ps x-ray pulses enables the dynamics and kinetics to be correlated in time

  8. Traversible wormholes and the negative-stress-energy problem in the nonsymmetric gravitational theory

    International Nuclear Information System (INIS)

    Moffat, J.W.; Svoboda, T.

    1991-01-01

    The stress-energy tensor for a a general spherically symmetric matter distribution in the nonsymmetric gravitational theory (NGT) is determined using a heuristic argument. Using this tensor and the NGT field equations, it is shown that a wormhole threaded with matter must necessarily have a radial tension greater than the mass-energy density in the throat region. Hence, as in general relativity, a traversible wormhole in NGT must contain matter with a negative stress energy

  9. Time-dependent density-functional tight-binding method with the third-order expansion of electron density.

    Science.gov (United States)

    Nishimoto, Yoshio

    2015-09-07

    We develop a formalism for the calculation of excitation energies and excited state gradients for the self-consistent-charge density-functional tight-binding method with the third-order contributions of a Taylor series of the density functional theory energy with respect to the fluctuation of electron density (time-dependent density-functional tight-binding (TD-DFTB3)). The formulation of the excitation energy is based on the existing time-dependent density functional theory and the older TD-DFTB2 formulae. The analytical gradient is computed by solving Z-vector equations, and it requires one to calculate the third-order derivative of the total energy with respect to density matrix elements due to the inclusion of the third-order contributions. The comparison of adiabatic excitation energies for selected small and medium-size molecules using the TD-DFTB2 and TD-DFTB3 methods shows that the inclusion of the third-order contributions does not affect excitation energies significantly. A different set of parameters, which are optimized for DFTB3, slightly improves the prediction of adiabatic excitation energies statistically. The application of TD-DFTB for the prediction of absorption and fluorescence energies of cresyl violet demonstrates that TD-DFTB3 reproduced the experimental fluorescence energy quite well.

  10. Improved Accuracy of Density Functional Theory Calculations for CO2 Reduction and Metal-Air Batteries

    DEFF Research Database (Denmark)

    Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Density functional theory (DFT) calculations have greatly contributed to the atomic level understanding of electrochemical reactions. However, in some cases, the accuracy can be prohibitively low for a detailed understanding of, e.g. reaction mechanisms. Two cases are examined here, i.e. the elec......Density functional theory (DFT) calculations have greatly contributed to the atomic level understanding of electrochemical reactions. However, in some cases, the accuracy can be prohibitively low for a detailed understanding of, e.g. reaction mechanisms. Two cases are examined here, i.......47 eV and 0.17 eV using metals as reference. The presented approach for error identification is expected to be applicable to a very broad range of systems. References: [1] A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, and J. K. Nørskov, Energy Environ. Sci., 3,1311 (2010) [2] F. Studt, F...

  11. Density functional theory calculations of charge transport properties ...

    Indian Academy of Sciences (India)

    ZIRAN CHEN

    2017-08-04

    Aug 4, 2017 ... properties of 'plate-like' coronene topological structures ... Keywords. Organic semiconductors; density functional theory; charge carrier mobility; ambipolar transport; ..... nology Department of Sichuan Province (Grant Number.

  12. Computationally simple, analytic, closed form solution of the Coulomb self-interaction problem in Kohn Sham density functional theory

    International Nuclear Information System (INIS)

    Gonis, Antonios; Daene, Markus W.; Nicholson, Don M.; Stocks, George Malcolm

    2012-01-01

    We have developed and tested in terms of atomic calculations an exact, analytic and computationally simple procedure for determining the functional derivative of the exchange energy with respect to the density in the implementation of the Kohn Sham formulation of density functional theory (KS-DFT), providing an analytic, closed-form solution of the self-interaction problem in KS-DFT. We demonstrate the efficacy of our method through ground-state calculations of the exchange potential and energy for atomic He and Be atoms, and comparisons with experiment and the results obtained within the optimized effective potential (OEP) method.

  13. Reduced density matrix functional theory via a wave function based approach

    Energy Technology Data Exchange (ETDEWEB)

    Schade, Robert; Bloechl, Peter [Institute for Theoretical Physics, Clausthal University of Technology, Clausthal (Germany); Pruschke, Thomas [Institute for Theoretical Physics, University of Goettingen, Goettingen (Germany)

    2016-07-01

    We propose a new method for the calculation of the electronic and atomic structure of correlated electron systems based on reduced density matrix functional theory (rDMFT). The density-matrix functional is evaluated on the fly using Levy's constrained search formalism. The present implementation rests on a local approximation of the interaction reminiscent to that of dynamical mean field theory (DMFT). We focus here on additional approximations to the exact density-matrix functional in the local approximation and evaluate their performance.

  14. Energy vs. density on paths toward exact density functionals

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2018-01-01

    Recently, the progression toward more exact density functional theory has been questioned, implying a need for more formal ways to systematically measure progress, i.e. a “path”. Here I use the Hohenberg-Kohn theorems and the definition of normality by Burke et al. to define a path toward exactness...

  15. High density energy storage capacitor

    International Nuclear Information System (INIS)

    Whitham, K.; Howland, M.M.; Hutzler, J.R.

    1979-01-01

    The Nova laser system will use 130 MJ of capacitive energy storage and have a peak power capability of 250,000 MW. This capacitor bank is a significant portion of the laser cost and requires a large portion of the physical facilities. In order to reduce the cost and volume required by the bank, the Laser Fusion Program funded contracts with three energy storage capacitor producers: Aerovox, G.E., and Maxwell Laboratories, to develop higher energy density, lower cost energy storage capacitors. This paper describes the designs which resulted from the Aerovox development contract, and specifically addresses the design and initial life testing of a 12.5 kJ, 22 kV capacitor with a density of 4.2 J/in 3 and a projected cost in the range of 5 cents per joule

  16. The effective QCD theory at low energy; La theorie effective de QCD a basse energie

    Energy Technology Data Exchange (ETDEWEB)

    Knecht, M. [Paris-11 Univ., 91 - Orsay (France). Inst. de Physique Nucleaire

    1995-12-31

    Quantum chromodynamics is studied here in the range of low energies. The Chiral perturbation theory is presented, this theory is based on a thorough study of QCD symmetry, of general field theory principles and of S-matrices. Ward identities are defined within the scope of current algebras and by using functional method. Their consequences on Chiral structure of QCD emptiness and on strong interaction at low energies are studied. The pion-pion diffusion at low energies is treated as an example. (A.C.) 70 refs.

  17. A theoretical study of lithium-doped gallium clusters by density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Sentuerk, Suekrue; Ekincioglu, Yavuz [Dumlupinar Univ., Kutahya (Turkey). Dept. of Physics

    2012-05-15

    The geometrical structures, stabilities, and electronic properties of Ga{sub n}Li (n = 1-13) clusters were investigated within the density functional theory (DFT). The impurity lithium atom enhances the stability of Ga{sub n}Li (n = 1-13) clusters, especially Ga{sub n}Li (n = 9-13) compared to Ga{sub n} (n = 9-14), that is at either apex position or side position. The dissociation energy, second-order energy differences, and the energy gaps between highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) indicate that the Ga{sub 7}Li, Ga{sub 9}Li, and Ga{sub 11}Li clusters are more stable within the studied cluster range. Moreover, the variation of the average bond length of Ga - Li is due to the surface effect, and the binding strength increases resulting from the increase of charge amount. (orig.)

  18. Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculations

    International Nuclear Information System (INIS)

    Streek, Jacco van de; Neumann, Marcus A.

    2010-01-01

    The accuracy of a dispersion-corrected density functional theory method is validated against 241 experimental organic crystal structures from Acta Cryst. Section E. This paper describes the validation of a dispersion-corrected density functional theory (d-DFT) method for the purpose of assessing the correctness of experimental organic crystal structures and enhancing the information content of purely experimental data. 241 experimental organic crystal structures from the August 2008 issue of Acta Cryst. Section E were energy-minimized in full, including unit-cell parameters. The differences between the experimental and the minimized crystal structures were subjected to statistical analysis. The r.m.s. Cartesian displacement excluding H atoms upon energy minimization with flexible unit-cell parameters is selected as a pertinent indicator of the correctness of a crystal structure. All 241 experimental crystal structures are reproduced very well: the average r.m.s. Cartesian displacement for the 241 crystal structures, including 16 disordered structures, is only 0.095 Å (0.084 Å for the 225 ordered structures). R.m.s. Cartesian displacements above 0.25 Å either indicate incorrect experimental crystal structures or reveal interesting structural features such as exceptionally large temperature effects, incorrectly modelled disorder or symmetry breaking H atoms. After validation, the method is applied to nine examples that are known to be ambiguous or subtly incorrect

  19. Accuracy of finite-difference harmonic frequencies in density functional theory.

    Science.gov (United States)

    Liu, Kuan-Yu; Liu, Jie; Herbert, John M

    2017-07-15

    Analytic Hessians are often viewed as essential for the calculation of accurate harmonic frequencies, but the implementation of analytic second derivatives is nontrivial and solution of the requisite coupled-perturbed equations engenders a sizable memory footprint for large systems, given that these equations are not required for energy and gradient calculations in density functional theory. Here, we benchmark the alternative approach to harmonic frequencies based on finite differences of analytic first derivatives, a procedure that is amenable to large-scale parallelization. Not only for absolute frequencies but also for isotopic and conformer-dependent frequency shifts in flexible molecules, we find that the finite-difference approach exhibits mean errors numbers. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  20. Hydrodynamic perspective on memory in time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Thiele, M.; Kuemmel, S.

    2009-01-01

    The adiabatic approximation of time-dependent density-functional theory is studied in the context of nonlinear excitations of two-electron singlet systems. We compare the exact time evolution of these systems to the adiabatically exact one obtained from time-dependent Kohn-Sham calculations relying on the exact ground-state exchange-correlation potential. Thus, we can show under which conditions the adiabatic approximation breaks down and memory effects become important. The hydrodynamic formulation of quantum mechanics allows us to interpret these results and relate them to dissipative effects in the Kohn-Sham system. We show how the breakdown of the adiabatic approximation can be inferred from the rate of change of the ground-state noninteracting kinetic energy.

  1. Unification of field theory and maximum entropy methods for learning probability densities

    Science.gov (United States)

    Kinney, Justin B.

    2015-09-01

    The need to estimate smooth probability distributions (a.k.a. probability densities) from finite sampled data is ubiquitous in science. Many approaches to this problem have been described, but none is yet regarded as providing a definitive solution. Maximum entropy estimation and Bayesian field theory are two such approaches. Both have origins in statistical physics, but the relationship between them has remained unclear. Here I unify these two methods by showing that every maximum entropy density estimate can be recovered in the infinite smoothness limit of an appropriate Bayesian field theory. I also show that Bayesian field theory estimation can be performed without imposing any boundary conditions on candidate densities, and that the infinite smoothness limit of these theories recovers the most common types of maximum entropy estimates. Bayesian field theory thus provides a natural test of the maximum entropy null hypothesis and, furthermore, returns an alternative (lower entropy) density estimate when the maximum entropy hypothesis is falsified. The computations necessary for this approach can be performed rapidly for one-dimensional data, and software for doing this is provided.

  2. Unification of field theory and maximum entropy methods for learning probability densities.

    Science.gov (United States)

    Kinney, Justin B

    2015-09-01

    The need to estimate smooth probability distributions (a.k.a. probability densities) from finite sampled data is ubiquitous in science. Many approaches to this problem have been described, but none is yet regarded as providing a definitive solution. Maximum entropy estimation and Bayesian field theory are two such approaches. Both have origins in statistical physics, but the relationship between them has remained unclear. Here I unify these two methods by showing that every maximum entropy density estimate can be recovered in the infinite smoothness limit of an appropriate Bayesian field theory. I also show that Bayesian field theory estimation can be performed without imposing any boundary conditions on candidate densities, and that the infinite smoothness limit of these theories recovers the most common types of maximum entropy estimates. Bayesian field theory thus provides a natural test of the maximum entropy null hypothesis and, furthermore, returns an alternative (lower entropy) density estimate when the maximum entropy hypothesis is falsified. The computations necessary for this approach can be performed rapidly for one-dimensional data, and software for doing this is provided.

  3. Time-dependent density functional theory of open quantum systems in the linear-response regime.

    Science.gov (United States)

    Tempel, David G; Watson, Mark A; Olivares-Amaya, Roberto; Aspuru-Guzik, Alán

    2011-02-21

    Time-dependent density functional theory (TDDFT) has recently been extended to describe many-body open quantum systems evolving under nonunitary dynamics according to a quantum master equation. In the master equation approach, electronic excitation spectra are broadened and shifted due to relaxation and dephasing of the electronic degrees of freedom by the surrounding environment. In this paper, we develop a formulation of TDDFT linear-response theory (LR-TDDFT) for many-body electronic systems evolving under a master equation, yielding broadened excitation spectra. This is done by mapping an interacting open quantum system onto a noninteracting open Kohn-Sham system yielding the correct nonequilibrium density evolution. A pseudoeigenvalue equation analogous to the Casida equations of the usual LR-TDDFT is derived for the Redfield master equation, yielding complex energies and Lamb shifts. As a simple demonstration, we calculate the spectrum of a C(2 +) atom including natural linewidths, by treating the electromagnetic field vacuum as a photon bath. The performance of an adiabatic exchange-correlation kernel is analyzed and a first-order frequency-dependent correction to the bare Kohn-Sham linewidth based on the Görling-Levy perturbation theory is calculated.

  4. Transition matrices and orbitals from reduced density matrix theory

    Energy Technology Data Exchange (ETDEWEB)

    Etienne, Thibaud [Université de Lorraine – Nancy, Théorie-Modélisation-Simulation, SRSMC, Boulevard des Aiguillettes 54506, Vandoeuvre-lès-Nancy (France); CNRS, Théorie-Modélisation-Simulation, SRSMC, Boulevard des Aiguillettes 54506, Vandoeuvre-lès-Nancy (France); Unité de Chimie Physique Théorique et Structurale, Université de Namur, Rue de Bruxelles 61, 5000 Namur (Belgium)

    2015-06-28

    In this contribution, we report two different methodologies for characterizing the electronic structure reorganization occurring when a chromophore undergoes an electronic transition. For the first method, we start by setting the theoretical background necessary to the reinterpretation through simple tensor analysis of (i) the transition density matrix and (ii) the natural transition orbitals in the scope of reduced density matrix theory. This novel interpretation is made more clear thanks to a short compendium of the one-particle reduced density matrix theory in a Fock space. The formalism is further applied to two different classes of excited states calculation methods, both requiring a single-determinant reference, that express an excited state as a hole-particle mono-excited configurations expansion, to which particle-hole correlation is coupled (time-dependent Hartree-Fock/time-dependent density functional theory) or not (configuration interaction single/Tamm-Dancoff approximation). For the second methodology presented in this paper, we introduce a novel and complementary concept related to electronic transitions with the canonical transition density matrix and the canonical transition orbitals. Their expression actually reflects the electronic cloud polarisation in the orbital space with a decomposition based on the actual contribution of one-particle excitations from occupied canonical orbitals to virtual ones. This approach validates our novel interpretation of the transition density matrix elements in terms of the Euclidean norm of elementary transition vectors in a linear tensor space. A proper use of these new concepts leads to the conclusion that despite the different principles underlying their construction, they provide two equivalent excited states topological analyses. This connexion is evidenced through simple illustrations of (in)organic dyes electronic transitions analysis.

  5. Research on high energy density plasmas and applications

    International Nuclear Information System (INIS)

    1999-01-01

    Recently, technologies on lasers, accelerators, and pulse power machines have been significantly advanced and input power density covers the intensity range from 10 10 W/cm 2 to higher than 10 20 W/cm 2 . As the results, high pressure gas and solid targets can be heated up to very high temperature to create hot dense plasmas which have never appeared on the earth. The high energy density plasmas opened up new research fields such as inertial confinement fusion, high brightness X-ray radiation sources, interiors of galactic nucleus,supernova, stars and planets, ultra high pressure condensed matter physics, plasma particle accelerator, X-ray laser, and so on. Furthermore, since these fields are intimately connected with various industrial sciences and technologies, the high energy density plasma is now studied in industries, government institutions, and so on. This special issue of the Journal of Plasma Physics and Nuclear Fusion Research reviews the high energy density plasma science for the comprehensive understanding of such new fields. In May, 1998, the review committee for investigating the present status and the future prospects of high energy density plasma science was established in the Japan Society of Plasma Science and Nuclear Fusion Research. We held three committee meetings to discuss present status and critical issues of research items related to high energy density plasmas. This special issue summarizes the understandings of the committee. This special issue consists of four chapters: They are Chapter 1: Physics important in the high energy density plasmas, Chapter 2: Technologies related to the plasma generation; drivers such as lasers, pulse power machines, particle beams and fabrication of various targets, Chapter 3: Plasma diagnostics important in high energy density plasma experiments, Chapter 4: A variety of applications of high energy density plasmas; X-ray radiation, particle acceleration, inertial confinement fusion, laboratory astrophysics

  6. Density functional theory study on the ionic liquid pyridinium hydrogen sulfate

    Science.gov (United States)

    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.

  7. Dietary energy density: Applying behavioural science to weight management.

    Science.gov (United States)

    Rolls, B J

    2017-09-01

    Studies conducted by behavioural scientists show that energy density (kcal/g) provides effective guidance for healthy food choices to control intake and promote satiety. Energy density depends upon a number of dietary components, especially water (0 kcal/g) and fat (9 kcal/g). Increasing the proportion of water or water-rich ingredients, such as vegetables or fruit, lowers a food's energy density. A number of studies show that when the energy density of the diet is reduced, both adults and children spontaneously decrease their ad libitum energy intake. Other studies show that consuming a large volume of a low-energy-dense food such as soup, salad, or fruit as a first course preload can enhance satiety and reduce overall energy intake at a meal. Current evidence suggests that energy density influences intake through a complex interplay of cognitive, sensory, gastrointestinal, hormonal and neural influences. Other studies that focus on practical applications show how the strategic incorporation of foods lower in energy density into the diet allows people to eat satisfying portions while improving dietary patterns. This review discusses studies that have led to greater understanding of the importance of energy density for food intake regulation and weight management.

  8. Sensing behavior of acetone vapors on TiO_2 nanostructures — application of density functional theory

    Directory of Open Access Journals (Sweden)

    V. Nagarajan

    2017-12-01

    Full Text Available The electronic properties of TiO_2 nanostructure are explored using density functional theory. The adsorption properties of acetone on TiO_2 nanostructure are studied in terms of adsorption energy, average energy gap variation and Mulliken charge transfer. The density of states spectrum and the band structure clearly reveals the adsorption of acetone on TiO_2 nanostructures. The variation in the energy gap and changes in the density of charge are observed upon adsorption of acetone on n-type TiO_2 base material. The results of DOS spectrum reveal that the transfer of electrons takes place between acetone vapor and TiO_2 base material. The findings show that the adsorption property of acetone is more favorable on TiO_2 nanostructure. Suitable adsorption sites of acetone on TiO_2 nanostructure are identified at atomistic level. From the results, it is confirmed that TiO_2 nanostructure can be efficiently utilized as a sensing element for the detection of acetone vapor in a mixed environment.

  9. Late forming dark matter in theories of neutrino dark energy

    International Nuclear Information System (INIS)

    Das, Subinoy; Weiner, Neal

    2011-01-01

    We study the possibility of late forming dark matter, where a scalar field, previously trapped in a metastable state by thermal or finite density effects, goes through a phase transition near the era matter-radiation equality and begins to oscillate about its true minimum. Such a theory is motivated generally if the dark energy is of a similar form, but has not yet made the transition to dark matter, and, in particular, arises automatically in recently considered theories of neutrino dark energy. If such a field comprises the present dark matter, the matter power spectrum typically shows a sharp break at small, presently nonlinear scales, below which power is highly suppressed and previously contained acoustic oscillations. If, instead, such a field forms a subdominant component of the total dark matter, such acoustic oscillations may imprint themselves in the linear regime.

  10. Why Density Dependent Propulsion?

    Science.gov (United States)

    Robertson, Glen A.

    2011-01-01

    In 2004 Khoury and Weltman produced a density dependent cosmology theory they call the Chameleon, as at its nature, it is hidden within known physics. The Chameleon theory has implications to dark matter/energy with universe acceleration properties, which implies a new force mechanism with ties to the far and local density environment. In this paper, the Chameleon Density Model is discussed in terms of propulsion toward new propellant-less engineering methods.

  11. Oenin and Quercetin Copigmentation: Highlights From Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Yunkui Li

    2018-06-01

    Full Text Available Making use of anthocyanin copigmentation, it is possible to effectively improve color quality and stability of red wines and other foods. This can be done by selecting strong copigments, but a 1-fold experimental screening usually entails a high cost and a low efficiency. The aim of this work is to show how a theoretical model based on density functional theory can be useful for an accurate and rapid prediction of copigmentation ability of a copigment. The present study, concerning the copigmentation between oenin and quercetin under the framework of implicit solvent, indicates that, in these conditions, the intermolecular hydrogen bonds play an important role in the system stabilization. The dispersion interaction slightly affects the structure, energies and UV-Vis spectral properties of the copigmentation complex.

  12. Rare earth substitutional impurities in germanium: A hybrid density functional theory study

    Science.gov (United States)

    Igumbor, E.; Omotoso, E.; Tunhuma, S. M.; Danga, H. T.; Meyer, W. E.

    2017-10-01

    The Heyd, Scuseria, and Ernzerhof (HSE06) hybrid functional by means of density functional theory has been used to model the electronic and structural properties of rare earth (RE) substitutional impurities in germanium (REGe) . The formation and charge state transition energies for the REGe (RE = Ce, Pr, Er and Eu) were calculated. The energy of formation for the neutral charge state of the REGe lies between -0.14 and 3.13 eV. The formation energy result shows that the Pr dopant in Ge (PrGe) has the lowest formation energy of -0.14 eV, and is most energetically favourable under equilibrium conditions. The REGe induced charge state transition levels within the band gap of Ge. Shallow acceptor levels were induced by both the Eu (EuGe) and Pr (PrGe) dopants in Ge. The CeGe and ErGe exhibited properties of negative-U ordering with effective-U values of -0.85 and -1.07 eV, respectively.

  13. Mechanical confinement for improved energy storage density in BNT-BT-KNN lead-free ceramic capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chauhan, Aditya; Patel, Satyanarayan; Vaish, Rahul, E-mail: rahul@iitmandi.ac.in [School of Engineering, Indian Institute of Technology Mandi, 175 001 (India)

    2014-08-15

    With the advent of modern power electronics, embedded circuits and non-conventional energy harvesting, the need for high performance capacitors is bound to become indispensible. The current state-of-art employs ferroelectric ceramics and linear dielectrics for solid state capacitance. However, lead-free ferroelectric ceramics propose to offer significant improvement in the field of electrical energy storage owing to their high discharge efficiency and energy storage density. In this regards, the authors have investigated the effects of compressive stress as a means of improving the energy storage density of lead-free ferroelectric ceramics. The energy storage density of 0.91(Bi{sub 0.5}Na{sub 0.5})TiO{sub 3}-0.07BaTiO{sub 3}-0.02(K{sub 0.5}Na{sub 0.5})NbO{sub 3} ferroelectric bulk ceramic was analyzed as a function of varying levels of compressive stress and operational temperature .It was observed that a peak energy density of 387 mJ.cm{sup -3} was obtained at 100 MPa applied stress (25{sup o}C). While a maximum energy density of 568 mJ.cm{sup -3} was obtained for the same stress at 80{sup o}C. These values are indicative of a significant, 25% and 84%, improvement in the value of stored energy compared to an unloaded material. Additionally, material's discharge efficiency has also been discussed as a function of operational parameters. The observed phenomenon has been explained on the basis of field induced structural transition and competitive domain switching theory.

  14. Total energy calculations from self-energy models

    International Nuclear Information System (INIS)

    Sanchez-Friera, P.

    2001-06-01

    Density-functional theory is a powerful method to calculate total energies of large systems of interacting electrons. The usefulness of this method, however, is limited by the fact that an approximation is required for the exchange-correlation energy. Currently used approximations (LDA and GGA) are not sufficiently accurate in many physical problems, as for instance the study of chemical reactions. It has been shown that exchange-correlation effects can be accurately described via the self-energy operator in the context of many-body perturbation theory. This is, however, a computationally very demanding approach. In this thesis a new scheme for calculating total energies is proposed, which combines elements from many-body perturbation theory and density-functional theory. The exchange-correlation energy functional is built from a simplified model of the self-energy, that nevertheless retains the main features of the exact operator. The model is built in such way that the computational effort is not significantly increased with respect to that required in a typical density-functional theory calculation. (author)

  15. Decay of autoionizing states in time-dependent density functional and reduced density matrix functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Varun; Brics, Martins; Bauer, Dieter [Institut fuer Physik, Universitaet Rostock, 18051 Rostock (Germany)

    2013-07-01

    Autoionizing states are inaccessible to time-dependent density functional theory (TDDFT) using known, adiabatic Kohn-Sham (KS) potentials. We determine the exact KS potential for a numerically exactly solvable model Helium atom interacting with a laser field that is populating an autoionizing state. The exact single-particle density of the population in the autoionizing state corresponds to that of the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose height and width allows for the density to tunnel out and decay with the same rate as in the ab initio time-dependent Schroedinger calculation. However, devising a useful exchange-correlation potential that is capable of governing such a scenario in general and in more complex systems is hopeless. As an improvement over TDDFT, time-dependent reduced density matrix functional theory has been proposed. We are able to obtain for the above described autoionization process the exact time-dependent natural orbitals (i.e., the eigenfunctions of the exact, time-dependent one-body reduced density matrix) and study the potentials that appear in the equations of motion for the natural orbitals and the structure of the two-body density matrix expanded in them.

  16. Effective theory for heavy quark QCD at finite temperature and density with stochastic quantization

    Energy Technology Data Exchange (ETDEWEB)

    Neuman, Mathias

    2015-07-01

    corrections are sufficient to reach β∼6, which translates to lattice spacings down to a ∼0.1 fm. Furthermore we determined the convergence in κ by simulating the action truncated at different orders. Due to the three dimensional nature of our theory the convergence depends on the temporal extent N{sub τ}. We concluded that our theory converges well up to values of at least (N{sub τ}κ{sup 2})/(3) ∼ 0.04. Both results can be improved by deriving further corrections. In chapter 5 we presented the numerical treatment of our theory. While the sign problem is still present, it is mild compared to the case of full LQCD. This allowed us to use both Monte-Carlo with reweighting and stochastic quantization in order to crosscheck results. This confirms the validity of stochastic quantization for our theory, which is our method of choice since, in contrast to reweighting, it is not limited to small lattice volumes. We presented results for two parameter regions, the region of large density and low temperatures, and the region of high temperature and low density. For the cold dense region we calculated several thermodynamical quantities and performed continuum extrapolations. This allows us to make a connection to continuum QCD, although in a parameter region far away from the physical point. The results show the onset from the vacuum to the region of finite density, displaying Silver Blaze behavior. We furthermore demonstrated the existence of a finite binding energy between baryonic states, which in the continuum are responsible for the formation of nuclear matter. Although experiments show the transition from the vacuum to the region of finite density to be of first order for low enough temperatures, the convergence region of our theory is not large enough to reproduce this. Nevertheless, we where able to find signals for a change from a crossover to a true phase transition when we left this region. This demonstrates that our theory is in principle able to reproduce the

  17. Comparison of exact-exchange calculations for solids in current-spin-density- and spin-density-functional theory

    DEFF Research Database (Denmark)

    Sharma, S.; Pittalis, S.; Kurth, S.

    2007-01-01

    The relative merits of current-spin-density- and spin-density-functional theory are investigated for solids treated within the exact-exchange-only approximation. Spin-orbit splittings and orbital magnetic moments are determined at zero external magnetic field. We find that for magnetic (Fe, Co......, and Ni) and nonmagnetic (Si and Ge) solids, the exact-exchange current-spin-density functional approach does not significantly improve the accuracy of the corresponding spin-density functional results....

  18. Comparison of three methods to reduce energy density. Effects on daily energy intake.

    Science.gov (United States)

    Williams, Rachel A; Roe, Liane S; Rolls, Barbara J

    2013-07-01

    Reductions in food energy density can decrease energy intake, but it is not known if the effects depend on the way that energy density is reduced. We investigated whether three methods of reducing energy density (decreasing fat, increasing fruit and vegetables, and adding water) differed in their effects on energy intake across the day. In a crossover design, 59 adults ate breakfast, lunch, and dinner in the laboratory once a week for 4 weeks. Across conditions, the entrées were either standard in energy density or were reduced in energy density by 20% using one of the three methods. Each meal included a manipulated entrée along with unmanipulated side dishes, and all foods were consumed ad libitum. Reducing the energy density of entrées significantly decreased daily energy intake compared to standard entrées (mean intake 2667 ± 77 kcal/day; 11,166 ± 322 kJ/day). The mean decrease was 396 ± 44 kcal/day (1658 ± 184 kJ/day) when fat was reduced, 308 ± 41 kcal/day (1290 ± 172 kJ/day) when fruit and vegetables were increased, and 230 ± 35 kcal/day (963 ± 147 kJ/day) when water was added. Daily energy intake was lower when fat was decreased compared to the other methods. These findings indicate that a variety of diet compositions can be recommended to reduce overall dietary energy density in order to moderate energy intake. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Lattice simulations of QCD-like theories at finite baryon density

    Energy Technology Data Exchange (ETDEWEB)

    Scior, Philipp Friedrich

    2016-07-13

    The exploration of the phase diagram of quantum chromodynamics (QCD) is of great importance to describe e.g. the properties of neutron stars or heavy-ion collisions. Due to the sign problem of lattice QCD at finite chemical potential we need effective theories to study QCD at finite density. Here, we use a three-dimensional Polyakov-loop theory to study the phase diagrams of QCD-like theories. In particular, we investigate the heavy quark limit of the QCD-like theories where the effective theory can be derived from the full theory by a combined strong coupling and hopping expansion. This expansion can be systematically improved order by order. Since there is no sign problem for the QCD-like theories we consider, we can compare our results to data from lattice calculations of the full theories to make qualitative and quantitative statements of the effective theory's validity. We start by deriving the effective theory up to next-to-next-to leading-order, in particular for two-color and G{sub 2}-QCD where replace the three colors in QCD with only two colors or respectively replace the gauge group SU(3) of QCD with G{sub 2}. We will then apply the effective theory at finite temperature mainly to test the theory and the implementation but also to make some predictions for the deconfinement phase transition in G{sub 2} Yang-Mills theory. Finally, we turn our attention to the cold and dense regime of the phase diagram where we observe a sharp increase of the baryon density with the quark chemical potential μ, when μ reaches half the diquark mass. At vanishing temperature this is expected to happen in a quantum phase transition with Bose-Einstein-condensation of diquarks. In contrast to the liquid-gas transition in QCD, the phase transition to the Bose-Einstein condensate is continuous. We find evidence that the effective theories for heavy quarks are able to describe the qualitative difference between first and second order phase transitions. For even higher μ we

  20. Lattice simulations of QCD-like theories at finite baryon density

    International Nuclear Information System (INIS)

    Scior, Philipp Friedrich

    2016-01-01

    The exploration of the phase diagram of quantum chromodynamics (QCD) is of great importance to describe e.g. the properties of neutron stars or heavy-ion collisions. Due to the sign problem of lattice QCD at finite chemical potential we need effective theories to study QCD at finite density. Here, we use a three-dimensional Polyakov-loop theory to study the phase diagrams of QCD-like theories. In particular, we investigate the heavy quark limit of the QCD-like theories where the effective theory can be derived from the full theory by a combined strong coupling and hopping expansion. This expansion can be systematically improved order by order. Since there is no sign problem for the QCD-like theories we consider, we can compare our results to data from lattice calculations of the full theories to make qualitative and quantitative statements of the effective theory's validity. We start by deriving the effective theory up to next-to-next-to leading-order, in particular for two-color and G_2-QCD where replace the three colors in QCD with only two colors or respectively replace the gauge group SU(3) of QCD with G_2. We will then apply the effective theory at finite temperature mainly to test the theory and the implementation but also to make some predictions for the deconfinement phase transition in G_2 Yang-Mills theory. Finally, we turn our attention to the cold and dense regime of the phase diagram where we observe a sharp increase of the baryon density with the quark chemical potential μ, when μ reaches half the diquark mass. At vanishing temperature this is expected to happen in a quantum phase transition with Bose-Einstein-condensation of diquarks. In contrast to the liquid-gas transition in QCD, the phase transition to the Bose-Einstein condensate is continuous. We find evidence that the effective theories for heavy quarks are able to describe the qualitative difference between first and second order phase transitions. For even higher μ we find the rise of the

  1. Density-functional theory of atoms and molecules

    CERN Document Server

    Parr, Robert G

    1995-01-01

    Provides an account of the fundamental principles of the density-functional theory of the electronic structure of matter and its applications to atoms and molecules. This book contains a discussion of the chemical potential and its derivatives. It is intended for physicists, chemists, and advanced students in chemistry.

  2. Six Decades of Spiral Density Wave Theory

    Science.gov (United States)

    Shu, Frank H.

    2016-09-01

    The theory of spiral density waves had its origin approximately six decades ago in an attempt to reconcile the winding dilemma of material spiral arms in flattened disk galaxies. We begin with the earliest calculations of linear and nonlinear spiral density waves in disk galaxies, in which the hypothesis of quasi-stationary spiral structure (QSSS) plays a central role. The earliest success was the prediction of the nonlinear compression of the interstellar medium and its embedded magnetic field; the earliest failure, seemingly, was not detecting color gradients associated with the migration of OB stars whose formation is triggered downstream from the spiral shock front. We give the reasons for this apparent failure with an update on the current status of the problem of OB star formation, including its relationship to the feathering substructure of galactic spiral arms. Infrared images can show two-armed, grand design spirals, even when the optical and UV images show flocculent structures. We suggest how the nonlinear response of the interstellar gas, coupled with overlapping subharmonic resonances, might introduce chaotic behavior in the dynamics of the interstellar medium and Population I objects, even though the underlying forces to which they are subject are regular. We then move to a discussion of resonantly forced spiral density waves in a planetary ring and their relationship to the ideas of disk truncation, and the shepherding of narrow rings by satellites orbiting nearby. The back reaction of the rings on the satellites led to the prediction of planet migration in protoplanetary disks, which has had widespread application in the exploding data sets concerning hot Jupiters and extrasolar planetary systems. We then return to the issue of global normal modes in the stellar disk of spiral galaxies and its relationship to the QSSS hypothesis, where the central theoretical concepts involve waves with negative and positive surface densities of energy and angular

  3. Coupled cluster and density functional theory calculations of atomic hydrogen chemisorption on pyrene and coronene as model systems for graphene hydrogenation.

    Science.gov (United States)

    Wang, Ying; Qian, Hu-Jun; Morokuma, Keiji; Irle, Stephan

    2012-07-05

    Ab initio coupled cluster and density functional theory studies of atomic hydrogen addition to the central region of pyrene and coronene as molecular models for graphene hydrogenation were performed. Fully relaxed potential energy curves (PECs) were computed at the spin-unrestricted B3LYP/cc-pVDZ level of theory for the atomic hydrogen attack of a center carbon atom (site A), the midpoint of a neighboring carbon bond (site B), and the center of a central hexagon (site C). Using the B3LYP/cc-pVDZ PEC geometries, we evaluated energies at the PBE density functional, as well as ab initio restricted open-shell ROMP2, ROCCSD, and ROCCSD(T) levels of theory, employing cc-pVDZ and cc-pVTZ basis sets, and performed a G2MS extrapolation to the ROCCSD(T)/cc-pVTZ level of theory. In agreement with earlier studies, we find that only site A attack leads to chemisorption. The G2MS entrance channel barrier heights, binding energies, and PEC profiles are found to agree well with a recent ab initio multireference wave function theory study (Bonfanti et al. J. Chem. Phys.2011, 135, 164701), indicating that single-reference open-shell methods including B3LYP are sufficient for the theoretical treatment of the interaction of graphene with a single hydrogen atom.

  4. Configurational forces in electronic structure calculations using Kohn-Sham density functional theory

    Science.gov (United States)

    Motamarri, Phani; Gavini, Vikram

    2018-04-01

    We derive the expressions for configurational forces in Kohn-Sham density functional theory, which correspond to the generalized variational force computed as the derivative of the Kohn-Sham energy functional with respect to the position of a material point x . These configurational forces that result from the inner variations of the Kohn-Sham energy functional provide a unified framework to compute atomic forces as well as stress tensor for geometry optimization. Importantly, owing to the variational nature of the formulation, these configurational forces inherently account for the Pulay corrections. The formulation presented in this work treats both pseudopotential and all-electron calculations in a single framework, and employs a local variational real-space formulation of Kohn-Sham density functional theory (DFT) expressed in terms of the nonorthogonal wave functions that is amenable to reduced-order scaling techniques. We demonstrate the accuracy and performance of the proposed configurational force approach on benchmark all-electron and pseudopotential calculations conducted using higher-order finite-element discretization. To this end, we examine the rates of convergence of the finite-element discretization in the computed forces and stresses for various materials systems, and, further, verify the accuracy from finite differencing the energy. Wherever applicable, we also compare the forces and stresses with those obtained from Kohn-Sham DFT calculations employing plane-wave basis (pseudopotential calculations) and Gaussian basis (all-electron calculations). Finally, we verify the accuracy of the forces on large materials systems involving a metallic aluminum nanocluster containing 666 atoms and an alkane chain containing 902 atoms, where the Kohn-Sham electronic ground state is computed using a reduced-order scaling subspace projection technique [P. Motamarri and V. Gavini, Phys. Rev. B 90, 115127 (2014), 10.1103/PhysRevB.90.115127].

  5. Dissipation Effects in Schrödinger and Quantal Density Functional Theories of Electrons in an Electromagnetic Field

    Directory of Open Access Journals (Sweden)

    Xiao-Yin Pan

    2018-03-01

    Full Text Available Dissipative effects arise in an electronic system when it interacts with a time-dependent environment. Here, the Schrödinger theory of electrons in an electromagnetic field including dissipative effects is described from a new perspective. Dissipation is accounted for via the effective Hamiltonian approach in which the electron mass is time-dependent. The perspective is that of the individual electron: the corresponding equation of motion for the electron or time-dependent differential virial theorem—the ‘Quantal Newtonian’ second law—is derived. According to the law, each electron experiences an external field comprised of a binding electric field, the Lorentz field, and the electromagnetic field. In addition, there is an internal field whose components are representative of electron correlations due to the Pauli exclusion principle and Coulomb repulsion, kinetic effects, and density. There is also an internal contribution due to the magnetic field. The response of the electron is governed by the current density field in which a damping coefficient appears. The law leads to further insights into Schrödinger theory, and in particular the intrinsic self-consistent nature of the Schrödinger equation. It is proved that in the presence of dissipative effects, the basic variables (gauge-invariant properties, knowledge of which determines the Hamiltonian are the density and physical current density. Finally, a local effective potential theory of dissipative systems—quantal density functional theory (QDFT—is developed. This constitutes the mapping from the interacting dissipative electronic system to one of noninteracting fermions possessing the same dissipation and basic variables. Attributes of QDFT are the separation of the electron correlations due to the Pauli exclusion principle and Coulomb repulsion, and the determination of the correlation contributions to the kinetic energy. Hence, Schrödinger theory in conjunction with QDFT

  6. Self-interaction corrections in density functional theory

    International Nuclear Information System (INIS)

    Tsuneda, Takao; Hirao, Kimihiko

    2014-01-01

    Self-interaction corrections for Kohn-Sham density functional theory are reviewed for their physical meanings, formulations, and applications. The self-interaction corrections get rid of the self-interaction error, which is the sum of the Coulomb and exchange self-interactions that remains because of the use of an approximate exchange functional. The most frequently used self-interaction correction is the Perdew-Zunger correction. However, this correction leads to instabilities in the electronic state calculations of molecules. To avoid these instabilities, several self-interaction corrections have been developed on the basis of the characteristic behaviors of self-interacting electrons, which have no two-electron interactions. These include the von Weizsäcker kinetic energy and long-range (far-from-nucleus) asymptotic correction. Applications of self-interaction corrections have shown that the self-interaction error has a serious effect on the states of core electrons, but it has a smaller than expected effect on valence electrons. This finding is supported by the fact that the distribution of self-interacting electrons indicates that they are near atomic nuclei rather than in chemical bonds

  7. Rational Density Functional Selection Using Game Theory.

    Science.gov (United States)

    McAnanama-Brereton, Suzanne; Waller, Mark P

    2018-01-22

    Theoretical chemistry has a paradox of choice due to the availability of a myriad of density functionals and basis sets. Traditionally, a particular density functional is chosen on the basis of the level of user expertise (i.e., subjective experiences). Herein we circumvent the user-centric selection procedure by describing a novel approach for objectively selecting a particular functional for a given application. We achieve this by employing game theory to identify optimal functional/basis set combinations. A three-player (accuracy, complexity, and similarity) game is devised, through which Nash equilibrium solutions can be obtained. This approach has the advantage that results can be systematically improved by enlarging the underlying knowledge base, and the deterministic selection procedure mathematically justifies the density functional and basis set selections.

  8. General approach for solving the density gradient theory in the interfacial tension calculations

    DEFF Research Database (Denmark)

    Liang, Xiaodong; Michelsen, Michael Locht

    2017-01-01

    Within the framework of the density gradient theory, the interfacial tension can be calculated by finding the density profiles that minimize an integral of two terms over the system of infinite width. It is found that the two integrands exhibit a constant difference along the interface for a finite...... property evaluations compared to other methods. The performance of the algorithm with recommended parameters is analyzed for various systems, and the efficiency is further compared with the geometric-mean density gradient theory, which only needs to solve nonlinear algebraic equations. The results show...... that the algorithm is only 5-10 times less efficient than solving the geometric-mean density gradient theory....

  9. A classical density functional theory of ionic liquids.

    Science.gov (United States)

    Forsman, Jan; Woodward, Clifford E; Trulsson, Martin

    2011-04-28

    We present a simple, classical density functional approach to the study of simple models of room temperature ionic liquids. Dispersion attractions as well as ion correlation effects and excluded volume packing are taken into account. The oligomeric structure, common to many ionic liquid molecules, is handled by a polymer density functional treatment. The theory is evaluated by comparisons with simulations, with an emphasis on the differential capacitance, an experimentally measurable quantity of significant practical interest.

  10. Instanton density in a theory with massless quarks

    International Nuclear Information System (INIS)

    Shifman, M.A.; Vainshtein, A.I.; Zakharov, V.I.

    1979-01-01

    Effect of the complex structure of the QCD vacuum on the density of small-sized instantons is discussed. The method which allows to account for this effect of vacuum quark and gluon condensate is developed. Evaluation of the instanton density is given in the framework of the theory with one, two or three massless quarks. The results of the paper are presented for the cases of SU(2) and SU(3) color groups

  11. Thermodynamic and kinetic properties of hydrogen defect pairs in SrTiO3 from density functional theory

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan

    2011-01-01

    A density functional theory investigation of the thermodynamic and kinetic properties of hydrogen–hydrogen defect interactions in the cubic SrTiO3 perovskite is presented. We find a net attraction between two hydrogen atoms with an optimal separation of ∼2.3 Å. The energy gain is ca. 0.33 eV comp...

  12. Doping strategies to control A-centres in silicon: Insights from hybrid density functional theory

    KAUST Repository

    Wang, Hao; Chroneos, Alexander I.; Londos, Charalampos A.; Sgourou, Efstratia N.; Schwingenschlö gl, Udo

    2014-01-01

    Hybrid density functional theory is used to gain insights into the interaction of intrinsic vacancies (V) and oxygen-vacancy pairs (VO, known as A-centres) with the dopants (D) germanium (Ge), tin (Sn), and lead (Pb) in silicon (Si). We determine the structures as well as binding and formation energies of the DVO and DV complexes. The results are discussed in terms of the density of states and in view of the potential of isovalent doping to control A-centres in Si. We argue that doping with Sn is the most efficient isovalent doping strategy to suppress A-centres by the formation of SnVO complexes, as these are charge neutral and strongly bound. © 2014 the Owner Societies.

  13. Quantum Drude friction for time-dependent density functional theory

    Science.gov (United States)

    Neuhauser, Daniel; Lopata, Kenneth

    2008-10-01

    way to very simple finite grid description of scattering and multistage conductance using time-dependent density functional theory away from the linear regime, just as absorbing potentials and self-energies are useful for noninteracting systems and leads.

  14. Comparison of three methods to reduce energy density: effects on daily energy intake

    OpenAIRE

    Williams, Rachel A.; Roe, Liane S.; Rolls, Barbara J.

    2013-01-01

    Reductions in food energy density can decrease energy intake, but it is not known if the effects depend on the way that energy density is reduced. We investigated whether three methods of reducing energy density (decreasing fat, increasing fruit and vegetables, and adding water) differed in their effects on energy intake across the day. In a crossover design, 59 adults ate breakfast, lunch, and dinner in the laboratory once a week for four weeks. Across conditions, the entrées were either sta...

  15. Interface structure and stabilization of metastable B2-FeSi/Si(111) studied with low-energy electron diffraction and density functional theory

    International Nuclear Information System (INIS)

    Walter, S; Blobner, F; Krause, M; Mueller, S; Heinz, K; Starke, U

    2003-01-01

    We present a combined experimental and theoretical investigation of the interface between a B2-type FeSi film and Si(111). Using an ultra-thin B2-FeSi film grown on Si(111), the interface is still reached by electrons, so quantitative low-energy electron diffraction (LEED) could be applied to determine the bonding geometry experimentally. As a result, the local configuration at the shallow buried interface is characterized by near-substrate Fe atoms being 8-fold coordinated to Si atoms and by the silicide unit cell being rotated by 180 deg. with respect to the Si unit cell (B8 configuration). The interface energetics were explored by total-energy calculations using density functional theory (DFT). The B8-type interface proves to be the most stable one, consistent with the experimental findings. The atomic geometries obtained experimentally (LEED) and theoretically (DFT) agree within the limits of errors. Additionally, the calculations explain the stabilization of the B2 phase, which is unstable as bulk material: the analysis of the elastic behaviour reveals a reversed energy hierarchy of B2 and the bulk stable B20 phase when epitaxial growth on Si(111) is enforced

  16. High-Power-Density, High-Energy-Density Fluorinated Graphene for Primary Lithium Batteries

    Directory of Open Access Journals (Sweden)

    Guiming Zhong

    2018-03-01

    Full Text Available Li/CFx is one of the highest-energy-density primary batteries; however, poor rate capability hinders its practical applications in high-power devices. Here we report a preparation of fluorinated graphene (GFx with superior performance through a direct gas fluorination method. We find that the so-called “semi-ionic” C-F bond content in all C-F bonds presents a more critical impact on rate performance of the GFx in comparison with sp2 C content in the GFx, morphology, structure, and specific surface area of the materials. The rate capability remains excellent before the semi-ionic C-F bond proportion in the GFx decreases. Thus, by optimizing semi-ionic C-F content in our GFx, we obtain the optimal x of 0.8, with which the GF0.8 exhibits a very high energy density of 1,073 Wh kg−1 and an excellent power density of 21,460 W kg−1 at a high current density of 10 A g−1. More importantly, our approach opens a new avenue to obtain fluorinated carbon with high energy densities without compromising high power densities.

  17. Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme.

    Science.gov (United States)

    Li, Shaohong L; Truhlar, Donald G

    2015-07-14

    Time-dependent density functional theory (TDDFT) with conventional local and hybrid functionals such as the local and hybrid generalized gradient approximations (GGA) seriously underestimates the excitation energies of Rydberg states, which limits its usefulness for applications such as spectroscopy and photochemistry. We present here a scheme that modifies the exchange-enhancement factor to improve GGA functionals for Rydberg excitations within the TDDFT framework while retaining their accuracy for valence excitations and for the thermochemical energetics calculated by ground-state density functional theory. The scheme is applied to a popular hybrid GGA functional and tested on data sets of valence and Rydberg excitations and atomization energies, and the results are encouraging. The scheme is simple and flexible. It can be used to correct existing functionals, and it can also be used as a strategy for the development of new functionals.

  18. Density functional theory study of Al-doped hematite

    International Nuclear Information System (INIS)

    Rivera, Richard; Stashans, Arvids; Piedra, Lorena; Pinto, Henry P

    2012-01-01

    Using first-principles density functional theory calculations within the generalized gradient approximation (GGA) as well as the GGA+U approach, we study Al-doped α-Fe 2 O 3 crystals. Structural, electronic, magnetic and optical properties due to impurity incorporation have been investigated and discussed in detail. Atomic displacements and Bader charges on atoms have been computed, showing that Al dopant converts the chemical bonding in its neighbourhood into a more ionic one. This work enhances our knowledge about how a crystalline lattice reacts in the presence of an Al impurity. It was found that Al incorporation produces some local changes in the band structure of the material without the creation of local energy levels within the band gap. The results provide evidence for changes in the magnetic moments in the vicinity of a defect, which means that α-Fe 2 O 3 doped with aluminum might not act as an antiferromagnetic substance.

  19. Nitrotyrosine adsorption on defective graphene: A density functional theory study

    Science.gov (United States)

    Majidi, R.; Karami, A. R.

    2015-06-01

    We have applied density functional theory to study adsorption of nitrotyrosine on perfect and defective graphene sheets. The graphene sheets with Stone-Wales (SW) defect, pentagon-nonagon (5-9) single vacancy, and pentagon-octagon-pentagon (5-8-5) double vacancy were considered. The calculations of adsorption energy showed that nitrotyrosine presents a more strong interaction with defective graphene rather than with perfect graphene sheet. The order of interaction strength is: SW>5-9>5-8-5>perfect graphene. It is found that the electronic properties of perfect and defective graphene are sensitive to the presence of nitrotyrosine. Hence, graphene sheets can be considered as a good sensor for detection of nitrotyrosine molecule which is observed in connection with several human disorders, such as Parkinson's and Alzheimer's disease.

  20. Corrections to the density-functional theory electronic spectrum: Copper phthalocyanine

    DEFF Research Database (Denmark)

    Vazquez, Hector; Jelinek, P.; Brandbyge, Mads

    2009-01-01

    A method for improving the electronic spectrum of standard Density-Functional Theory (DFT) calculations (i.e., LDA or GGA approximations) is presented, and its application is discussed for the case of the copper phthalocyanine (CuPc) molecule. The method is based on a treatment of exchange...... and correlation in a many-body Hamiltonian, and it leads to easy-to-evaluate corrections to the DFT eigenvalues. Self-interaction is largely corrected, so that the modified energy levels do not suffer from spurious crossings, as often encountered for CuPc in DFT, and they remedy the standard underestimation...... or semiempirical functionals for molecular levels, it can be easily applied to any local-orbital DFT approach, improving on several important limitations of standard DFT methods....

  1. Describing long-range charge-separation processes with subsystem density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Solovyeva, Alisa; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Simulation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany); Pavanello, Michele, E-mail: m.pavanello@rutgers.edu [Department of Chemistry, Rutgers University, 73 Warren St., Newark, New Jersey 07102 (United States)

    2014-04-28

    Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants in Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states.

  2. Describing long-range charge-separation processes with subsystem density-functional theory

    International Nuclear Information System (INIS)

    Solovyeva, Alisa; Neugebauer, Johannes; Pavanello, Michele

    2014-01-01

    Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants in Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states

  3. Are energy-dense foods really cheaper? Reexamining the relation between food price and energy density.

    Science.gov (United States)

    Lipsky, Leah M

    2009-11-01

    The inverse relation between energy density (kcal/g) and energy cost (price/kcal) has been interpreted to suggest that produce (fruit, vegetables) is more expensive than snacks (cookies, chips). The objective of this study was to show the methodologic weakness of comparing energy density with energy cost. The relation between energy density and energy cost was replicated in a random-number data set. Additionally, observational data were collected for produce and snacks from an online supermarket. Variables included total energy (kcal), total weight (g), total number of servings, serving size (g/serving), and energy density (kcal/g). Price measures included energy cost ($/kcal), total price ($), unit price ($/g), and serving price ($/serving). Two-tailed t tests were used to compare price measures by food category. Relations between energy density and price measures within food categories were examined with the use of Spearman rank correlation analysis. The relation between energy density and energy cost was shown to be driven by the algebraic properties of these variables. Food category was strongly correlated with both energy density and food price measures. Energy cost was higher for produce than for snacks. However, total price and unit price were lower for produce. Serving price and serving size were greater for produce than for snacks. Within food categories, energy density was uncorrelated with most measures of food price, except for a weak positive correlation with serving price within the produce category. The findings suggest the relation between energy density and food price is confounded by food category and depends on which measure of price is used.

  4. Building a Universal Nuclear Energy Density Functional (UNEDF): SciDAC-2 Project

    Energy Technology Data Exchange (ETDEWEB)

    Carlson, Joe; Furnstahl, Dick; Lusk, Rusty; Nazarewicz, Witek; Ng, Esmond; Thompson, Ian; Vary, James

    2012-06-30

    An understanding of the properties of atomic nuclei is crucial for a complete nuclear theory, for element formation, for properties of stars, and for present and future energy and defense applications. During the period of Dec. 1, 2006 - Jun. 30, 2012, the UNEDF collaboration carried out a comprehensive study of all nuclei based on the most accurate knowledge of the strong nuclear interaction, the most reliable theoretical approaches, the most advanced algorithms, and extensive computational resources, with a view towards scaling to the petaflop platforms and beyond. The long-term vision initiated with UNEDF is to arrive at a comprehensive, quantitative, and unified description of nuclei and their reactions, grounded in the fundamental interactions between the constituent nucleons. We seek to replace current phenomenological models of nuclear structure and reactions with a well-founded microscopic theory that delivers maximum predictive power with well-quantified uncertainties. Specifically, the mission of this project has been three-fold: first, to find an optimal energy density functional (EDF) using all our knowledge of the nucleonic Hamiltonian and basic nuclear properties; second, to apply the EDF theory and its extensions to validate the functional using all the available relevant nuclear structure and reaction data; and third, to apply the validated theory to properties of interest that cannot be measured, in particular the properties needed for reaction theory.

  5. Condensation pressures in small pores: An analytical model based on density functional theory

    International Nuclear Information System (INIS)

    Nilson, R.H.; Griffiths, S.K.

    1999-01-01

    Integral methods are used to derive an analytical expression describing fluid condensation pressures in slit pores bounded by parallel plane walls. To obtain this result, the governing equations of density functional theory (DFT) are integrated across the pore width assuming that fluid densities within adsorbed layers are spatially uniform. The thickness, density, and free energy of these layers are expressed as composite functions constructed from asymptotic limits applicable to small and large pores. By equating the total free energy of the adsorbed layers to that of a liquid-full pore, we arrive at a closed-form expression for the condensation pressure in terms of the pore size, surface tension, and Lennard-Jones parameters of the adsorbent and adsorbate molecules. The resulting equation reduces to the Kelvin equation in the large-pore limit. It further reproduces the condensation pressures computed by means of the full DFT equations for all pore sizes in which phase transitions are abrupt. Finally, in the limit of extremely small pores, for which phase transitions may be smooth and continuous, this simple analytical expression provides a good approximation to the apparent condensation pressure indicated by the steepest portion of the adsorption isotherm computed via DFT. copyright 1999 American Institute of Physics

  6. Density functional theory investigation of oxygen interaction with boron-doped graphite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Juan; Wang, Chen [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Liang, Tongxiang, E-mail: txliang@tsinghua.edu.cn [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Lai, Wensheng [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Density-functional approach is applied to study the interaction of oxygen with boron-doped graphite. • Adsorption and diffusion of oxygen atoms on boron doped graphite surfaces are studied. • Recombination of oxygen is investigated by ER and LH mechanisms. • Low boron concentration facilitates O{sub 2} formation while high boron loading inhibits the recombination. • The presence of B−B bonds due to boron accumulation makes it impossible for oxygen recombination. - Abstract: Boron inserted as impurity by substitution of carbon atoms in graphite is known to change (improve or deteriorate) oxidation resistance of nuclear graphite, but the reason for both catalytic and inhibiting oxidation is still uncertain. As a first step, this work is more specially devoted to the adsorption and diffusion of oxygen atoms on the surface and related to the problem of oxygen retention on the pure and boron-containing graphite surfaces. Adsorption energies and energy barriers associated to the diffusion for molecular oxygen recombination are calculated in the density functional theory framework. The existence of boron modifies the electronic structure of the surface, which results in an increase of the adsorption energy for O. However, low boron loading makes it easier for the recombination into molecular oxygen. For high boron concentration, it induces a better O retention capability in graphite because the presence of B-B bonds decreases recombination of the adsorbed oxygen atoms. A possible explanation for both catalytic and inhibiting effects of boron in graphite is proposed.

  7. Benchmark density functional theory calculations for nanoscale conductance

    DEFF Research Database (Denmark)

    Strange, Mikkel; Bækgaard, Iben Sig Buur; Thygesen, Kristian Sommer

    2008-01-01

    We present a set of benchmark calculations for the Kohn-Sham elastic transmission function of five representative single-molecule junctions. The transmission functions are calculated using two different density functional theory methods, namely an ultrasoft pseudopotential plane-wave code...

  8. Energy density of marine pelagic fish eggs

    DEFF Research Database (Denmark)

    Riis-Vestergaard, J.

    2002-01-01

    Analysis of the literature on pelagic fish eggs enabled generalizations to be made of their energy densities, because the property of being buoyant in sea water appears to constrain the proximate composition of the eggs and thus to minimize interspecific variation. An energy density of 1.34 J mul......(-1) of total egg volume is derived for most species spawning eggs without visible oil globules. The energy density of eggs with oil globules is predicted by (σ) over cap = 1.34 + 40.61 x (J mul(-1)) where x is the fractional volume of the oil globule. (C) 2002 The Fisheries Society of the British...

  9. Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory

    Science.gov (United States)

    2017-04-23

    Our approach represents a full solid-state calculation, allowing for polarization ef- fects while still capable of capturing inter-molecular dis...AFRL-AFOSR-UK-TR-2017-0030 Optical absorption in molecular crystals from time-dependent density functional theory Leeor Kronik WEIZMANN INSTITUTE OF...from time-dependent density functional theory 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-15-1-0290 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S

  10. Modeling of a piezoelectric/piezomagnetic nano energy harvester based on two dimensional theory

    Science.gov (United States)

    Yan, Zhi

    2018-01-01

    This work presents a two dimensional theory for a piezoelectric/piezomagnetic bilayer nanoplate in coupled extensional and flexural vibrations with both flexoelectric and surface effects. The magneto-electro-elastic (MEE) coupling equations are derived from three-dimensional equations and Kirchhoff plate theory. Based on the developed theory, a piezoelectric/piezomagnetic nano energy harvester is proposed, which can generate electricity under time-harmonic applied magnetic field. The approximate solutions for the mechanical responses and voltage of the energy harvester are obtained using the weighted residual method. Results show that the properties of the proposed energy harvester are size-dependent due to the flexoelectric and surface effects, and such effects are more pronounced when the bilayer thickness is reduced to dozens of nanometers. It is also found that the magnetoelectric coupling coefficient and power density of the energy harvester are sensitive to the load resistance, the thickness fraction of the piezoelectric or the piezomagnetic layer and damping ratios. Moreover, results indicate that the flexoelectric effect could be made use to build a dielectric/piezomagnetic nano energy harvester. This work provides modeling techniques and numerical methods for investigating the size-dependent properties of MEE nanoplate-based energy harvester and could be helpful for designing nano energy harvesters using the principle of flexoelectricity.

  11. Quantum theory with an energy operator defined as a quartic form of the momentum

    Energy Technology Data Exchange (ETDEWEB)

    Bezák, Viktor, E-mail: bezak@fmph.uniba.sk

    2016-09-15

    Quantum theory of the non-harmonic oscillator defined by the energy operator proposed by Yurke and Buks (2006) is presented. Although these authors considered a specific problem related to a model of transmission lines in a Kerr medium, our ambition is not to discuss the physical substantiation of their model. Instead, we consider the problem from an abstract, logically deductive, viewpoint. Using the Yurke–Buks energy operator, we focus attention on the imaginary-time propagator. We derive it as a functional of the Mehler kernel and, alternatively, as an exact series involving Hermite polynomials. For a statistical ensemble of identical oscillators defined by the Yurke–Buks energy operator, we calculate the partition function, average energy, free energy and entropy. Using the diagonal element of the canonical density matrix of this ensemble in the coordinate representation, we define a probability density, which appears to be a deformed Gaussian distribution. A peculiarity of this probability density is that it may reveal, when plotted as a function of the position variable, a shape with two peaks located symmetrically with respect to the central point.

  12. Laser fusion and high energy density science

    International Nuclear Information System (INIS)

    Kodama, Ryosuke

    2005-01-01

    High-power laser technology is now opening a variety of new fields of science and technology using laser-produced plasmas. The laser plasma is now recognized as one of the important tools for the investigation and application of matter under extreme conditions, which is called high energy density science. This chapter shows a variety of applications of laser-produced plasmas as high energy density science. One of the more attractive industrial and science applications is the generation of intense pulse-radiation sources, such as the generation of electro-magnetic waves in the ranges of EUV (Extreme Ultra Violet) to gamma rays and laser acceleration of charged particles. The laser plasma is used as an energy converter in this regime. The fundamental science applications of high energy density physics are shown by introducing laboratory astrophysics, the equation of state of high pressure matter, including warm dense matter and nuclear science. Other applications are also presented, such as femto-second laser propulsion and light guiding. Finally, a new systematization is proposed to explore the possibility of the high energy density plasma application, which is called high energy plasma photonics''. This is also exploration of the boundary regions between laser technology and beam optics based on plasma physics. (author)

  13. Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Olsen, Jógvan Magnus Haugaard; Knecht, Stefan

    2015-01-01

    . To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality......We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE......-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory...

  14. Symmetry Energy as a Function of Density and Mass

    International Nuclear Information System (INIS)

    Danielewicz, Pawel; Lee, Jenny

    2007-01-01

    Energy in nuclear matter is, in practice, completely characterized at different densities and asymmetries, when the density dependencies of symmetry energy and of energy of symmetric matter are specified. The density dependence of the symmetry energy at subnormal densities produces mass dependence of nuclear symmetry coefficient and, thus, can be constrained by that latter dependence. We deduce values of the mass dependent symmetry coefficients, by using excitation energies to isobaric analog states. The coefficient systematic, for intermediate and high masses, is well described in terms of the symmetry coefficient values of a a V = (31.5-33.5) MeV for the volume coefficient and a a S = (9-12) MeV for the surface coefficient. These two further correspond to the parameter values describing density dependence of symmetry energy, of L∼95 MeV and K sym ∼25 MeV

  15. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory.

    Science.gov (United States)

    Derricotte, Wallace D; Evangelista, Francesco A

    2015-06-14

    Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree-Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine.

  16. Density functional theory of polydisperse fluid interfaces

    International Nuclear Information System (INIS)

    Baus, M.; Bellier-Castella, L.; Xu, H.

    2002-01-01

    Most colloids usually exhibit one or several polydispersities. A natural framework for the theoretical description of polydisperse systems is provided by the extension of density functional theory to 'continuous' mixtures. This will be illustrated here by the study of both the bulk and interfacial properties of a simple van der Waals model for a polydisperse colloidal fluid. (author)

  17. COMBINATION OF DENSITY AND ENERGY MODULATION IN MICROBUNCHING ANALYSIS

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Cheng Ying [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Li, Rui [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

    2016-05-01

    Microbunching instability (MBI) has been one of the most challenging issues in the transport of high-brightness electron beams for modern recirculating or energy recovery linac machines. Recently we have developed and implemented a Vlasov solver [1] to calculate the microbunching gain for an arbitrary beamline lattice, based on the extension of existing theoretical formulation [2-4] for the microbunching amplification from an initial density perturbation to the final density modulation. For more thorough analyses, in addition to the case of (initial) density to (final) density amplification, we extend in this paper the previous formulation to more general cases, including energy to density, density to energy and energy to energy amplifications for a recirculation machine. Such semi-analytical formulae are then incorporated into our Vlasov solver, and qualitative agreement is obtained when the semi-analytical Vlasov results are compared with particle tracking simulation using ELEGANT [5].

  18. Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries

    Science.gov (United States)

    Li, Jianlin; Du, Zhijia; Ruther, Rose E.; AN, Seong Jin; David, Lamuel Abraham; Hays, Kevin; Wood, Marissa; Phillip, Nathan D.; Sheng, Yangping; Mao, Chengyu; Kalnaus, Sergiy; Daniel, Claus; Wood, David L.

    2017-09-01

    Reducing cost and increasing energy density are two barriers for widespread application of lithium-ion batteries in electric vehicles. Although the cost of electric vehicle batteries has been reduced by 70% from 2008 to 2015, the current battery pack cost (268/kWh in 2015) is still >2 times what the USABC targets (125/kWh). Even though many advancements in cell chemistry have been realized since the lithium-ion battery was first commercialized in 1991, few major breakthroughs have occurred in the past decade. Therefore, future cost reduction will rely on cell manufacturing and broader market acceptance. This article discusses three major aspects for cost reduction: (1) quality control to minimize scrap rate in cell manufacturing; (2) novel electrode processing and engineering to reduce processing cost and increase energy density and throughputs; and (3) material development and optimization for lithium-ion batteries with high-energy density. Insights on increasing energy and power densities of lithium-ion batteries are also addressed.

  19. Functional approach for pairing in finite systems: How to define restoration of broken symmetries in Energy Density Functional theory?

    International Nuclear Information System (INIS)

    Hupin, G; Lacroix, D; Bender, M

    2011-01-01

    The Multi-Reference Energy Density Functional (MR-EDF) approach (also called configuration mixing or Generator Coordinate Method), that is commonly used to treat pairing in finite nuclei and project onto particle number, is re-analyzed. It is shown that, under certain conditions, the MR-EDF energy can be interpreted as a functional of the one-body density matrix of the projected state with good particle number. Based on this observation, we propose a new approach, called Symmetry-Conserving EDF (SC-EDF), where the breaking and restoration of symmetry are accounted for simultaneously. We show, that such an approach is free from pathologies recently observed in MR-EDF and can be used with a large flexibility on the density dependence of the functional.

  20. Magnetized Anisotropic Dark Energy Models in Barber’s Second Self-Creation Theory

    Directory of Open Access Journals (Sweden)

    D. D. Pawar

    2014-01-01

    Full Text Available The present paper deals with Bianchi type IX cosmological model with magnetized anisotropic dark energy by using Barber’s self-creation theory. The energy momentum tensor consists of anisotropic fluid with EoS parameter ω and a uniform magnetic field of energy density ρB. In order to obtain the exact solution we have assumed that dark energy components and the components of magnetic field interact minimally and obey the law of conservation of energy momentum tensors. We have also used the special law of variation for the mean generalized Hubble parameter and power law relation between scalar field and scale factor. Some physical and kinematical properties of the models have been discussed.

  1. Multiple exciton generation in chiral carbon nanotubes: Density functional theory based computation

    Science.gov (United States)

    Kryjevski, Andrei; Mihaylov, Deyan; Kilina, Svetlana; Kilin, Dmitri

    2017-10-01

    We use a Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory based on density functional theory simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of the relaxation. We apply this approach to chiral single-wall carbon nanotubes (SWCNTs), such as (6,2) and (6,5). We predict efficient MEG in the (6,2) and (6,5) SWCNTs within the solar spectrum range starting at the 2Eg energy threshold and with QE reaching ˜1.6 at about 3Eg, where Eg is the electronic gap.

  2. Diffusion of hydrogen into and through γ-iron by density functional theory

    Science.gov (United States)

    Chohan, Urslaan K.; Koehler, Sven P. K.; Jimenez-Melero, Enrique

    2018-06-01

    This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.

  3. Theoretical investigation of cyromazine tautomerism using density functional theory and Møller–Plesset perturbation theory methods

    Science.gov (United States)

    A computational chemistry analysis of six unique tautomers of cyromazine, a pesticide used for fly control, was performed with density functional theory (DFT) and canonical second order Møller–Plesset perturbation theory (MP2) methods to gain insight into the contributions of molecular structure to ...

  4. Postmortem validation of breast density using dual-energy mammography

    Energy Technology Data Exchange (ETDEWEB)

    Molloi, Sabee, E-mail: symolloi@uci.edu; Ducote, Justin L.; Ding, Huanjun; Feig, Stephen A. [Department of Radiological Sciences, University of California, Irvine, California 92697 (United States)

    2014-08-15

    Purpose: Mammographic density has been shown to be an indicator of breast cancer risk and also reduces the sensitivity of screening mammography. Currently, there is no accepted standard for measuring breast density. Dual energy mammography has been proposed as a technique for accurate measurement of breast density. The purpose of this study is to validate its accuracy in postmortem breasts and compare it with other existing techniques. Methods: Forty postmortem breasts were imaged using a dual energy mammography system. Glandular and adipose equivalent phantoms of uniform thickness were used to calibrate a dual energy basis decomposition algorithm. Dual energy decomposition was applied after scatter correction to calculate breast density. Breast density was also estimated using radiologist reader assessment, standard histogram thresholding and a fuzzy C-mean algorithm. Chemical analysis was used as the reference standard to assess the accuracy of different techniques to measure breast composition. Results: Breast density measurements using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean algorithm, and dual energy were in good agreement with the measured fibroglandular volume fraction using chemical analysis. The standard error estimates using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean, and dual energy were 9.9%, 8.6%, 7.2%, and 4.7%, respectively. Conclusions: The results indicate that dual energy mammography can be used to accurately measure breast density. The variability in breast density estimation using dual energy mammography was lower than reader assessment rankings, standard histogram thresholding, and fuzzy C-mean algorithm. Improved quantification of breast density is expected to further enhance its utility as a risk factor for breast cancer.

  5. Postmortem validation of breast density using dual-energy mammography

    International Nuclear Information System (INIS)

    Molloi, Sabee; Ducote, Justin L.; Ding, Huanjun; Feig, Stephen A.

    2014-01-01

    Purpose: Mammographic density has been shown to be an indicator of breast cancer risk and also reduces the sensitivity of screening mammography. Currently, there is no accepted standard for measuring breast density. Dual energy mammography has been proposed as a technique for accurate measurement of breast density. The purpose of this study is to validate its accuracy in postmortem breasts and compare it with other existing techniques. Methods: Forty postmortem breasts were imaged using a dual energy mammography system. Glandular and adipose equivalent phantoms of uniform thickness were used to calibrate a dual energy basis decomposition algorithm. Dual energy decomposition was applied after scatter correction to calculate breast density. Breast density was also estimated using radiologist reader assessment, standard histogram thresholding and a fuzzy C-mean algorithm. Chemical analysis was used as the reference standard to assess the accuracy of different techniques to measure breast composition. Results: Breast density measurements using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean algorithm, and dual energy were in good agreement with the measured fibroglandular volume fraction using chemical analysis. The standard error estimates using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean, and dual energy were 9.9%, 8.6%, 7.2%, and 4.7%, respectively. Conclusions: The results indicate that dual energy mammography can be used to accurately measure breast density. The variability in breast density estimation using dual energy mammography was lower than reader assessment rankings, standard histogram thresholding, and fuzzy C-mean algorithm. Improved quantification of breast density is expected to further enhance its utility as a risk factor for breast cancer

  6. Density functional theory study on the formation of reactive benzoquinone imines by hydrogen abstraction

    DEFF Research Database (Denmark)

    Leth, Rasmus; Rydberg, Patrik; Jørgensen, Flemming Steen

    2015-01-01

    Many drug compounds are oxidized by cytochrome P450 (CYP) enzymes to form reactive metabolites. This study presents density functional theory calculations of the CYP-mediated metabolism of acetaminophen and a series of related compounds that can form reactive metabolites by hydrogen abstraction....... The substitution pattern affects the activation barrier for hydrogen abstraction by up to 30 kJ/mol. A correlation (R(2) = 0.72) between the transition-state energies and the corresponding substrate radical energies has been established. Using this correlation is significantly less time-demanding than using...... the porphyrin model to determine the activation energies. We have used this correlation on monosubstituted phenols to rationalize the effect of the various substituents in the drug compounds. In addition to facilitating a chemical interpretation, the approach is sufficiently fast and reliable to be used...

  7. Perspective: Fundamental aspects of time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Maitra, Neepa T. [Department of Physics and Astronomy, Hunter College and the Physics Program at the Graduate Center of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States)

    2016-06-14

    In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.

  8. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.

    2002-01-01

    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...... the nitrogen binding energies of the optimal catalysts at different temperatures, pressures, and synthesis gas compositions. Using this concept together with the ability to prepare catalysts with desired binding energies it is possible to optimize the ammonia process. In this way a link between first...

  9. Time-dependent density functional theory for multi-component systems

    International Nuclear Information System (INIS)

    Tiecheng Li; Peiqing Tong

    1985-10-01

    The Runge-Gross version of Hohenberg-Kohn-Sham's density functional theory is generalized to multi-component systems, both for arbitrary time-dependent pure states and for arbitrary time-dependent ensembles. (author)

  10. A confrontation of density wave theories with observations

    International Nuclear Information System (INIS)

    Kalnajs, A.J.

    1978-01-01

    The author proposes that it is a mistake to think that the density wave theories of spiral structure have reached the maturity where they can make unconditional predictions which can be tested. They are still very dependent on observations for help and guidance. (C.F.)

  11. Time dependent density matrix theory and effective interaction

    Energy Technology Data Exchange (ETDEWEB)

    Tohyama, Mitsuru [Kyorin Univ., Mitaka, Tokyo (Japan). School of Medicine

    1998-07-01

    A correlated ground state of {sup 16}O and an E2 giant resonance built on it are calculated using an extended version of the time-dependent Hartree-Fock theory called the time-dependent density-matrix theory (TDDM). The Skyrme force is used in the calculation of both a mean field and two-body correlations. It is found that TDDM gives reasonable ground-state correlations and a large spreading width of the E2 giant resonance when single-particle states in the continuum are treated appropriately. (author)

  12. Nonlocal kinetic-energy-density functionals

    International Nuclear Information System (INIS)

    Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E.

    1996-01-01

    In this paper we present nonlocal kinetic-energy functionals T[n] within the average density approximation (ADA) framework, which do not require any extra input when applied to any electron system and recover the exact kinetic energy and the linear response function of a homogeneous system. In contrast with previous ADA functionals, these present good behavior of the long-range tail of the exact weight function. The averaging procedure for the kinetic functional (averaging the Fermi momentum of the electron gas, instead of averaging the electron density) leads to a functional without numerical difficulties in the calculation of extended systems, and it gives excellent results when applied to atoms and jellium surfaces. copyright 1996 The American Physical Society

  13. Properties of short-range and long-range correlation energy density functionals from electron-electron coalescence

    International Nuclear Information System (INIS)

    Gori-Giorgi, Paola; Savin, Andreas

    2006-01-01

    The combination of density-functional theory with other approaches to the many-electron problem through the separation of the electron-electron interaction into a short-range and a long-range contribution is a promising method, which is raising more and more interest in recent years. In this work some properties of the corresponding correlation energy functionals are derived by studying the electron-electron coalescence condition for a modified (long-range-only) interaction. A general relation for the on-top (zero electron-electron distance) pair density is derived, and its usefulness is discussed with some examples. For the special case of the uniform electron gas, a simple parametrization of the on-top pair density for a long-range only interaction is presented and supported by calculations within the ''extended Overhauser model.'' The results of this work can be used to build self-interaction corrected short-range correlation energy functionals

  14. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  15. Density and energy of supernova remnants

    Energy Technology Data Exchange (ETDEWEB)

    Canto, J [Manchester Univ. (UK). Dept. of Astronomy

    1977-12-01

    The effects of an interstellar magnetic field on the gas flow behind a strong shock front are considered. The ambient density and energy of supernova remnants are estimated from the intensity ratio of sulphur lines I(6717)/I(6731). It is found that, on average, the ambient density around galactic supernova remnants is 4 cm/sup -3/. The total energy appears to be the same for all supernova remnants (to within a factor = approximately 5). A mean value of 4 10/sup 51/ erg is found.

  16. Theory study of global density influence and soils chemical composition at neutron probes response

    International Nuclear Information System (INIS)

    Crispino, M.L.

    1980-06-01

    Three energy group diffusion theory is applied to calculate the thermal neutron flux through a soil-water mixture at the neutron source. The soils studies are taken from two horizons of different composition, of a representative soil of the Litoral-Mata Zone of Pernambuco State. The thermal flux is obtained taking into consideration increasing values of the water volume percent, H, and the bulk density of the soil. The cross-sections of the mixture are calculated from the chemical composition of the soils. (author)

  17. Rayleigh Scattering Density Measurements, Cluster Theory, and Nucleation Calculations at Mach 10

    Science.gov (United States)

    Balla, R. Jeffrey; Everhart, Joel L.

    2012-01-01

    In an exploratory investigation, quantitative unclustered laser Rayleigh scattering measurements of density were performed in the air in the NASA Langley Research Center's 31 in. Mach 10 wind tunnel. A review of 20 previous years of data in supersonic and Mach 6 hypersonic flows is presented where clustered signals typically overwhelmed molecular signals. A review of nucleation theory and accompanying nucleation calculations are also provided to interpret the current observed lack of clustering. Data were acquired at a fixed stagnation temperature near 990Kat five stagnation pressures spanning 2.41 to 10.0 MPa (350 to 1454 psi) using a pulsed argon fluoride excimer laser and double-intensified charge-coupled device camera. Data averaged over 371 images and 210 pixels along a 36.7mmline measured freestream densities that agree with computed isentropic-expansion densities to less than 2% and less than 6% at the highest and lowest densities, respectively. Cluster-free Mach 10 results are compared with previous clustered Mach 6 and condensation-free Mach 14 results. Evidence is presented indicating vibrationally excited oxygen and nitrogen molecules are absorbed as the clusters form, release their excess energy, and inhibit or possibly reverse the clustering process. Implications for delaying clustering and condensation onset in hypersonic and hypervelocity facilities are discussed.

  18. New aspects of high energy density plasma

    International Nuclear Information System (INIS)

    Hotta, Eiki

    2005-10-01

    The papers presented at the symposium on 'New aspects of high energy density plasma' held at National Institute for Fusion Science are collected in this proceedings. The papers reflect the present status and recent progress in the experiments and theoretical works on high energy density plasma produced by pulsed power technology. The 13 of the presented papers are indexed individually. (J.P.N.)

  19. Higgs phase in non-Abelian gauge theories

    International Nuclear Information System (INIS)

    Kaymakcalan, O.S.

    1981-06-01

    A non-Abelian gauge theory involving scalar fields with non-tachyonic mass terms in the Lagrangian is considered, in order to construct a finite energy density trial vacuum for this theory. The usual scalar potential arguments suggest that the vacuum of such a theory would be in the perturbative phase. However, the obvious choices for a vacuum in this phase, the Axial gauge and the Coulomb gauge bare vacua, do not have finite energy densities even with an ultraviolet cutoff. Indeed, it is a non-trivial problem to construct finite energy density vacua for non-Abelian gauge theories and this is intimately connected with the gauge fixing degeneracies of these theories. Since the gauge fixing is achieved in the Unitary gauge, this suggests that the Unitary gauge bare vacuum might be a finite energy trial vacuum and, despite the form of the scalar potential, the vacuum of this theory might be in a Higgs phase rather than the perturbative phase

  20. Evaluation for the models of neutron diffusion theory in terms of power density distributions of the HTTR

    International Nuclear Information System (INIS)

    Takamatsu, Kuniyoshi; Shimakawa, Satoshi; Nojiri, Naoki; Fujimoto, Nozomu

    2003-10-01

    In the case of evaluations for the highest temperature of the fuels in the HTTR, it is very important to expect the power density distributions accurately; therefore, it is necessary to improve the analytical model with the neutron diffusion and the burn-up theory. The power density distributions are analyzed in terms of two models, the one mixing the fuels and the burnable poisons homogeneously and the other modeling them heterogeneously. Moreover these analytical power density distributions are compared with the ones derived from the gross gamma-ray measurements and the Monte Carlo calculational code with continuous energy. As a result the homogeneous mixed model isn't enough to expect the power density distributions of the core in the axial direction; on the other hand, the heterogeneous model improves the accuracy. (author)

  1. First principles density functional theory study of Pb doped α-MnO2 catalytic materials

    Science.gov (United States)

    Song, Zilin; Yan, Zhiguo; Yang, Xiaojun; Bai, Hang; Duan, Yuhua; Yang, Bin; Leng, Li

    2018-03-01

    The impact of Pb in the tunnels of manganese oxide octahedral molecular sieves on chemical state of Mn species and lattice oxygen were investigated utilizing density functional theory calculations. The results show that the Pb dopant in the tunnels of OMS-2 could reduce the average valence states of Mn. The lower energy required for bulk oxygen defects formation in Pb-OMS-2 validates the activation of lattice oxygen by inclusion of tunnel dopant. The inclusion of Pb promotes the catalytic oxidation activity of OMS-2 by reducing the energy required for the surface lattice oxygen migration during the Mars - van Krevelen oxidation process.

  2. Aspects of renormalization in finite-density field theory

    Energy Technology Data Exchange (ETDEWEB)

    Fitzpatrick, A. Liam; Torroba, Gonzalo; Wang, Huajia

    2015-05-26

    We study the renormalization of the Fermi surface coupled to a massless boson near three spatial dimensions. For this, we set up a Wilsonian RG with independent decimation procedures for bosons and fermions, where the four-fermion interaction “Landau parameters” run already at tree level. Our explicit one-loop analysis resolves previously found obstacles in the renormalization of finite-density field theory, including logarithmic divergences in nonlocal interactions and the appearance of multilogarithms. The key aspects of the RG are the above tree-level running, and a UV-IR mixing between virtual bosons and fermions at the quantum level, which is responsible for the renormalization of the Fermi velocity. We apply this approach to the renormalization of 2 k F singularities, and to Fermi surface instabilities in a companion paper, showing how multilogarithms are properly renormalized. We end with some comments on the renormalization of finite-density field theory with the inclusion of Landau damping of the boson.

  3. Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes.

    Science.gov (United States)

    Chai, Jeng-Da

    2017-01-28

    We propose hybrid schemes incorporating exact exchange into thermally assisted-occupation-density functional theory (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)] for an improved description of nonlocal exchange effects. With a few simple modifications, global and range-separated hybrid functionals in Kohn-Sham density functional theory (KS-DFT) can be combined seamlessly with TAO-DFT. In comparison with global hybrid functionals in KS-DFT, the resulting global hybrid functionals in TAO-DFT yield promising performance for systems with strong static correlation effects (e.g., the dissociation of H 2 and N 2 , twisted ethylene, and electronic properties of linear acenes), while maintaining similar performance for systems without strong static correlation effects. Besides, a reasonably accurate description of noncovalent interactions can be efficiently achieved through the inclusion of dispersion corrections in hybrid TAO-DFT. Relative to semilocal density functionals in TAO-DFT, global hybrid functionals in TAO-DFT are generally superior in performance for a wide range of applications, such as thermochemistry, kinetics, reaction energies, and optimized geometries.

  4. Condensation pressures in small pores: An analytical model based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    R. H. Nilson; S. K. Griffiths

    1999-02-01

    Adsorption and condensation are critical to many applications of porous materials including filtration, separation, and the storage of gases. Integral methods are used to derive an analytical expression describing fluid condensation pressures in slit pores bounded by parallel plane walls. To obtain this result, the governing equations of Density Functional Theory (DFT) are integrated across the pore width assuming that fluid densities within adsorbed layers are spatially uniform. The thickness, density, and energy of these layers are expressed as composite functions constructed from asymptotic limits applicable to small and large pores. By equating the total energy of the adsorbed layers to that of a liquid-full pore, the authors arrive at a closed-form expression for the condensation pressure in terms of the pore size, surface tension, and Lennard-Jones parameters of the adsorbent and adsorbate molecules. The resulting equation reduces to the Kelvin equation in the large-pore limit. It further reproduces the condensation pressures computed by means of the full DFT equations for all pore sizes in which phase transitions are abrupt. Finally, in the limit of extremely small pores, for which phase transitions may be smooth and continuous, this simple analytical expression provides a good approximation to the apparent condensation pressure indicated by the steepest portion of the adsorption isotherm computed via DFT.

  5. Updating energy security and environmental policy: Energy security theories revisited.

    Science.gov (United States)

    Proskuryakova, L

    2018-06-18

    The energy security theories are based on the premises of sufficient and reliable supply of fossil fuels at affordable prices in centralized supply systems. Policy-makers and company chief executives develop energy security strategies based on the energy security theories and definitions that dominate in the research and policy discourse. It is therefore of utmost importance that scientists revisit these theories in line with the latest changes in the energy industry: the rapid advancement of renewables and smart grid, decentralization of energy systems, new environmental and climate challenges. The study examines the classic energy security concepts (neorealism, neoliberalism, constructivism and international political economy) and assesses if energy technology changes are taken into consideration. This is done through integrative literature review, comparative analysis, identification of 'international relations' and 'energy' research discourse with the use of big data, and case studies of Germany, China, and Russia. The paper offers suggestions for revision of energy security concepts through integration of future technology considerations. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

    KAUST Repository

    Salawu, Omotayo Akande

    2016-09-29

    Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

  7. Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

    KAUST Repository

    Salawu, Omotayo Akande; Chroneos, Alexander; Vasilopoulou, Maria; Kennou, Stella; Schwingenschlö gl, Udo

    2016-01-01

    Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

  8. Multicomponent Density Functional Theory: Impact of Nuclear Quantum Effects on Proton Affinities and Geometries.

    Science.gov (United States)

    Brorsen, Kurt R; Yang, Yang; Hammes-Schiffer, Sharon

    2017-08-03

    Nuclear quantum effects such as zero point energy play a critical role in computational chemistry and often are included as energetic corrections following geometry optimizations. The nuclear-electronic orbital (NEO) multicomponent density functional theory (DFT) method treats select nuclei, typically protons, quantum mechanically on the same level as the electrons. Electron-proton correlation is highly significant, and inadequate treatments lead to highly overlocalized nuclear densities. A recently developed electron-proton correlation functional, epc17, has been shown to provide accurate nuclear densities for molecular systems. Herein, the NEO-DFT/epc17 method is used to compute the proton affinities for a set of molecules and to examine the role of nuclear quantum effects on the equilibrium geometry of FHF - . The agreement of the computed results with experimental and benchmark values demonstrates the promise of this approach for including nuclear quantum effects in calculations of proton affinities, pK a 's, optimized geometries, and reaction paths.

  9. Visualisation and orbital-free parametrisation of the large-Z scaling of the kinetic energy density of atoms

    Science.gov (United States)

    Cancio, Antonio C.; Redd, Jeremy J.

    2017-03-01

    The scaling of neutral atoms to large Z, combining periodicity with a gradual trend to homogeneity, is a fundamental probe of density functional theory, one that has driven recent advances in understanding both the kinetic and exchange-correlation energies. Although research focus is normally upon the scaling of integrated energies, insights can also be gained from energy densities. We visualise the scaling of the positive-definite kinetic energy density (KED) in closed-shell atoms, in comparison to invariant quantities based upon the gradient and Laplacian of the density. We notice a striking fit of the KED within the core of any atom to a gradient expansion using both the gradient and the Laplacian, appearing as an asymptotic limit around which the KED oscillates. The gradient expansion is qualitatively different from that derived from first principles for a slowly varying electron gas and is correlated with a nonzero Pauli contribution to the KED near the nucleus. We propose and explore orbital-free meta-GGA models for the kinetic energy to describe these features, with some success, but the effects of quantum oscillations in the inner shells of atoms make a complete parametrisation difficult. We discuss implications for improved orbital-free description of molecular properties.

  10. A high energy density relaxor antiferroelectric pulsed capacitor dielectric

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Hwan Ryul; Lynch, Christopher S. [Department of Mechanical and Aerospace Engineering, University of California, Los Angeles (UCLA), Los Angeles, California 90095 (United States)

    2016-01-14

    Pulsed capacitors require high energy density and low loss, properties that can be realized through selection of composition. Ceramic (Pb{sub 0.88}La{sub 0.08})(Zr{sub 0.91}Ti{sub 0.09})O{sub 3} was found to be an ideal candidate. La{sup 3+} doping and excess PbO were used to produce relaxor antiferroelectric behavior with slim and slanted hysteresis loops to reduce the dielectric hysteresis loss, to increase the dielectric strength, and to increase the discharge energy density. The discharge energy density of this composition was found to be 3.04 J/cm{sup 3} with applied electric field of 170 kV/cm, and the energy efficiency, defined as the ratio of the discharge energy density to the charging energy density, was 0.920. This high efficiency reduces the heat generated under cyclic loading and improves the reliability. The properties were observed to degrade some with temperature increase above 80 °C. Repeated electric field cycles up to 10 000 cycles were applied to the specimen with no observed performance degradation.

  11. Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

    Science.gov (United States)

    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.

  12. Time-dependent density functional theory for many-electron systems interacting with cavity photons.

    Science.gov (United States)

    Tokatly, I V

    2013-06-07

    Time-dependent (current) density functional theory for many-electron systems strongly coupled to quantized electromagnetic modes of a microcavity is proposed. It is shown that the electron-photon wave function is a unique functional of the electronic (current) density and the expectation values of photonic coordinates. The Kohn-Sham system is constructed, which allows us to calculate the above basic variables by solving self-consistent equations for noninteracting particles. We suggest possible approximations for the exchange-correlation potentials and discuss implications of this approach for the theory of open quantum systems. In particular we show that it naturally leads to time-dependent density functional theory for systems coupled to the Caldeira-Leggett bath.

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

    International Nuclear Information System (INIS)

    Bewerunge, Jörg; Capellmann, Ronja F.; Platten, Florian; Egelhaaf, Stefan U.; Sengupta, Ankush; Sengupta, Surajit

    2016-01-01

    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 (1) (r) and an analogue of the Edwards-Anderson order parameter g (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.

  14. Electronic properties of T graphene-like C-BN sheets: A density functional theory study

    Science.gov (United States)

    Majidi, R.

    2015-11-01

    We have used density functional theory to study the electronic properties of T graphene-like C, C-BN and BN sheets. The planar T graphene with metallic property has been considered. The results show that the presence of BN has a considerable effect on the electronic properties of T graphene. The T graphene-like C-BN and BN sheets show semiconducting properties. The energy band gap is increased by enhancing the number of BN units. The possibility of opening and controlling band gap opens the door for T graphene in switchable electronic devices.

  15. Problem of energy-momentum and theory of gravitation

    International Nuclear Information System (INIS)

    Logunov, A.A.; Folomeshkin, V.N.

    1977-01-01

    General properties of geometrised theories of gravitation are considered. Covariant formulation of conservation laws in arbitrary riemannian space-time is given. In the Einstein theory the symmetric as well as canonical energy-momentum tensor of the system ''matter plus gravitational field'' and in particular, the energy-momentum of free gravitational waves, turns out to be equal to zero. To understand the origin of the problems and difficulties concerning the energy-momentum in the Einstein theory, the gravitational filed is considered in the usual framework of the Lorentz invariant field theory, just like any other physical field. Combination of the approach proposed with the Einstein's idea of geometrization makes it possible to formulate the geometrised gravitation theory, in which there are no inner contradictions, the energy-momentum of gravitational field is defined precisely and all the known experimental facts are described successfully. For strong gravitational fields the predictions of the quasilinear geometrised theory under consideration are different from those of the gravitational theory in the Einstein formulation. Black holes are absent in the theory. Evaluation of the energy-flux of gravitational waves leads to unambiguous results and shows that the gravitational waves transfer the positive-definite energy

  16. 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

    Science.gov (United States)

    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.

  17. Relationship of Quantum Entanglement to Density Functional Theory

    OpenAIRE

    Rajagopal, A. K.; Rendell, R. W.

    2005-01-01

    The maximum von Neumann entropy principle subject to given constraints of mean values of some physical observables determines the density matrix. Similarly the stationary action principle in the case of time-dependent (dissipative) situations under similar constraints yields the density matrix. The free energy and measures of entanglement are expressed in terms of such a density matrix and thus define respective functionals of the mean values. In the light of several model calculations, it is...

  18. Solvent effects in ionic liquids: empirical linear energy-density relationships.

    Science.gov (United States)

    Cerda-Monje, A; Aizman, A; Tapia, R A; Chiappe, C; Contreras, R

    2012-07-28

    Multiparameter linear energy-density relationships to model solvent effects in room temperature ionic liquids (RTILs) are introduced and tested. The model incorporates two solvent dependent and two specific solute-solvent parameters represented by a set of electronic indexes derived from the conceptual density functional theory. The specific solute-solvent interactions are described in terms of the electronic chemical potential for proton migration between the anion or cation and the transition state structure of a specific reaction. These indexes provide a quantitative estimation of the hydrogen bond (HB) acceptor basicity and the hydrogen bond donor acidity of the ionic solvent, respectively. A sound quantitative scale of HB strength is thereby obtained. The solvent dependent contributions are described by the global electrophilicity of the cation and nucleophilicity of the anion forming the ionic liquid. The model is illustrated for the kinetics of cycloaddition of cyclopentadiene towards acrolein. In general, cation HB acidity outweighs the remaining parameters for this reaction.

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

    Science.gov (United States)

    Sosa Vazquez, Xochitl A; Isborn, Christine M

    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 potential 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.

  20. Existence of time-dependent density-functional theory for open electronic systems: time-dependent holographic electron density theorem.

    Science.gov (United States)

    Zheng, Xiao; Yam, ChiYung; Wang, Fan; Chen, GuanHua

    2011-08-28

    We present the time-dependent holographic electron density theorem (TD-HEDT), which lays the foundation of time-dependent density-functional theory (TDDFT) for open electronic systems. For any finite electronic system, the TD-HEDT formally establishes a one-to-one correspondence between the electron density inside any finite subsystem and the time-dependent external potential. As a result, any electronic property of an open system in principle can be determined uniquely by the electron density function inside the open region. Implications of the TD-HEDT on the practicality of TDDFT are also discussed.

  1. Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

    International Nuclear Information System (INIS)

    Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk

    2016-01-01

    The adsorption, diffusion, and dissociation of pyridine, C 5 H 5 N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom. The origin of the diffusion pathway is discussed in terms of the C 2 –Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).

  2. PREFACE: Classical density functional theory methods in soft and hard matter Classical density functional theory methods in soft and hard matter

    Science.gov (United States)

    Haataja, Mikko; Gránásy, László; Löwen, Hartmut

    2010-08-01

    considered, the computational effort is greatly reduced; see, e.g., [36, 51, 52]. (d) The role of fluctuations in DDFT and PFC. There is a continuing debate about the role of noise in the dynamical density functional theory (see e.g. [53]) and correspondingly also in the phase-field crystal models. Derivations of DDFT from the Smoluchowski level [54] and also within the projection operator technique [5] quite naturally lead to a deterministic equation without any noise. Clearly this is an approximation, which becomes problematic in the vicinity of a critical point or in the case of nucleation problems, where the system has to leave a metastable minimum of the free energy; in the former case, fluctuations are required in order to capture the correct critical behavior (i.e., critical exponents), while in the latter case, fluctuations are needed to establish an escape route of the system from a metastable phase. Other approaches add noise on a more phenomenological level. However, the actual strength of the noise, though fundamentally correlated with the thermal energy, is not known exactly and is treated in most applications as a phenomenological fit parameter; see, e.g., [55, 56]. This problem is a very fundamental one, and, of course, shared by the DDFT and PFC approaches. In more general terms, the addition of noise to the equation of motion in continuum models is not without conceptual difficulties (see [57]), even if noise is properly discretized in the course of the numerical integration. With the noise added, the equilibrium physical properties of the system change. Furthermore, transformation kinetics generally depend on the spatial and temporal steps, and in the limit of infinitely small steps an ultraviolet 'catastrophe' (divergence of the free energy) may occur. Evidently, an 'ultraviolet cut-off', i.e. filtering out the highest frequencies, is required to regularize the unphysical singularity. In the PFC case, a straightforward choice for the cut-off length is the

  3. Density dependence of the nuclear energy-density functional

    Science.gov (United States)

    Papakonstantinou, Panagiota; Park, Tae-Sun; Lim, Yeunhwan; Hyun, Chang Ho

    2018-01-01

    Background: The explicit density dependence in the coupling coefficients entering the nonrelativistic nuclear energy-density functional (EDF) is understood to encode effects of three-nucleon forces and dynamical correlations. The necessity for the density-dependent coupling coefficients to assume the form of a preferably small fractional power of the density ρ is empirical and the power is often chosen arbitrarily. Consequently, precision-oriented parametrizations risk overfitting in the regime of saturation and extrapolations in dilute or dense matter may lose predictive power. Purpose: Beginning with the observation that the Fermi momentum kF, i.e., the cubic root of the density, is a key variable in the description of Fermi systems, we first wish to examine if a power hierarchy in a kF expansion can be inferred from the properties of homogeneous matter in a domain of densities, which is relevant for nuclear structure and neutron stars. For subsequent applications we want to determine a functional that is of good quality but not overtrained. Method: For the EDF, we fit systematically polynomial and other functions of ρ1 /3 to existing microscopic, variational calculations of the energy of symmetric and pure neutron matter (pseudodata) and analyze the behavior of the fits. We select a form and a set of parameters, which we found robust, and examine the parameters' naturalness and the quality of resulting extrapolations. Results: A statistical analysis confirms that low-order terms such as ρ1 /3 and ρ2 /3 are the most relevant ones in the nuclear EDF beyond lowest order. It also hints at a different power hierarchy for symmetric vs. pure neutron matter, supporting the need for more than one density-dependent term in nonrelativistic EDFs. The functional we propose easily accommodates known or adopted properties of nuclear matter near saturation. More importantly, upon extrapolation to dilute or asymmetric matter, it reproduces a range of existing microscopic

  4. Electrode/Dielectric Strip For High-Energy-Density Capacitor

    Science.gov (United States)

    Yen, Shiao-Ping S.

    1994-01-01

    Improved unitary electrode/dielectric strip serves as winding in high-energy-density capacitor in pulsed power supply. Offers combination of qualities essential for high energy density: high permittivity of dielectric layers, thinness, and high resistance to breakdown of dielectric at high electric fields. Capacitors with strip material not impregnated with liquid.

  5. Communication: Density functional theory model for multi-reference systems based on the exact-exchange hole normalization.

    Science.gov (United States)

    Laqua, Henryk; Kussmann, Jörg; Ochsenfeld, Christian

    2018-03-28

    The correct description of multi-reference electronic ground states within Kohn-Sham density functional theory (DFT) requires an ensemble-state representation, employing fractionally occupied orbitals. However, the use of fractional orbital occupation leads to non-normalized exact-exchange holes, resulting in large fractional-spin errors for conventional approximative density functionals. In this communication, we present a simple approach to directly include the exact-exchange-hole normalization into DFT. Compared to conventional functionals, our model strongly improves the description for multi-reference systems, while preserving the accuracy in the single-reference case. We analyze the performance of our proposed method at the example of spin-averaged atoms and spin-restricted bond dissociation energy surfaces.

  6. Communication: Density functional theory model for multi-reference systems based on the exact-exchange hole normalization

    Science.gov (United States)

    Laqua, Henryk; Kussmann, Jörg; Ochsenfeld, Christian

    2018-03-01

    The correct description of multi-reference electronic ground states within Kohn-Sham density functional theory (DFT) requires an ensemble-state representation, employing fractionally occupied orbitals. However, the use of fractional orbital occupation leads to non-normalized exact-exchange holes, resulting in large fractional-spin errors for conventional approximative density functionals. In this communication, we present a simple approach to directly include the exact-exchange-hole normalization into DFT. Compared to conventional functionals, our model strongly improves the description for multi-reference systems, while preserving the accuracy in the single-reference case. We analyze the performance of our proposed method at the example of spin-averaged atoms and spin-restricted bond dissociation energy surfaces.

  7. The free-energy principle: a unified brain theory?

    Science.gov (United States)

    Friston, Karl

    2010-02-01

    A free-energy principle has been proposed recently that accounts for action, perception and learning. This Review looks at some key brain theories in the biological (for example, neural Darwinism) and physical (for example, information theory and optimal control theory) sciences from the free-energy perspective. Crucially, one key theme runs through each of these theories - optimization. Furthermore, if we look closely at what is optimized, the same quantity keeps emerging, namely value (expected reward, expected utility) or its complement, surprise (prediction error, expected cost). This is the quantity that is optimized under the free-energy principle, which suggests that several global brain theories might be unified within a free-energy framework.

  8. Electronic hole transfer in rutile and anatase TiO2: Effect of a delocalization error in the density functional theory on the charge transfer barrier height

    DEFF Research Database (Denmark)

    Zawadzki, Pawel; Rossmeisl, Jan; Jacobsen, Karsten Wedel

    2011-01-01

    We analyze the deformation of the potential energy surface (PES) due to the incorrect description of fractional electron systems (the nonlinearity of the energy with electron number) within a (semi) local density functional theory (DFT). Particularly sensitive to this failure are polaronic systems...

  9. Gentlest ascent dynamics for calculating first excited state and exploring energy landscape of Kohn-Sham density functionals.

    Science.gov (United States)

    Li, Chen; Lu, Jianfeng; Yang, Weitao

    2015-12-14

    We develop the gentlest ascent dynamics for Kohn-Sham density functional theory to search for the index-1 saddle points on the energy landscape of the Kohn-Sham density functionals. These stationary solutions correspond to excited states in the ground state functionals. As shown by various examples, the first excited states of many chemical systems are given by these index-1 saddle points. Our novel approach provides an alternative, more robust way to obtain these excited states, compared with the widely used ΔSCF approach. The method can be easily generalized to target higher index saddle points. Our results also reveal the physical interest and relevance of studying the Kohn-Sham energy landscape.

  10. Probing the density content of the nuclear symmetry energy

    Indian Academy of Sciences (India)

    Abstract. The nature of equation of state for the neutron star matter is crucially governed by the density dependence of the nuclear symmetry energy. We attempt to probe the behaviour of the nuclear symmetry energy around the saturation density by exploiting the empirical values for volume and surface symmetry energy ...

  11. Ultimate energy density of observable cold baryonic matter.

    Science.gov (United States)

    Lattimer, James M; Prakash, Madappa

    2005-03-25

    We demonstrate that the largest measured mass of a neutron star establishes an upper bound to the energy density of observable cold baryonic matter. An equation of state-independent expression satisfied by both normal neutron stars and self-bound quark matter stars is derived for the largest energy density of matter inside stars as a function of their masses. The largest observed mass sets the lowest upper limit to the density. Implications from existing and future neutron star mass measurements are discussed.

  12. Local Finite Density Theory, Statistical Blocking and Color Superconductivity

    OpenAIRE

    Ying, S.

    2000-01-01

    The motivation for the development of a local finite density theory is discussed. One of the problems related to an instability in the baryon number fluctuation of the chiral symmetry breaking phase of the quark system in the local theory is shown to exist. Such an instability problem is removed by taking into account the statistical blocking effects for the quark propagator, which depends on a macroscopic {\\em statistical blocking parameter} $\\epsilon$. This new frame work is then applied to...

  13. Trajectory-based nonadiabatic dynamics with time-dependent density functional theory.

    Science.gov (United States)

    Curchod, Basile F E; Rothlisberger, Ursula; Tavernelli, Ivano

    2013-05-10

    Understanding the fate of an electronically excited molecule constitutes an important task for theoretical chemistry, and practical implications range from the interpretation of atto- and femtosecond spectroscopy to the development of light-driven molecular machines, the control of photochemical reactions, and the possibility of capturing sunlight energy. However, many challenging conceptual and technical problems are involved in the description of these phenomena such as 1) the failure of the well-known Born-Oppenheimer approximation; 2) the need for accurate electronic properties such as potential energy surfaces, excited nuclear forces, or nonadiabatic coupling terms; and 3) the necessity of describing the dynamics of the photoexcited nuclear wavepacket. This review provides an overview of the current methods to address points 1) and 3) and shows how time-dependent density functional theory (TDDFT) and its linear-response extension can be used for point 2). First, the derivation of Ehrenfest dynamics and nonadiabatic Bohmian dynamics is discussed and linked to Tully's trajectory surface hopping. Second, the coupling of these trajectory-based nonadiabatic schemes with TDDFT is described in detail with special emphasis on the derivation of the required electronic structure properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Negative vacuum energy densities and the causal diamond measure

    International Nuclear Information System (INIS)

    Salem, Michael P.

    2009-01-01

    Arguably a major success of the landscape picture is the prediction of a small, nonzero vacuum energy density. The details of this prediction depend in part on how the diverging spacetime volume of the multiverse is regulated, a question that remains unresolved. One proposal, the causal diamond measure, has demonstrated many phenomenological successes, including predicting a distribution of positive vacuum energy densities in good agreement with observation. In the string landscape, however, the vacuum energy density is expected to take positive and negative values. We find the causal diamond measure gives a poor fit to observation in such a landscape - in particular, 99.6% of observers in galaxies seemingly just like ours measure a vacuum energy density smaller than we do, most of them measuring it to be negative.

  15. Validation of molecular crystal structures from powder diffraction data with dispersion-corrected density functional theory (DFT-D)

    International Nuclear Information System (INIS)

    Streek, Jacco van de; Neumann, Marcus A.

    2014-01-01

    The accuracy of 215 experimental organic crystal structures from powder diffraction data is validated against a dispersion-corrected density functional theory method. In 2010 we energy-minimized 225 high-quality single-crystal (SX) structures with dispersion-corrected density functional theory (DFT-D) to establish a quantitative benchmark. For the current paper, 215 organic crystal structures determined from X-ray powder diffraction (XRPD) data and published in an IUCr journal were energy-minimized with DFT-D and compared to the SX benchmark. The on average slightly less accurate atomic coordinates of XRPD structures do lead to systematically higher root mean square Cartesian displacement (RMSCD) values upon energy minimization than for SX structures, but the RMSCD value is still a good indicator for the detection of structures that deserve a closer look. The upper RMSCD limit for a correct structure must be increased from 0.25 Å for SX structures to 0.35 Å for XRPD structures; the grey area must be extended from 0.30 to 0.40 Å. Based on the energy minimizations, three structures are re-refined to give more precise atomic coordinates. For six structures our calculations provide the missing positions for the H atoms, for five structures they provide corrected positions for some H atoms. Seven crystal structures showed a minor error for a non-H atom. For five structures the energy minimizations suggest a higher space-group symmetry. For the 225 SX structures, the only deviations observed upon energy minimization were three minor H-atom related issues. Preferred orientation is the most important cause of problems. A preferred-orientation correction is the only correction where the experimental data are modified to fit the model. We conclude that molecular crystal structures determined from powder diffraction data that are published in IUCr journals are of high quality, with less than 4% containing an error in a non-H atom

  16. Theoretical investigation of pressure-induced structural transitions in americium using GGA+U and hybrid density functional theory methods

    DEFF Research Database (Denmark)

    Verma, Ashok K.; Modak, P.; Sharma, Surinder M.

    2013-01-01

    First-principles calculations have been performed for americium (Am) metal using the generalized gradient approximation + orbital-dependent onsite Coulomb repulsion via Hubbard interaction (GGA+U) and hybrid density functional theory (HYB-DFT) methods to investigate various ground state properties......-I to Am-II transition. Good agreement was found between calculated and experimental equations of states for all phases, but the first three phases need larger U (α) parameters (where α represents the fraction of Hartree-Fock exchange energy replacing the DFT exchange energy) than the fourth phase in order...

  17. Controlling the sign problem in finite-density quantum field theory

    Energy Technology Data Exchange (ETDEWEB)

    Garron, Nicolas; Langfeld, Kurt [University of Liverpool, Theoretical Physics Division, Department of Mathematical Sciences, Liverpool (United Kingdom)

    2017-07-15

    Quantum field theories at finite matter densities generically possess a partition function that is exponentially suppressed with the volume compared to that of the phase quenched analog. The smallness arises from an almost uniform distribution for the phase of the fermion determinant. Large cancellations upon integration is the origin of a poor signal to noise ratio. We study three alternatives for this integration: the Gaussian approximation, the ''telegraphic'' approximation, and a novel expansion in terms of theory-dependent moments and universal coefficients. We have tested the methods for QCD at finite densities of heavy quarks. We find that for two of the approximations the results are extremely close - if not identical - to the full answer in the strong sign-problem regime. (orig.)

  18. Controlling the sign problem in finite-density quantum field theory

    Science.gov (United States)

    Garron, Nicolas; Langfeld, Kurt

    2017-07-01

    Quantum field theories at finite matter densities generically possess a partition function that is exponentially suppressed with the volume compared to that of the phase quenched analog. The smallness arises from an almost uniform distribution for the phase of the fermion determinant. Large cancellations upon integration is the origin of a poor signal to noise ratio. We study three alternatives for this integration: the Gaussian approximation, the "telegraphic" approximation, and a novel expansion in terms of theory-dependent moments and universal coefficients. We have tested the methods for QCD at finite densities of heavy quarks. We find that for two of the approximations the results are extremely close—if not identical—to the full answer in the strong sign-problem regime.

  19. Moderate energy ions for high energy density physics experiments

    International Nuclear Information System (INIS)

    Grisham, L.R.

    2004-01-01

    This paper gives the results of a preliminary exploration of whether moderate energy ions (≅0.3-3 MeV/amu) could be useful as modest-cost drivers for high energy density physics experiments. It is found that if the target thickness is chosen so that the ion beam enters and then leaves the target in the vicinity of the peak of the dE/dX (stopping power) curve, high uniformity of energy deposition may be achievable while also maximizing the amount of energy per beam particle deposited within the target

  20. Development of gradient-corrected exchange-correlation functionals in the density functional theory; Developpement de fonctionnelles corrigees du gradient en theorie de la fonctionnelle de la densite

    Energy Technology Data Exchange (ETDEWEB)

    Lembarki, A.

    1994-12-01

    In this work, we have developed some gradient-corrected exchange-correlation functionals. This study is in keeping with the density functional theory (DFT) formalism. In the first part of this memory, a description of Hartree-Fock (HF), post-HF and density functional theories is given. The second part is devoted the study the different approximations of DFT exchange-correlation functionals which have been proposed in the last years. In particular, we have underlined the approximations used for the construction of these functionals. The third part of this memory consists in the development of new gradient-corrected functionals. In this study, we have established a new relation between exchange energy, correlation energy and kinetic energy. We have deduced two new possible forms of exchange or correlation functionals, respectively. In the fourth part, we have studied the exchange potential, for which the actual formulation does not satisfy some theoretical conditions, such as the asymptotic behavior -1/r. Our contribution lies in the development of an exchange potential with a correct asymptotic -1/r behavior for large values of r. In this chapter, we have proposed a model which permits the obtention of the exchange energy from the exchange potential, using the virial theorem. The fifth part of this memory is devoted the application of these different functionals to simple systems (H{sub 2}O, CO, N{sub 2}O, H{sub 3}{sup +} and H{sub 5}{sup +}) in order to characterize the performance of DFT calculations in regards to those obtained with post-HF methods. (author). 215 refs., 8 figs., 28 tabs.

  1. International Workshop on Electronic Density Functional Theory : Recent Progress and New Directions

    CERN Document Server

    Vignale, Giovanni; Das, Mukunda

    1998-01-01

    This book is an outcome of the International Workshop on Electronic Density Functional Theory, held at Griffith University in Brisbane, Australia, in July 1996. Density functional theory, standing as it does at the boundary between the disciplines of physics, chemistry, and materials science, is a great mixer. Invited experts from North America, Europe, and Australia mingled with students from several disciplines, rapidly taking up the informal style for which Australia is famous. A list of participants is given at the end of the book. Density functional theory (DFT) is a subtle approach to the very difficult problem of predicting the behavior of many interacting particles. A major application is the study of many-electron systems. This was the workshop theme, embracing inter alia computational chemistry and condensed matter physics. DFT circumvents the more conceptually straightforward (but more computationally intensive) approach in which one solves the many-body Schrodinger equation. It relies instead on r...

  2. Foldable, High Energy Density Lithium Ion Batteries

    Science.gov (United States)

    Suresh, Shravan

    Lithium Ion Batteries (LIBs) have become ubiquitous owing to its low cost, high energy density and, power density. Due to these advantages, LIBs have garnered a lot of attention as the primary energy storage devices in consumer electronics and electric vehicles. Recent advances in the consumer electronics research and, the drive to reduce greenhouse gases have created a demand for a shape conformable, high energy density batteries. This thesis focuses on the aforementioned two aspects of LIBs: (a) shape conformability (b) energy density and provides potential solutions to enhance them. This thesis is divided into two parts viz. (i) achieving foldability in batteries and, (ii) improving its energy density. Conventional LIBs are not shape conformable due to two limitations viz. inelasticity of metallic foils, and delamination of the active materials while bending. In the first part of the thesis (in Chapter 3), this problem is solved by replacing metallic current collector with Carbon Nanotube Macrofilms (CNMs). CNMs are superelastic films comprising of porous interconnected nanotube network. Using Molecular Dynamics (MD) simulation, we found that in the presence of an interconnected nanotube network CNMs can be fully folded. This is because the resultant stress due to bending and, the effective bending angle at the interface is reduced due to the network of nanotubes. Hence, unlike an isolated nanotube (which ruptures beyond 120 degrees of bending), a network of nanotubes can be completely folded. Thus, by replacing metallic current collector foils with CNMs, the flexibility limitation of a conventional LIB can be transcended. The second part of this thesis focusses on enhancing the energy density of LIBs. Two strategies adopted to achieve this goal are (a) removing the dead weight of the batteries, and (b) incorporating high energy density electrode materials. By incorporating CNMs, the weight of the batteries was reduced by 5-10 times due to low mass loading of

  3. Plasma Photonic Devices for High Energy Density Science

    International Nuclear Information System (INIS)

    Kodama, R.

    2005-01-01

    High power laser technologies are opening a variety of attractive fields of science and technology using high energy density plasmas such as plasma physics, laboratory astrophysics, material science, nuclear science including medical applications and laser fusion. The critical issues in the applications are attributed to the control of intense light and enormous density of charged particles including efficient generation of the particles such as MeV electrons and protons with a current density of TA/cm2. Now these application possibilities are limited only by the laser technology. These applications have been limited in the control of the high power laser technologies and their optics. However, if we have another device consisted of the 4th material, i.e. plasma, we will obtain a higher energy density condition and explore the application possibilities, which could be called high energy plasma device. One of the most attractive devices has been demonstrated in the fast ignition scheme of the laser fusion, which is cone-guiding of ultra-intense laser light in to high density regions1. This is one of the applications of the plasma device to control the ultra-intense laser light. The other role of the devices consisted of transient plasmas is control of enormous energy-density particles in a fashion analogous to light control with a conventional optical device. A plasma fibre (5?m/1mm), as one example of the devices, has guided and deflected the high-density MeV electrons generated by ultra-intense laser light 2. The electrons have been well collimated with either a lens-like plasma device or a fibre-like plasma, resulting in isochoric heating and creation of ultra-high pressures such as Giga bar with an order of 100J. Plasmas would be uniquely a device to easily control the higher energy density particles like a conventional optical device as well as the ultra-intense laser light, which could be called plasma photonic device. (Author)

  4. Casimir energy density for spherical universes in n-dimensional spacetime

    International Nuclear Information System (INIS)

    Oezcan, Mustafa

    2006-01-01

    We consider the Casimir effect for the massless conformal scalar field in an n-dimensional, closed, static universe. We calculate the renormalized vacuum energy density using the covariant point-splitting method, the mode-sum regularization and the renormalized vacuum energy with the zeta-function regularization. We observe that all odd spacetime dimensions give us the zero renormalized vacuum energy density. For even spacetime dimensions the renormalized vacuum energy density oscillates in sign. The result agrees with three regularization techniques. The Casimir energy density for spherical universes in n-dimensional spacetime is regarded as interesting both to understand the correspondence between the sign of the effect and the dimension of manifold in topology and as a key to confirming the Casimir energy for half spherical universes (manifold with boundary) in n-dimensional spacetime

  5. Computational complexity of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Whitfield, J D; Yung, M-H; Tempel, D G; Aspuru-Guzik, A; Boixo, S

    2014-01-01

    Time-dependent density functional theory (TDDFT) is rapidly emerging as a premier method for solving dynamical many-body problems in physics and chemistry. The mathematical foundations of TDDFT are established through the formal existence of a fictitious non-interacting system (known as the Kohn–Sham system), which can reproduce the one-electron reduced probability density of the actual system. We build upon these works and show that on the interior of the domain of existence, the Kohn–Sham system can be efficiently obtained given the time-dependent density. We introduce a V-representability parameter which diverges at the boundary of the existence domain and serves to quantify the numerical difficulty of constructing the Kohn-Sham potential. For bounded values of V-representability, we present a polynomial time quantum algorithm to generate the time-dependent Kohn–Sham potential with controllable error bounds. (paper)

  6. Reaction energetics on long-range corrected density functional theory: Diels-Alder reactions.

    Science.gov (United States)

    Singh, Raman K; Tsuneda, Takao

    2013-02-15

    The possibility of quantitative reaction analysis on the orbital energies of long-range corrected density functional theory (LC-DFT) is presented. First, we calculated the Diels-Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long-range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long-range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels-Alder reactions quantitatively. After confirming that LC-DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels-Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels-Alder reactions were computed. We noticed that LC-DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO-LUMO gap variations are close to the reaction enthalpies for these Diels-Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. Copyright © 2012 Wiley Periodicals, Inc.

  7. Density Functional Theory (DFT Study of Edaravone Derivatives as Antioxidants

    Directory of Open Access Journals (Sweden)

    Walace G. Leal

    2012-06-01

    Full Text Available Quantum chemical calculations at the B3LYP/6–31G* level of theory were employed for the structure-activity relationship and prediction of the antioxidant activity of edaravone and structurally related derivatives using energy (E, ionization potential (IP, bond dissociation energy (BDE, and stabilization energies (∆Eiso. Spin density calculations were also performed for the proposed antioxidant activity mechanism. The electron abstraction is related to electron-donating groups (EDG at position 3, decreasing the IP when compared to substitution at position 4. The hydrogen abstraction is related to electron-withdrawing groups (EDG at position 4, decreasing the BDECH when compared to other substitutions, resulting in a better antioxidant activity. The unpaired electron formed by the hydrogen abstraction from the C–H group of the pyrazole ring is localized at 2, 4, and 6 positions. The highest scavenging activity prediction is related to the lowest contribution at the carbon atom. The likely mechanism is related to hydrogen transfer. It was found that antioxidant activity depends on the presence of EDG at the C2 and C4 positions and there is a correlation between IP and BDE. Our results identified three different classes of new derivatives more potent than edaravone.

  8. DGDFT: A massively parallel method for large scale density functional theory calculations.

    Science.gov (United States)

    Hu, Wei; Lin, Lin; Yang, Chao

    2015-09-28

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10(-4) Hartree/atom in terms of the error of energy and 6.2 × 10(-4) Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

  9. Dibenzothiophene adsorption at boron doped carbon nanoribbons studied within density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    López-Albarrán, P. [Facultad de Ingeniería en Tecnología de la Madera, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Navarro-Santos, P., E-mail: pnavarrosa@conacyt.mx [Instituto de Investigaciones Químico-Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Garcia-Ramirez, M. A. [Research Centre for Innovation in Aeronautical Engineering, Universidad Autónoma de Nuevo León, Ciudad Universitaria, San Nicolás de los Garza, CP 66451 Nuevo León (Mexico); Ricardo-Chávez, J. L. [Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa San José 2055, Lomas 4" asección, CP 78216, San Luis Potosí, S. L. P. (Mexico)

    2015-06-21

    The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC{sub 3} island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

  10. DGDFT: A massively parallel method for large scale density functional theory calculations

    International Nuclear Information System (INIS)

    Hu, Wei; Yang, Chao; Lin, Lin

    2015-01-01

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10 −4 Hartree/atom in terms of the error of energy and 6.2 × 10 −4 Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail

  11. DGDFT: A massively parallel method for large scale density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Wei, E-mail: whu@lbl.gov; Yang, Chao, E-mail: cyang@lbl.gov [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Lin, Lin, E-mail: linlin@math.berkeley.edu [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Mathematics, University of California, Berkeley, California 94720 (United States)

    2015-09-28

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10{sup −4} Hartree/atom in terms of the error of energy and 6.2 × 10{sup −4} Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

  12. Spin-adapted open-shell time-dependent density functional theory. II. Theory and pilot application.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian; Zhang, Yong; Suo, Bingbing

    2011-04-07

    The excited states of open-shell systems calculated by unrestricted Kohn-Sham-based time-dependent density functional theory (U-TD-DFT) are often heavily spin-contaminated and hence meaningless. This is solved ultimately by the recently proposed spin-adapted time-dependent density functional theory (TD-DFT) (S-TD-DFT) [J. Chem. Phys. 133, 064106 (2010)]. Unlike the standard restricted open-shell Kohn-Sham-based TD-DFT (R-TD-DFT) which can only access the singlet-coupled single excitations, the S-TD-DFT can capture both the singlet- and triplet-coupled single excitations with the same computational effort as the U-TD-DFT. The performances of the three approaches (U-TD-DFT, R-TD-DFT, and S-TD-DFT) are compared for both the spin-conserving and spin-flip excitations of prototypical open-shell systems, the nitrogen (N(2)(+)) and naphthalene (C(10)H(8)(+)) cations. The results show that the S-TD-DFT gives rise to balanced descriptions of excited states of open-shell systems.

  13. A density functional theory study on the interactions between dibenzothiophene and tetrafluoroborate-based ionic liquids.

    Science.gov (United States)

    Lin, Jin; Lü, Renqing; Wu, Chongchong; Xiao, Ye; Liang, Fei; Famakinwa, Temilola

    2017-04-01

    The interactions between dibenzothiophene (DBT) and N-butyl-N-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), N-butyl-N-methylmorpholinium tetrafluoroborate ([Bmmorpholinium][BF 4 ]), N-butyl-N-methylpiperdinium tetrafluoroborate ([BMPiper][BF 4 ]), N-butyl-N-methylpyrrolidinium tetrafluoroborate ([BMPyrro][BF 4 ]), and N-butylpyridinium tetrafluoroborate ([BPY][BF 4 ]) were investigated using density functional theory approach. Geometric, electron, and topological properties were analyzed using natural bond orbital, atoms in molecules theory, and noncovalent interaction methods in order to understand intermolecular interactions between DBT and ionic liquids. The result shows that hydrogen bond and van der Waals interactions are widespread in all the ionic liquids-DBT systems. Ion-π interactions between DBT and cation or anion are also observed, while π + -π interactions are only found in the [BMIM][BF 4 ]-DBT and [BPY][BF 4 ]-DBT systems. The order of interaction energy is [BPY][BF4]-DBT > [BMIM][BF 4 ]-DBT > [BMPiper][BF 4 ]-DBT > [BMPyrro][BF 4 ]-DBT > [BMmorpholinum][BF 4 ]-DBT. The energies between DBT and the two ionic liquids containing aromatic cations are significantly higher.

  14. High-energy behavior of non-Abelian gauge theories

    International Nuclear Information System (INIS)

    Nieh, H.T.; Yao, Y.

    1976-01-01

    This paper is a detailed account of a study in perturbation theory of the high-energy behavior of non-Abelian gauge theories. The fermion-fermion scattering amplitude is calculated up to sixth order in the coupling constant in the high-energy limit s → infinity with fixed t, in the approximation of keeping only the leading logarithmic terms. Results indicate that the high-energy behavior of non-Abelian gauge theories are complicated, and quite different from the known behaviors of other field theories studied so far

  15. Exact vacuum energy of orbifold lattice theories

    International Nuclear Information System (INIS)

    Matsuura, So

    2007-01-01

    We investigate the orbifold lattice theories constructed from supersymmetric Yang-Mills matrix theories (mother theories) with four and eight supercharges. We show that the vacuum energy of these theories does not receive any quantum correction perturbatively

  16. Synthesis, Crystal Structure, Density Function Theory, Molecular ...

    African Journals Online (AJOL)

    Tropical Journal of Pharmaceutical Research ... Purpose: To determine the exact structure and antimicrobial activity of 2-(3-(4 phenylpiperazin-1-yl) ... Besides HOMO– LUMO energy gap was performed at B3LYP/6-31G (d,p) level of theory.

  17. Number theory an introduction via the density of primes

    CERN Document Server

    Fine, Benjamin

    2016-01-01

    Now in its second edition, this textbook provides an introduction and overview of number theory based on the density and properties of the prime numbers. This unique approach offers both a firm background in the standard material of number theory, as well as an overview of the entire discipline. All of the essential topics are covered, such as the fundamental theorem of arithmetic, theory of congruences, quadratic reciprocity, arithmetic functions, and the distribution of primes. New in this edition are coverage of p-adic numbers, Hensel's lemma, multiple zeta-values, and elliptic curve methods in primality testing. Key topics and features include: A solid introduction to analytic number theory, including full proofs of Dirichlet's Theorem and the Prime Number Theorem Concise treatment of algebraic number theory, including a complete presentation of primes, prime factorizations in algebraic number fields, and unique factorization of ideals Discussion of the AKS algorithm, which shows that primality testing is...

  18. Gaussian-3 theory using scaled energies

    International Nuclear Information System (INIS)

    Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C.; Pople, John A.

    2000-01-01

    A modification of Guassian-3 (G3) theory using multiplicative scale factors, instead of the additive higher level correction, is presented. In this method, referred to as G3S, the correlation energy is scaled by five parameters and the Hartree-Fock energy by one parameter. The six parameters are fitted to the G2/97 test set of 299 energies and the resulting mean absolute deviation from experiment is 0.99 kcal/mol compared to 1.01 kcal/mol for G3 theory. The G3S method has the advantage compared to G3 theory in that it can be used for studying potential energy surfaces where the products and reactants have a different number of paired electrons. In addition, versions of the computationally less intensive G3(MP3) and G3(MP2) methods that use scaled energies are also presented. These methods, referred to as G3S(MP3) and G3S(MP2), have mean absolute deviations of 1.16 and 1.35 kcal/mol, respectively. (c) 2000 American Institute of Physics

  19. Prediction of core level binding energies in density functional theory: Rigorous definition of initial and final state contributions and implications on the physical meaning of Kohn-Sham energies.

    Science.gov (United States)

    Pueyo Bellafont, Noèlia; Bagus, Paul S; Illas, Francesc

    2015-06-07

    A systematic study of the N(1s) core level binding energies (BE's) in a broad series of molecules is presented employing Hartree-Fock (HF) and the B3LYP, PBE0, and LC-BPBE density functional theory (DFT) based methods with a near HF basis set. The results show that all these methods give reasonably accurate BE's with B3LYP being slightly better than HF but with both PBE0 and LCBPBE being poorer than HF. A rigorous and general decomposition of core level binding energy values into initial and final state contributions to the BE's is proposed that can be used within either HF or DFT methods. The results show that Koopmans' theorem does not hold for the Kohn-Sham eigenvalues. Consequently, Kohn-Sham orbital energies of core orbitals do not provide estimates of the initial state contribution to core level BE's; hence, they cannot be used to decompose initial and final state contributions to BE's. However, when the initial state contribution to DFT BE's is properly defined, the decompositions of initial and final state contributions given by DFT, with several different functionals, are very similar to those obtained with HF. Furthermore, it is shown that the differences of Kohn-Sham orbital energies taken with respect to a common reference do follow the trend of the properly calculated initial state contributions. These conclusions are especially important for condensed phase systems where our results validate the use of band structure calculations to determine initial state contributions to BE shifts.

  20. New variational formulation of Maxwell-Vlasov and guiding center theories

    International Nuclear Information System (INIS)

    Pfirsch, D.

    1983-07-01

    A new variational formulation of Maxwell-Vlasov and related theories is given in terms of a common Lagrangian density for both the 'Vlasov particles' and the Maxwell fields. This formulation is used to derive in a consistent way, on the one hand, correct charge and current densities and, on the other, corresponding energy and energy flux densities. All of these densities generally show in addition to particle like contributions electric polarization and magnetization terms. By some limiting procedure collisionless guiding center theories with polarization drifts included are also treated. In this way local energy conservation laws are formulated for such theories, which has not been possible up to now. (orig.)

  1. Uncertainty quantification for nuclear density functional theory and information content of new measurements.

    Science.gov (United States)

    McDonnell, J D; Schunck, N; Higdon, D; Sarich, J; Wild, S M; Nazarewicz, W

    2015-03-27

    Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squares optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. The example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.

  2. Relativistic mean field theory with density dependent coupling constants for nuclear matter and finite nuclei with large charge asymmetry

    Energy Technology Data Exchange (ETDEWEB)

    Typel, S; Wolter, H H [Sektion Physik, Univ. Muenchen, Garching (Germany)

    1998-06-01

    Nuclear matter and ground state properties for (proton and neutron) semi-closed shell nuclei are described in relativistic mean field theory with coupling constants which depend on the vector density. The parametrization of the density dependence for {sigma}-, {omega}- and {rho}-mesons is obtained by fitting to properties of nuclear matter and some finite nuclei. The equation of state for symmetric and asymmetric nuclear matter is discussed. Finite nuclei are described in Hartree approximation, including a charge and an improved center-of-mass correction. Pairing is considered in the BCS approximation. Special attention is directed to the predictions for properties at the neutron and proton driplines, e.g. for separation energies, spin-orbit splittings and density distributions. (orig.)

  3. Electron-density critical points analysis and catastrophe theory to forecast structure instability in periodic solids.

    Science.gov (United States)

    Merli, Marcello; Pavese, Alessandro

    2018-03-01

    The critical points analysis of electron density, i.e. ρ(x), from ab initio calculations is used in combination with the catastrophe theory to show a correlation between ρ(x) topology and the appearance of instability that may lead to transformations of crystal structures, as a function of pressure/temperature. In particular, this study focuses on the evolution of coalescing non-degenerate critical points, i.e. such that ∇ρ(x c ) = 0 and λ 1 , λ 2 , λ 3 ≠ 0 [λ being the eigenvalues of the Hessian of ρ(x) at x c ], towards degenerate critical points, i.e. ∇ρ(x c ) = 0 and at least one λ equal to zero. The catastrophe theory formalism provides a mathematical tool to model ρ(x) in the neighbourhood of x c and allows one to rationalize the occurrence of instability in terms of electron-density topology and Gibbs energy. The phase/state transitions that TiO 2 (rutile structure), MgO (periclase structure) and Al 2 O 3 (corundum structure) undergo because of pressure and/or temperature are here discussed. An agreement of 3-5% is observed between the theoretical model and experimental pressure/temperature of transformation.

  4. Optimization theory for ballistic energy conversion

    NARCIS (Netherlands)

    Xie, Yanbo; Versluis, Michel; Van Den Berg, Albert; Eijkel, Jan C.T.

    2016-01-01

    The growing demand of renewable energy stimulates the exploration of new materials and methods for clean energy. We recently demonstrated a high efficiency and power density energy conversion mechanism by using jetted charged microdroplets, termed as ballistic energy conversion. Hereby, we model and

  5. Low-energy meson physics (chiral theory)

    International Nuclear Information System (INIS)

    Volkov, M.K.; Pervushin, V.N.

    1976-01-01

    A quantum chiral theory which allows to obtain low-energy expansions of various hadron processes without introducing arbitrary parameters into the theory with the exception of hadron masses and interaction constants is presented. A hypothesis about the dynamic symmetry of strong interactions is suggested. The interaction lagrangian is derived which satisfies conditions of the dynamic symmetry. Examples of the use of the quantum chiral theory for describing low-energy processes of meson interaction are given. It is noted that the results obtained reproduce the actual qualitative pattern of various physical processes and in most cases result in good quantitative agreement with experiments

  6. Nuclear energy technology: theory and practice of commercial nuclear power

    International Nuclear Information System (INIS)

    Knief, R.A.

    1982-01-01

    Reviews Nuclear Energy Technology: Theory and Practice of Commercial Nuclear Power by Ronald Allen Knief, whose contents include an overview of the basic concepts of reactors and the nuclear fuel cycle; the basics of nuclear physics; reactor theory; heat removal; economics; current concerns at the front and back ends of the fuel cycle; design descriptions of domestic and foreign reactor systems; reactor safety and safeguards; Three Mile Island; and a brief overview of the basic concepts of nuclear fusion. Both magnetic and inertial confinement techniques are clearly outlined. Also reviews Nuclear Fuel Management by Harry W. Graves, Jr., consisting of introductory subjects (e.g. front end of fuel cycle); core physics methodology required for fuel depletion calculations; power capability evaluation (analyzes physical parameters that limit potential core power density); and fuel management topics (economics, loading arrangements and core operation strategies)

  7. Paths to dark energy theory and observation

    CERN Document Server

    Valtonen, Mauri; Chernin, Arthur D; Byrd, Gene

    2012-01-01

    This work provides the current theory and observations behind the cosmological phenomenon of dark energy. The approach is comprehensivewith rigorous mathematical theory and relevant astronomical observations discussed in context.The book treats the background and history starting with the new-found importance of Einstein's cosmological constant (proposed long ago for the opposite purpose) in dark energy formulation, as well as the frontiers of dark energy.

  8. Exact differential equation for the density and ionization energy of a many-particle system

    Science.gov (United States)

    Levy, M.; Perdew, J. P.; Sahni, V.

    1984-01-01

    The present investigation is concerned with relations studied by Hohenberg and Kohn (1964) and Kohn and Sham (1965). The properties of a ground-state many-electron system are determined by the electron density. The correct differential equation for the density, as dictated by density-functional theory, is presented. It is found that the ground-state density n of a many-electron system obeys a Schroedinger-like differential equation which may be solved by standard Kohn-Sham programs. Results are connected to the traditional exact Kohn-Sham theory. It is pointed out that the results of the current investigations are readily extended to spin-density functional theory.

  9. Optimization Parameters and Some Electronic Properties of AlSb Diamondoids: A Density Function Theory Study

    Directory of Open Access Journals (Sweden)

    Hayder M. Abduljalil

    2018-05-01

    Full Text Available Density function theory with LSDA/3-21G basis set is used to investigate the optimization parameters such as (angles and bonds and some electronic properties include (cohesive energy, energy gap and lattice constant of AlSb at nano diamantine and different size of(Linear, Ring, Diamantine and Tetramantine. The results of the present work show that the angles of AlSbH nano molecule in range (96,21-126.05 Å are near to standard angle of diamond (109.47 Å. Therefore, it is found that the cohesive energy for molecules of studied in decrease state with increase size but the energy gap decreased in gradually shape from (5.2-2.1eV with increase of the number of atoms, that typical is on the lattice constant. It is finally shown that the size molecules has direct effect on electronic properties to material studied that can used this material in different applications and according to the purpose asked for

  10. Energy expressions in density-functional theory using line integrals.

    NARCIS (Netherlands)

    van Leeuwen, R.; Baerends, E.J.

    1995-01-01

    In this paper we will address the question of how to obtain energies from functionals when only the functional derivative is given. It is shown that one can obtain explicit expressions for the exchange-correlation energy from approximate exchange-correlation potentials using line integrals along

  11. Time-dependent quantum fluid density functional theory of hydrogen ...

    Indian Academy of Sciences (India)

    A time-dependent generalized non-linear Schrödinger equation (GNLSE) of motion was earlier derived in our laboratory by combining density functional theory and quantum fluid dynamics in threedimensional space. In continuation of the work reported previously, the GNLSE is applied to provide additional knowledge on ...

  12. Statistical properties of kinetic and total energy densities in reverberant spaces

    DEFF Research Database (Denmark)

    Jacobsen, Finn; Molares, Alfonso Rodriguez

    2010-01-01

    Many acoustical measurements, e.g., measurement of sound power and transmission loss, rely on determining the total sound energy in a reverberation room. The total energy is usually approximated by measuring the mean-square pressure (i.e., the potential energy density) at a number of discrete....... With the advent of a three-dimensional particle velocity transducer, it has become somewhat easier to measure total rather than only potential energy density in a sound field. This paper examines the ensemble statistics of kinetic and total sound energy densities in reverberant enclosures theoretically...... positions. The idea of measuring the total energy density instead of the potential energy density on the assumption that the former quantity varies less with position than the latter goes back to the 1930s. However, the phenomenon was not analyzed until the late 1970s and then only for the region of high...

  13. Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

    Science.gov (United States)

    Jin, Zhen; Yang, Meng; Chen, Shao-Hua; Liu, Jin-Huai; Li, Qun-Xiang; Huang, Xing-Jiu

    2017-02-21

    Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO 2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO 2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

  14. Structure and Electronic Properties of Neutral and Negatively Charged RhBn Clusters (n = 3-10): A Density Functional Theory Study.

    Science.gov (United States)

    Li, Peifang; Mei, Tingting; Lv, Linxia; Lu, Cheng; Wang, Weihua; Bao, Gang; Gutsev, Gennady L

    2017-08-31

    The geometrical structure and electronic properties of the neutral RhB n and singly negatively charged RhB n - clusters are obtained in the range of 3 ≤ n ≤ 10 using the unbiased CALYPSO structure search method and density functional theory (DFT). A combination of the PBE0 functional and the def2-TZVP basis set is used for determining global minima on potential energy surfaces of the Rh-doped B n clusters. The photoelectron spectra of the anions are simulated using the time-dependent density functional theory (TD-DFT) method. Good agreement between our simulated and experimentally obtained photoelectron spectra for RhB 9 - provides support to the validity of our theoretical method. The relative stabilities of the ground-state RhB n and RhB n - clusters are estimated using the calculated binding energies, second-order total energy differences, and HOMO-LUMO gaps. It is found that RhB 7 and RhB 8 - are the most stable species in the neutral and anionic series, respectively. The chemical bonding analysis reveals that the RhB 8 - cluster possesses two sets of delocalized σ and π bonds. In both cases, the Hückel 4N + 2 rule is fulfilled and this cluster possesses both σ and π aromaticities.

  15. Modeling of oxygen incorporation in Th, ThC, and ThN by density functional theory calculations

    Science.gov (United States)

    Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.

    2017-12-01

    Oxygen incorporation in nuclear fuel materials is an important issue deserving investigation due to its influence on thermophysical and structural properties. Even if there has been a renewed interest in thorium and thorium compounds in the last years, there is still not much research done on this topic. In this work, we study, by means of density functional theory calculations, the incorporation of oxygen in Th, ThC, and ThN. We analyze the electronic structure finding a characteristic peak to be attributed to oxygen incorporation. We also calculate incorporation and solution energies and obtain migration energies of oxygen through different paths finding that migration through vacancy sites is more energetically favorable than through interstitial ones.

  16. Ab initio density functional theory investigation of electronic properties of semiconducting single-walled carbon nanotube bundles

    Science.gov (United States)

    Moradian, Rostam; Behzad, Somayeh; Azadi, Sam

    2008-09-01

    By using ab initio density functional theory we investigated the structural and electronic properties of semiconducting (7, 0), (8, 0) and (10, 0) carbon nanotube bundles. The energetic and electronic evolutions of nanotubes in the bundling process are also studied. The effects of inter-tube coupling on the electronic dispersions of semiconducting carbon nanotube bundles are demonstrated. Our results show that the inter-tube coupling decreases the energy gap in semiconducting nanotubes. We found that bundles of (7, 0) and (8, 0) carbon nanotubes have metallic feature, while (10, 0) bundle is a semiconductor with an energy gap of 0.22 eV. To clarify our results the band structures of isolated and bundled nanotubes are compared.

  17. High energy behaviour of nonabelian gauge theories

    International Nuclear Information System (INIS)

    Bartels, J.

    1979-10-01

    The high energy behavior (in the Regge limit) of nonabelian gauge theories is reviewed. After a general remark concerning the question to what extent the Regge limit can be approached within perturbation theory, we first review the reggeization of elementary particles within nonabelian gauge theories. Then the derivation of a unitary high energy description of a massive (= spontaneously broken) nonabelian gauge model is described, which results in a complete reggeon calculus. There is strong evidence that the zero mass limit of this reggeon calculus exists, thus giving rise to the hope that the Regge behavior in pure Yang-Mills theories (QCD) can be reached in this way. In the final part of these lectures two possible strategies for solving this reggeon calculus (both for the massive and the massless case) are outlined. One of them leads to a geometrical picture in which the distribution of the wee partons obeys a diffusion law. The other one makes contact with reggeon field theory and predicts that QCD in the high energy limit is described by critical reggeon field theory. (orig.)

  18. The relation between food price, energy density and diet quality

    Directory of Open Access Journals (Sweden)

    Margareta Bolarić

    2013-01-01

    Full Text Available Low energy density diet, high in fruits and vegetables, is related to lower obesity risk and to better health status, but is more expensive. High energy density diet, high in added sugar and fats, is more affordable, but is related to higher obesity and chronic diseases risk. The aim of this study was to report prices according to energy density (low vs. high of food items and to show how food affordability could affect food choice and consumers’ health. Data was collected for 137 raw and processed foods from three purchase sites in Zagreb (one representative for supermarket, one smaller shop and green market. Results showed that low energy density food is more expensive than high energy density food (for example, the price of 1000 kcal from green zucchini (15 kcal/100 g is 124.20 kn while the price of 1000 kcal from sour cream (138 kcal/100 g is 13.99 kn. Food energy price was significantly different (p<0.05 between food groups with highest price for vegetable products (159.04 ± 36.18 kn/1000 kcal and raw vegetables (97.90 ± 50.13 kn/1000 kcal and lowest for fats (8.49 ± 1.22 kn/1000 kcal and cereals and products (5.66 ± 0.76 kn/1000 kcal. Negative correlation (Spearman r=-0.72, p<0.0001 was observed for energy density (kcal/100 g and price of 1000 kcal. Therefore, it is advisable to develop strategies in order to reduce price of low energy density food and encourage its intake since it would improve diet quality, which could lead to better costumers’ health.

  19. Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory

    Science.gov (United States)

    Borah, Mukunda Madhab; Devi, Th. Gomti

    2018-06-01

    The vibrational spectral analysis of Serotonin and its dimer were carried out using the Fourier Transform Infrared (FTIR) and Raman techniques. The equilibrium geometrical parameters, harmonic vibrational wavenumbers, Frontier orbitals, Mulliken atomic charges, Natural Bond orbitals, first order hyperpolarizability and some optimized energy parameters were computed by density functional theory with 6-31G(d,p) basis set. The detailed analysis of the vibrational spectra have been carried out by computing Potential Energy Distribution (PED, %) with the help of Vibrational Energy Distribution Analysis (VEDA) program. The second order delocalization energies E(2) confirms the occurrence of intramolecular Charge Transfer (ICT) within the molecule. The computed wavenumbers of Serotonin monomer and dimer were found in good agreement with the experimental Raman and IR values.

  20. Density functional theory and dynamical mean-field theory. A way to model strongly correlated systems

    International Nuclear Information System (INIS)

    Backes, Steffen

    2017-04-01

    The study of the electronic properties of correlated systems is a very diverse field and has lead to valuable insight into the physics of real materials. In these systems, the decisive factor that governs the physical properties is the ratio between the electronic kinetic energy, which promotes delocalization over the lattice, and the Coulomb interaction, which instead favours localized electronic states. Due to this competition, correlated electronic systems can show unique and interesting properties like the Metal-Insulator transition, diverse phase diagrams, strong temperature dependence and in general a high sensitivity to the environmental conditions. A theoretical description of these systems is not an easy task, since perturbative approaches that do not preserve the competition between the kinetic and interaction terms can only be applied in special limiting cases. One of the most famous approaches to obtain the electronic properties of a real material is the ab initio density functional theory (DFT) method. It allows one to obtain the ground state density of the system under investigation by mapping onto an effective non-interacting system that has to be found self-consistently. While being an exact theory, in practical implementations certain approximations have to be made to the exchange-correlation potential. The local density approximation (LDA), which approximates the exchange-correlation contribution to the total energy by that of a homogeneous electron gas with the corresponding density, has proven quite successful in many cases. Though, this approximation in general leads to an underestimation of electronic correlations and is not able to describe a metal-insulator transition due to electronic localization in the presence of strong Coulomb interaction. A different approach to the interacting electronic problem is the dynamical mean-field theory (DMFT), which is non-perturbative in the kinetic and interaction term but neglects all non

  1. Density functional theory and dynamical mean-field theory. A way to model strongly correlated systems

    Energy Technology Data Exchange (ETDEWEB)

    Backes, Steffen

    2017-04-15

    The study of the electronic properties of correlated systems is a very diverse field and has lead to valuable insight into the physics of real materials. In these systems, the decisive factor that governs the physical properties is the ratio between the electronic kinetic energy, which promotes delocalization over the lattice, and the Coulomb interaction, which instead favours localized electronic states. Due to this competition, correlated electronic systems can show unique and interesting properties like the Metal-Insulator transition, diverse phase diagrams, strong temperature dependence and in general a high sensitivity to the environmental conditions. A theoretical description of these systems is not an easy task, since perturbative approaches that do not preserve the competition between the kinetic and interaction terms can only be applied in special limiting cases. One of the most famous approaches to obtain the electronic properties of a real material is the ab initio density functional theory (DFT) method. It allows one to obtain the ground state density of the system under investigation by mapping onto an effective non-interacting system that has to be found self-consistently. While being an exact theory, in practical implementations certain approximations have to be made to the exchange-correlation potential. The local density approximation (LDA), which approximates the exchange-correlation contribution to the total energy by that of a homogeneous electron gas with the corresponding density, has proven quite successful in many cases. Though, this approximation in general leads to an underestimation of electronic correlations and is not able to describe a metal-insulator transition due to electronic localization in the presence of strong Coulomb interaction. A different approach to the interacting electronic problem is the dynamical mean-field theory (DMFT), which is non-perturbative in the kinetic and interaction term but neglects all non

  2. Toward accurate prediction of potential energy surfaces and the spectral density of hydrogen bonded systems

    International Nuclear Information System (INIS)

    Rekik, Najeh

    2014-01-01

    Despite the considerable progress made in quantum theory and computational methods, detailed descriptions of the potential energy surfaces of hydrogen-bonded systems have not yet been achieved. In addition, the hydrogen bond (H-bond) itself is still so poorly understood at the fundamental level that it remains unclear exactly what geometry constitutes a “real” H-bond. Therefore, in order to investigate features essential for hydrogen bonded complexes, a simple, efficient, and general method for calculating matrix elements of vibrational operators capable of describing the stretching modes and the H-bond bridges of hydrogen-bonded systems is proposed. The derived matrix elements are simple and computationally easy to evaluate, which makes the method suitable for vibrational studies of multiple-well potentials. The method is illustrated by obtaining potential energy surfaces for a number of two-dimensional systems with repulsive potentials chosen to be in Gaussian form for the stretching mode and of the Morse-type for the H-bond bridge dynamics. The forms of potential energy surfaces of weak and strong hydrogen bonds are analyzed by varying the asymmetry of the Gaussian potential. Moreover, the choice and applicability of the selected potential for the stretching mode and comparison with other potentials used in the area of hydrogen bond research are discussed. The approach for the determination of spectral density has been constructed in the framework of the linear response theory for which spectral density is obtained by Fourier transform of the autocorrelation function of the dipole moment operator of the fast mode. The approach involves anharmonic coupling between the high frequency stretching vibration (double well potential) and low-frequency donor-acceptor stretching mode (Morse potential) as well as the electrical anharmonicity of the dipole moment operator of the fast mode. A direct relaxation mechanism is incorporated through a time decaying exponential

  3. High Energy Density Polymer Film Capacitors

    National Research Council Canada - National Science Library

    Boufelfel, Ali

    2006-01-01

    High-energy-density capacitors that are compact and light-weight are extremely valuable in a number of critical DoD systems that include portable field equipment, pulsed lasers, detection equipment...

  4. The energy density distribution of an ideal gas and Bernoulli’s equations

    Science.gov (United States)

    Santos, Leonardo S. F.

    2018-05-01

    This work discusses the energy density distribution in an ideal gas and the consequences of Bernoulli’s equation and the corresponding relation for compressible fluids. The aim of this work is to study how Bernoulli’s equation determines the energy flow in a fluid, although Bernoulli’s equation does not describe the energy density itself. The model from molecular dynamic considerations that describes an ideal gas at rest with uniform density is modified to explore the gas in motion with non-uniform density and gravitational effects. The difference between the component of the speed of a particle that is parallel to the gas speed and the gas speed itself is called ‘parallel random speed’. The pressure from the ‘parallel random speed’ is denominated as parallel pressure. The modified model predicts that the energy density is the sum of kinetic and potential gravitational energy densities plus two terms with static and parallel pressures. The application of Bernoulli’s equation and the corresponding relation for compressible fluids in the energy density expression has resulted in two new formulations. For incompressible and compressible gas, the energy density expressions are written as a function of stagnation, static and parallel pressures, without any dependence on kinetic or gravitational potential energy densities. These expressions of the energy density are the main contributions of this work. When the parallel pressure was uniform, the energy density distribution for incompressible approximation and compressible gas did not converge to zero for the limit of null static pressure. This result is rather unusual because the temperature tends to zero for null pressure. When the gas was considered incompressible and the parallel pressure was equal to static pressure, the energy density maintained this unusual behaviour with small pressures. If the parallel pressure was equal to static pressure, the energy density converged to zero for the limit of the

  5. Derivative discontinuity and exchange-correlation potential of meta-GGAs in density-functional theory.

    Science.gov (United States)

    Eich, F G; Hellgren, Maria

    2014-12-14

    We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state and exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative.

  6. Derivative discontinuity and exchange-correlation potential of meta-GGAs in density-functional theory

    International Nuclear Information System (INIS)

    Eich, F. G.; Hellgren, Maria

    2014-01-01

    We investigate fundamental properties of meta-generalized-gradient approximations (meta-GGAs) to the exchange-correlation energy functional, which have an implicit density dependence via the Kohn-Sham kinetic-energy density. To this purpose, we construct the most simple meta-GGA by expressing the local exchange-correlation energy per particle as a function of a fictitious density, which is obtained by inverting the Thomas-Fermi kinetic-energy functional. This simple functional considerably improves the total energy of atoms as compared to the standard local density approximation. The corresponding exchange-correlation potentials are then determined exactly through a solution of the optimized effective potential equation. These potentials support an additional bound state and exhibit a derivative discontinuity at integer particle numbers. We further demonstrate that through the kinetic-energy density any meta-GGA incorporates a derivative discontinuity. However, we also find that for commonly used meta-GGAs the discontinuity is largely underestimated and in some cases even negative

  7. Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework I: Total energy calculation

    International Nuclear Information System (INIS)

    Lin Lin; Lu Jianfeng; Ying Lexing; Weinan, E

    2012-01-01

    Kohn–Sham density functional theory is one of the most widely used electronic structure theories. In the pseudopotential framework, uniform discretization of the Kohn–Sham Hamiltonian generally results in a large number of basis functions per atom in order to resolve the rapid oscillations of the Kohn–Sham orbitals around the nuclei. Previous attempts to reduce the number of basis functions per atom include the usage of atomic orbitals and similar objects, but the atomic orbitals generally require fine tuning in order to reach high accuracy. We present a novel discretization scheme that adaptively and systematically builds the rapid oscillations of the Kohn–Sham orbitals around the nuclei as well as environmental effects into the basis functions. The resulting basis functions are localized in the real space, and are discontinuous in the global domain. The continuous Kohn–Sham orbitals and the electron density are evaluated from the discontinuous basis functions using the discontinuous Galerkin (DG) framework. Our method is implemented in parallel and the current implementation is able to handle systems with at least thousands of atoms. Numerical examples indicate that our method can reach very high accuracy (less than 1 meV) with a very small number (4–40) of basis functions per atom.

  8. Remarks on saturation of energy confinement in high density regime on LHD

    International Nuclear Information System (INIS)

    Yamada, Hiroshi; Morita, Shigeru; Murakami, Sadayoshi

    2003-01-01

    A study on energy confinement times in currentless helical plasmas has indicated a preferable density dependence like τ E ∝ n-bar e 0.5-0.6 . However, saturation of energy confinement time has been often observed during the density ramping-up phase by gas puffing in NBI heated plasmas in LHD. The power balance analysis indicates that the thermal diffusivity is improved by the increase in local density while the global energy confinement time loses the dependence on the density. The flat or hollow density profile, which is distinguished in the density-ramping phase, promotes a broad heat power deposition. This change explains the apparent contradiction between the density dependence of the thermal diffusivity and the global energy confinement time. This result suggests that central heating can maintain a favorable density dependence of the energy confinement time in the high density regime. (author)

  9. A density functional theory study of the TMG adsorption on the GaN surface

    Energy Technology Data Exchange (ETDEWEB)

    Ptasinska, Maria; Soltys, Jakub; Piechota, Jacek [Interdisciplinary Centre for Materials Modelling, University of Warsaw, ul. Pawinskiego 5a, 02-106 Warszawa (Poland); Krukowski, Stanislaw [Interdisciplinary Centre for Materials Modelling, University of Warsaw, ul. Pawinskiego 5a, 02-106 Warszawa (Poland); Institute of High Pressure Physics, Polish Academy of Sciences, ul. Sokolowska 29/37, 01-142 Warsaw (Poland)

    2011-07-01

    TMG (trimetylogallium) and NH{sub 3} (ammonia) are widely used reactants in the metal organic chemical vapor deposition (MOCVD) technique used in the growth of the GaN thin films. We have recently examined theoretically, with the help of the density functional theory (DFT), TMG adsorption on the GaN(0001) surface in order to study formation of bonds between Ga and N. Dangling bonds on the GaN(0001) surface were saturated with the hydrogen atoms. The slab polarization, which is due to the dangling bonds present on the GaN(0001) surface, and energy of the system in the vicinity of TMG was computed for different distances between the surface atoms and TMG. We also studied TMG diffusion on the GaN surface. As a result, the energy path for diffusion from Top N to Hollow was obtained.

  10. Absorbed dose in AgBr in direct film for photon energies (<150 keV): relation to optical density. Theoretical calculation and experimental evaluation

    International Nuclear Information System (INIS)

    Helmrot, E.; Alm Carlsson, G.

    1996-01-01

    Calculations of absorbed dose in the silver bromide were compared with measurements of optical densities in Ultra-speed and Ektaspeed films for a broad range (25-145 kV) of X-ray energy. The calculated absorbed dose values were appropriately averaged over the complete photon energy spectrum, which was determined experimentally using a Compton spectrometer. For the whole range of tube potentials used, the measured optical densities of the films were found to be proportional to the mean absorbed dose in the AgBr grains calculated according to GREENING's theory. They were also found to be proportional to the collision kerma in silver bromide (K c,AgBr ) indicating proportionality between K c,AgBr and the mean absorbed dose in silver bromide. While GREENING's theory shows that the quotient of the mean absorbed dose in silver bromide and K c,AgBr varies with photon energy, this is not apparent when averaged over the broad (diagnostic) X-ray energy spectra used here. Alternatively, proportionality between K c,AgBr and the mean absorbed dose in silver bromide can be interpreted as resulting from a combination of the SPIERS-CHARLTON theory, valid at low photon energies ( c,AgBr (at the position of the film) independent of photon energy. The importance of taking the complete X-ray energy spectrum into full account in deriving K c,AgBr is clearly demonstrated, showing that the concept of effective energy must be used with care. (orig./HP)

  11. High energy density capacitors fabricated by thin film technology

    International Nuclear Information System (INIS)

    Barbee, T W; Johnson, G W; Wagner, A V.

    1999-01-01

    Low energy density in conventional capacitors severely limits efforts to miniaturize power electronics and imposes design limitations on electronics in general. We have successfully applied physical vapor deposition technology to greatly increase capacitor energy density. The high dielectric breakdown strength we have achieved in alumina thin films allows high energy density to be achieved with this moderately low dielectric constant material. The small temperature dependence of the dielectric constant, and the high reliability, high resistivity, and low dielectric loss of Al 2 O 3 , make it even more appealing. We have constructed single dielectric layer thin film capacitors and shown that they can be stacked to form multilayered structures with no loss in yield for a given capacitance. Control of film growth morphology is critical for achieving the smooth, high quality interfaces between metal and dielectric necessary for device operation at high electric fields. Most importantly, high rate deposition with extremely low particle generation is essential for achieving high energy storage at a reasonable cost. This has been achieved by reactive magnetron sputtering in which the reaction to form the dielectric oxide has been confined to the deposition surface. By this technique we have achieved a yield of over 50% for 1 cm 2 devices with an energy density of 14 J per cubic centimeter of Al 2 O 3 dielectric material in 1.2 kV, 4 nF devices. By further reducing defect density and increasing the dielectric constant of the material, we will be able to increase capacitance and construct high energy density devices to meet the requirements of applications in power electronics

  12. Orientation of rod molecules in selective slits: a density functional theory

    International Nuclear Information System (INIS)

    Xu Xiaofei; Cao Dapeng; Wang Wenchuan

    2008-01-01

    A density functional theory (DFT) is used to investigate molecular orientation of rod fluids in selective slits. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect, the first-order thermodynamics perturbation theory for chain connectivity and the mean-field approximation for van der Waals (vdW) attraction. To study the molecular orientation, the intramolecular bonding orientation function is introduced into the DFT. First, we investigate the orientation of the surfactant-like rod molecule of AB 6 (i.e. ABBBBBB) in a nanoslit of H 20σ, where the walls selectively adsorb segment 'A'. It is observed that, with the increase of the surface energy of the wall to head segment (i.e. 'A' segment) of the rod molecule, the rod molecules adsorbed on the wall present the perpendicular orientation gradually, and assemble into a smectic-A-like monolayer finally. In addition, we also explore the molecular orientation of the rods with both end segments preferring to the wall, i.e. AB 8 A and AB 7 A, in a nanoslit of H = 10σ. Interestingly, the AB 8 A rod monolayer is compatible with either a smectic-A-like or a smectic-C-like organization, but AB 7 A rod molecules exhibit the smectic-A-like organization. The orientation factor of the AB 7 A rod molecule reaches 1, suggesting that AB 7 A rod molecules self-assemble into an ordered structure with perfectly perpendicular orientation to the wall.

  13. Semi-local machine-learned kinetic energy density functional with third-order gradients of electron density

    Science.gov (United States)

    Seino, Junji; Kageyama, Ryo; Fujinami, Mikito; Ikabata, Yasuhiro; Nakai, Hiromi

    2018-06-01

    A semi-local kinetic energy density functional (KEDF) was constructed based on machine learning (ML). The present scheme adopts electron densities and their gradients up to third-order as the explanatory variables for ML and the Kohn-Sham (KS) kinetic energy density as the response variable in atoms and molecules. Numerical assessments of the present scheme were performed in atomic and molecular systems, including first- and second-period elements. The results of 37 conventional KEDFs with explicit formulae were also compared with those of the ML KEDF with an implicit formula. The inclusion of the higher order gradients reduces the deviation of the total kinetic energies from the KS calculations in a stepwise manner. Furthermore, our scheme with the third-order gradient resulted in the closest kinetic energies to the KS calculations out of the presented functionals.

  14. Long-range corrected density functional theory with accelerated Hartree-Fock exchange integration using a two-Gaussian operator [LC-ωPBE(2Gau)].

    Science.gov (United States)

    Song, Jong-Won; Hirao, Kimihiko

    2015-10-14

    Since the advent of hybrid functional in 1993, it has become a main quantum chemical tool for the calculation of energies and properties of molecular systems. Following the introduction of long-range corrected hybrid scheme for density functional theory a decade later, the applicability of the hybrid functional has been further amplified due to the resulting increased performance on orbital energy, excitation energy, non-linear optical property, barrier height, and so on. Nevertheless, the high cost associated with the evaluation of Hartree-Fock (HF) exchange integrals remains a bottleneck for the broader and more active applications of hybrid functionals to large molecular and periodic systems. Here, we propose a very simple yet efficient method for the computation of long-range corrected hybrid scheme. It uses a modified two-Gaussian attenuating operator instead of the error function for the long-range HF exchange integral. As a result, the two-Gaussian HF operator, which mimics the shape of the error function operator, reduces computational time dramatically (e.g., about 14 times acceleration in C diamond calculation using periodic boundary condition) and enables lower scaling with system size, while maintaining the improved features of the long-range corrected density functional theory.

  15. Fifth International Conference on High Energy Density Physics

    Energy Technology Data Exchange (ETDEWEB)

    Beg, Farhat

    2017-07-05

    The Fifth International Conference on High Energy Density Physics (ICHED 2015) was held in the Catamaran Hotel in San Diego from August 23-27, 2015. This meeting was the fifth in a series which began in 2008 in conjunction with the April meeting of the American Physical Society (APS). The main goal of this conference has been to bring together researchers from all fields of High Energy Density Science (HEDS) into one, unified meeting.

  16. Optical excitation and electron relaxation dynamics at semiconductor surfaces: a combined approach of density functional and density matrix theory applied to the silicon (001) surface

    Energy Technology Data Exchange (ETDEWEB)

    Buecking, N

    2007-11-05

    In this work a new theoretical formalism is introduced in order to simulate the phononinduced relaxation of a non-equilibrium distribution to equilibrium at a semiconductor surface numerically. The non-equilibrium distribution is effected by an optical excitation. The approach in this thesis is to link two conventional, but approved methods to a new, more global description: while semiconductor surfaces can be investigated accurately by density-functional theory, the dynamical processes in semiconductor heterostructures are successfully described by density matrix theory. In this work, the parameters for density-matrix theory are determined from the results of density-functional calculations. This work is organized in two parts. In Part I, the general fundamentals of the theory are elaborated, covering the fundamentals of canonical quantizations as well as the theory of density-functional and density-matrix theory in 2{sup nd} order Born approximation. While the formalism of density functional theory for structure investigation has been established for a long time and many different codes exist, the requirements for density matrix formalism concerning the geometry and the number of implemented bands exceed the usual possibilities of the existing code in this field. A special attention is therefore attributed to the development of extensions to existing formulations of this theory, where geometrical and fundamental symmetries of the structure and the equations are used. In Part II, the newly developed formalism is applied to a silicon (001)surface in a 2 x 1 reconstruction. As first step, density-functional calculations using the LDA functional are completed, from which the Kohn-Sham-wave functions and eigenvalues are used to calculate interaction matrix elements for the electron-phonon-coupling an the optical excitation. These matrix elements are determined for the optical transitions from valence to conduction bands and for electron-phonon processes inside the

  17. States of high energy density

    International Nuclear Information System (INIS)

    Murray, M.

    1988-02-01

    The transverse energy, E/sub tau/ spectra for O 16 and S 32 incident for various elements at 200 GeVnucleon are shown. The target and projectile dependencies of the data are discussed. The energy density achieved is estimated. For O 16 on Tungsten the multiplicity spectrum is also presented as well as the pseudorapidity spectra as a function of the transverse energy. The multiplicity cross section dσdN as measured in the backward hemisphere (0.9 < /eta/ < 2.9/ is found to be very similar in shape to the transverse energy distribution dσdE/tau/ reflecting the particular geometry of nucleus nucleus nucleus collisions. The dependence on the atomic mass of the target, A/sub tau/ and projectile A/sub p/ is not what one would expect from naive considerations

  18. Calculations with the quasirelativistic local-spin-density-functional theory for high-Z atoms

    International Nuclear Information System (INIS)

    Guo, Y.; Whitehead, M.A.

    1988-01-01

    The generalized-exchange local-spin-density-functional theory (LSD-GX) with relativistic corrections of the mass velocity and Darwin terms has been used to calculate statistical total energies for the neutral atoms, the positive ions, and the negative ions for high-Z elements. The effect of the correlation and relaxation correction on the statistical total energy is discussed. Comparing the calculated results for the ionization potentials and electron affinities for the atoms (atomic number Z from 37 to 56 and 72 to 80) with experiment, shows that for the atoms rubidium to barium both the LSD-GX and the quasirelativistic LSD-GX, with self-interaction correction, Gopinathan, Whitehead, and Bogdanovic's Fermi-hole parameters [Phys. Rev. A 14, 1 (1976)], and Vosko, Wilk, and Nusair's correlation correction [Can. J. Phys. 58, 1200 (1980)], are very good methods for calculating ionization potentials and electron affinities. For the atoms hafnium to mercury the relativistic effect has to be considered

  19. Improved modification for the density-functional theory calculation of thermodynamic properties for C-H-O composite compounds.

    Science.gov (United States)

    Liu, Min Hsien; Chen, Cheng; Hong, Yaw Shun

    2005-02-08

    A three-parametric modification equation and the least-squares approach are adopted to calibrating hybrid density-functional theory energies of C(1)-C(10) straight-chain aldehydes, alcohols, and alkoxides to accurate enthalpies of formation DeltaH(f) and Gibbs free energies of formation DeltaG(f), respectively. All calculated energies of the C-H-O composite compounds were obtained based on B3LYP6-311++G(3df,2pd) single-point energies and the related thermal corrections of B3LYP6-31G(d,p) optimized geometries. This investigation revealed that all compounds had 0.05% average absolute relative error (ARE) for the atomization energies, with mean value of absolute error (MAE) of just 2.1 kJ/mol (0.5 kcal/mol) for the DeltaH(f) and 2.4 kJ/mol (0.6 kcal/mol) for the DeltaG(f) of formation.

  20. Thermodynamic Characterization of Hydration Sites from Integral Equation-Derived Free Energy Densities: Application to Protein Binding Sites and Ligand Series.

    Science.gov (United States)

    Güssregen, Stefan; Matter, Hans; Hessler, Gerhard; Lionta, Evanthia; Heil, Jochen; Kast, Stefan M

    2017-07-24

    Water molecules play an essential role for mediating interactions between ligands and protein binding sites. Displacement of specific water molecules can favorably modulate the free energy of binding of protein-ligand complexes. Here, the nature of water interactions in protein binding sites is investigated by 3D RISM (three-dimensional reference interaction site model) integral equation theory to understand and exploit local thermodynamic features of water molecules by ranking their possible displacement in structure-based design. Unlike molecular dynamics-based approaches, 3D RISM theory allows for fast and noise-free calculations using the same detailed level of solute-solvent interaction description. Here we correlate molecular water entities instead of mere site density maxima with local contributions to the solvation free energy using novel algorithms. Distinct water molecules and hydration sites are investigated in multiple protein-ligand X-ray structures, namely streptavidin, factor Xa, and factor VIIa, based on 3D RISM-derived free energy density fields. Our approach allows the semiquantitative assessment of whether a given structural water molecule can potentially be targeted for replacement in structure-based design. Finally, PLS-based regression models from free energy density fields used within a 3D-QSAR approach (CARMa - comparative analysis of 3D RISM Maps) are shown to be able to extract relevant information for the interpretation of structure-activity relationship (SAR) trends, as demonstrated for a series of serine protease inhibitors.