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Sample records for density-functional theory electronic

  1. Multistate Density Functional Theory for Effective Diabatic Electronic Coupling.

    Science.gov (United States)

    Ren, Haisheng; Provorse, Makenzie R; Bao, Peng; Qu, Zexing; Gao, Jiali

    2016-06-16

    Multistate density functional theory (MSDFT) is presented to estimate the effective transfer integral associated with electron and hole transfer reactions. In this approach, the charge-localized diabatic states are defined by block localization of Kohn-Sham orbitals, which constrain the electron density for each diabatic state in orbital space. This differs from the procedure used in constrained density functional theory that partitions the density within specific spatial regions. For a series of model systems, the computed transfer integrals are consistent with experimental data and show the expected exponential attenuation with the donor-acceptor separation. The present method can be used to model charge transfer reactions including processes involving coupled electron and proton transfer.

  2. Excitations and benchmark ensemble density functional theory for two electrons

    CERN Document Server

    Pribram-Jones, Aurora; Trail, John R; Burke, Kieron; Needs, Richard J; Ullrich, Carsten A

    2014-01-01

    A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the Hartree energy and the choice of degenerate eigenstates is explored. A new approximation, spin eigenstate Hartree-exchange (SEHX), is derived. Exact conditions that are proven include the signs of the correlation energy components, the virial theorem for both exchange and correlation, and the asymptotic behavior of the potential for small weights of the excited states. Many energy components are given as a function of the weights for two electrons in a one-dimensional flat box, in a box with a large barrier to create charge transfer excitations, in a three-dimensional harmonic well (Hooke's atom), and for the He atom singlet-triplet ensemble, singlet-triplet-singlet ensemble, and triplet bi-ensemble.

  3. Excitations and benchmark ensemble density functional theory for two electrons

    Energy Technology Data Exchange (ETDEWEB)

    Pribram-Jones, Aurora; Burke, Kieron [Department of Chemistry, University of California-Irvine, Irvine, California 92697 (United States); Yang, Zeng-hui; Ullrich, Carsten A. [Department of Physics and Astronomy, University of Missouri, Columbia, Missouri 65211 (United States); Trail, John R.; Needs, Richard J. [Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, Cambridge CB3 0HE (United Kingdom)

    2014-05-14

    A new method for extracting ensemble Kohn-Sham potentials from accurate excited state densities is applied to a variety of two-electron systems, exploring the behavior of exact ensemble density functional theory. The issue of separating the Hartree energy and the choice of degenerate eigenstates is explored. A new approximation, spin eigenstate Hartree-exchange, is derived. Exact conditions that are proven include the signs of the correlation energy components and the asymptotic behavior of the potential for small weights of the excited states. Many energy components are given as a function of the weights for two electrons in a one-dimensional flat box, in a box with a large barrier to create charge transfer excitations, in a three-dimensional harmonic well (Hooke's atom), and for the He atom singlet-triplet ensemble, singlet-triplet-singlet ensemble, and triplet bi-ensemble.

  4. 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...... moments are computed using the same geometries (MP2/6-31G*) and basis set (TZVP) as in our previous ab initio benchmark study on electronically excited states. The results from TD-DFT (with the functionals BP86, B3LYP, and BHLYP) and from DFT/MRCI are compared against the previous high-level ab initio...

  5. The electron-propagator approach to conceptual density-functional theory

    Indian Academy of Sciences (India)

    Junia Melin; Paul W Ayers; J V Ortiz

    2005-09-01

    Both electron propagator theory and density-functional theory provide conceptually useful information about chemical reactivity and, most especially, charge transfer. This paper elucidates thequalitative and quantitative links between the two theories, with emphasis on how the reactivity indicators of conceptual density-functional theory can be derived from electron propagator theory. Electron propagator theory could be used to compute reactivity indices with high accuracy at reasonable computational cost.

  6. 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...

  7. Partition density functional theory

    Science.gov (United States)

    Nafziger, Jonathan

    Partition density functional theory (PDFT) is a method for dividing a molecular electronic structure calculation into fragment calculations. The molecular density and energy corresponding to Kohn Sham density-functional theory (KS-DFT) may be exactly recovered from these fragments. Each fragment acts as an isolated system except for the influence of a global one-body 'partition' potential which deforms the fragment densities. In this work, the developments of PDFT are put into the context of other fragment-based density functional methods. We developed three numerical implementations of PDFT: One within the NWChem computational chemistry package using basis sets, and the other two developed from scratch using real-space grids. It is shown that all three of these programs can exactly reproduce a KS-DFT calculation via fragment calculations. The first of our in-house codes handles non-interacting electrons in arbitrary one-dimensional potentials with any number of fragments. This code is used to explore how the exact partition potential changes for different partitionings of the same system and also to study features which determine which systems yield non-integer PDFT occupations and which systems are locked into integer PDFT occupations. The second in-house code, CADMium, performs real-space calculations of diatomic molecules. Features of the exact partition potential are studied for a variety of cases and an analytical formula determining singularities in the partition potential is derived. We introduce an approximation for the non-additive kinetic energy and show how this quantity can be computed exactly. Finally a PDFT functional is developed to address the issues of static correlation and delocalization errors in approximations within DFT. The functional is applied to the dissociation of H2 + and H2.

  8. Quantal Density Functional Theory II

    CERN Document Server

    Sahni, Viraht

    2009-01-01

    Discusses approximation methods and applications of Quantal Density Functional Theory (QDFT), a local effective-potential-energy theory of electronic structure. This book describes approximations methods based on the incorporation of different electron correlations, as well as a many-body perturbation theory within the context of QDFT

  9. Multiconfiguration Pair-Density Functional Theory Is as Accurate as CASPT2 for Electronic Excitation.

    Science.gov (United States)

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

    2016-02-04

    A correct description of electronically excited states is critical to the interpretation of visible-ultraviolet spectra, photochemical reactions, and excited-state charge-transfer processes in chemical systems. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory and a new kind of density functional called an on-top density functional. Here, we show that MC-PDFT with a first-generation on-top density functional performs as well as CASPT2 for an organic chemistry database including valence, Rydberg, and charge-transfer excitations. The results are very encouraging for practical applications.

  10. 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...

  11. 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 co...

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

    Science.gov (United States)

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

    2012-08-01

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

  14. Quantum Electronic Stress: Density-Functional-Theory Formulation and Physical Manifestation

    Science.gov (United States)

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

    2012-08-01

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

  15. Electronic and structural investigation of buckled antimonene using density functional theory calculation

    Science.gov (United States)

    Khan, Md Shahzad; Ratn, Rahul; Srivastava, Anurag

    2017-07-01

    Electronic and structural analysis of buckled antimonene has been performed using density functional theory-based ab-initio approach. Geometrical parameters such as bond length and bond angle are very close to the single ruffle layer of rhombohedral antimony. Phonon dispersion along the high symmetry point of the Brillouin zone does not signify any soft mode. Electronic indirect band gap of 1.61 eV is observed for the single-layer antimonene. However, the occurrence of bilayered quasi-2D sheet consequent to metallic behaviour is due to significant electronic charge dispersion between interlayer region.

  16. Electronic and structural investigation of buckled antimonene using density functional theory calculation

    Indian Academy of Sciences (India)

    MD SHAHZAD KHAN; RAHUL RATN; ANURAG SRIVASTAVA

    2017-07-01

    Electronic and structural analysis of buckled antimonene has been performed using density functional theory-based $\\it{ab-initio}$ approach. Geometrical parameters such as bond length and bond angle are very close to the single ruffle layer of rhombohedral antimony. Phonon dispersion along the high symmetry point of the Brillouin zone does not signify any soft mode. Electronic indirect band gap of 1.61 eV is observed for the single-layer antimonene. However, the occurrence of bilayered quasi-2D sheet consequent to metallic behaviour is due to significant electronic charge dispersion between interlayer region.

  17. 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.

  18. Density functional theory/molecular mechanics approach for electronic g-tensors of solvated molecules.

    Science.gov (United States)

    Rinkevicius, Zilvinas; Murugan, N Arul; Kongsted, Jacob; Aidas, Kestutis; Steindal, Arnfinn Hykkerud; Agren, Hans

    2011-04-21

    A general density functional theory/molecular mechanics approach for computation of electronic g-tensors of solvated molecules is presented. We apply the theory to the commonly studied di-tert-butyl nitroxide molecule, the simplest model compound for nitroxide spin labels, and explore the role of an aqueous environment and of various approximations for its treatment. It is found that successive improvements of the solvent shift of the g-tensor are obtained by going from the polarizable continuum model to discrete solvent models of various levels of sophistication. The study shows that an accurate parametrization of the electrostatic potential and polarizability of the solvent molecules in terms of distributed multipole expansions and anisotropic polarizabilities to a large degree relieves the need to explicitly include water molecules in the quantum region, which is the common case in density functional/continuum model approaches. It is also shown that the local dynamics of the solvent around the solute significantly influences the electronic g-tensor and should be included in benchmarking of exchange-correlation functionals for evaluation of solvent shifts of g-tensors. These findings can have important ramifications for the use of advanced hybrid density functional theory/molecular mechanics approaches for modeling spin labels in solvents, proteins, and membrane environments.

  19. Effective electron displacements: A tool for time-dependent density functional theory computational spectroscopy

    Science.gov (United States)

    Guido, Ciro A.; Cortona, Pietro; Adamo, Carlo

    2014-03-01

    We extend our previous definition of the metric Δr for electronic excitations in the framework of the time-dependent density functional theory [C. A. Guido, P. Cortona, B. Mennucci, and C. Adamo, J. Chem. Theory Comput. 9, 3118 (2013)], by including a measure of the difference of electronic position variances in passing from occupied to virtual orbitals. This new definition, called Γ, permits applications in those situations where the Δr-index is not helpful: transitions in centrosymmetric systems and Rydberg excitations. The Γ-metric is then extended by using the Natural Transition Orbitals, thus providing an intuitive picture of how locally the electron density changes during the electronic transitions. Furthermore, the Γ values give insight about the functional performances in reproducing different type of transitions, and allow one to define a "confidence radius" for GGA and hybrid functionals.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-04-20

    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.

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

    Science.gov (United States)

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

    2009-04-14

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

  2. Ab initio downfolding for electron-phonon-coupled systems: Constrained density-functional perturbation theory

    Science.gov (United States)

    Nomura, Yusuke; Arita, Ryotaro

    2015-12-01

    We formulate an ab initio downfolding scheme for electron-phonon-coupled systems. In this scheme, we calculate partially renormalized phonon frequencies and electron-phonon coupling, which include the screening effects of high-energy electrons, to construct a realistic Hamiltonian consisting of low-energy electron and phonon degrees of freedom. We show that our scheme can be implemented by slightly modifying the density functional-perturbation theory (DFPT), which is one of the standard methods for calculating phonon properties from first principles. Our scheme, which we call the constrained DFPT, can be applied to various phonon-related problems, such as superconductivity, electron and thermal transport, thermoelectricity, piezoelectricity, dielectricity, and multiferroicity. We believe that the constrained DFPT provides a firm basis for the understanding of the role of phonons in strongly correlated materials. Here, we apply the scheme to fullerene superconductors and discuss how the realistic low-energy Hamiltonian is constructed.

  3. 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 modeled...... 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....

  4. Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules

    DEFF Research Database (Denmark)

    Hubert, Mickaël; Hedegård, Erik D.; Jensen, Hans Jørgen Aa

    2016-01-01

    inadequate when the molecule has near-degeneracies and/or low-lying double-excited states. To address these issues we have recently proposed multiconfiguration short-range density-functional theory-MC-srDFT-as a new tool in the toolbox. While initial applications for systems with multireference character......-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2...

  5. Electronic and magnetic properties of Pd-Ni multilayers: Study using density functional theory

    Science.gov (United States)

    Gómez, Guillermina; Cabeza, Gabriela F.; Belelli, Patricia G.

    2009-10-01

    Electronic and magnetic properties of Pd-Ni multilayers have been studied using VASP method in the framework of the density functional theory (DFT). The calculations performed for different configurations (Pd n/Ni m(1 1 1), where n Pd layers are piled up over m Ni layers with n=0 to 4 and n+m=4), reveal that the important magnetic moment of Ni is significantly enhanced according as n increases due to hybridization effects between Pd and Ni mostly localized at the interface. The results also indicate that the Pd atoms are strongly polarized in the studied systems when compared with the pure metal.

  6. Electronic and magnetic properties of Pd-Ni multilayers: Study using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Gomez, Guillermina [Grupo de Materiales y Sistemas Cataliticos, Departamento de Fisica, Universidad Nacional del Sur, Avda. Alem 1253, Bahia Blanca, B8000CPB (Argentina); Cabeza, Gabriela F. [CONICET (Argentina)], E-mail: gcabeza@uns.edu.ar; Belelli, Patricia G. [CONICET (Argentina)

    2009-10-15

    Electronic and magnetic properties of Pd-Ni multilayers have been studied using VASP method in the framework of the density functional theory (DFT). The calculations performed for different configurations (Pd{sub n}/Ni{sub m}(1 1 1), where n Pd layers are piled up over m Ni layers with n=0 to 4 and n+m=4), reveal that the important magnetic moment of Ni is significantly enhanced according as n increases due to hybridization effects between Pd and Ni mostly localized at the interface. The results also indicate that the Pd atoms are strongly polarized in the studied systems when compared with the pure metal.

  7. A density-functional theory study of tip electronic structures in scanning tunneling microscopy.

    Science.gov (United States)

    Choi, Heesung; Longo, Roberto C; Huang, Min; Randall, John N; Wallace, Robert M; Cho, Kyeongjae

    2013-03-15

    In this work, we report a detailed analysis of the atomic and electronic structures of transition metal scanning tunneling microscopy tips: Rh, Pd, W, Ir, and Pt pyramidal models, and transition metal (TM) atom tips supported on the W surface, by means of ab initio density-functional theory methods. The d electrons of the apex atoms of the TM tips (Rh, Pd, W, Ir, and Pt tetrahedral structures) show different behaviors near the Fermi level and, especially for the W tip, dz(2) states are shown to be predominant near the Fermi level. The electronic structures of larger pyramidal TM tip structures with a single apex atom are also reported. Their obtained density of states are thoroughly discussed in terms of the different d-electron occupations of the TM tips.

  8. Density Functional Theory Based on the Electron Distribution on the Energy Coordinate

    CERN Document Server

    Takahashi, Hideaki

    2016-01-01

    We introduced a new electron density n({\\epsilon}) by projecting the spatial electron density n(r) onto the energy coordinate {\\epsilon} defined with the external potential \\upsion (r) of interest. Then, a density functional theory (DFT) was formulated, where n({\\epsilon}) serves as a fundamental variable for the electronic energy. It was demonstrated that the Kohn-Sham equation can also be adapted to the DFT that employs the density n({\\epsilon}) as an argument to the exchange energy functional. An important attribute of the energy density is that it involves the spatially non-local population of the spin-adapted density n(r) at the bond dissociation. By taking advantage of this property we developed a prototype of the static correlation functional employing no empirical parameters, which realized a reasonable dissociation curve for H2 molecule.

  9. Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

    Energy Technology Data Exchange (ETDEWEB)

    Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurelien; Blumberger, Jochen; Elstner, Marcus

    2016-10-11

    In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

  10. Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.

    Science.gov (United States)

    Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurélien; Blumberger, Jochen; Elstner, Marcus

    2016-10-11

    In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

  11. The Density Functional Theory Study of Structural and Electronical Properties of ZnO Clusters

    Directory of Open Access Journals (Sweden)

    O.V. Bovgyra

    2013-03-01

    Full Text Available Density functional theory studies of structural and electronic properties of small clusters were performed. For each cluster an optimization of structure and the basic properties of the band structure were conducted. It was determined that with increasing (n energetically more efficient in the small clusters is stabilization from the ring to fulleren-like structures containing tetragonal and hexagonal faces and all atoms have coordination number equal three. Among the clusters (ZnO12 with doped atoms most stable are clusters where Zn was replaced by Mn, Cu and Co atoms. Band gap in the electronic spectrum of doped clusters decreases due to p-d hybridization orbitals of the impurity atom with the orbitals of the oxygen atom.

  12. The appropriateness of density-functional theory for the calculation of molecular electronics properties.

    Science.gov (United States)

    Reimers, Jeffrey R; Cai, Zheng-Li; Bilić, Ante; Hush, Noel S

    2003-12-01

    As molecular electronics advances, efficient and reliable computation procedures are required for the simulation of the atomic structures of actual devices, as well as for the prediction of their electronic properties. Density-functional theory (DFT) has had widespread success throughout chemistry and solid-state physics, and it offers the possibility of fulfilling these roles. In its modern form it is an empirically parameterized approach that cannot be extended toward exact solutions in a prescribed way, ab initio. Thus, it is essential that the weaknesses of the method be identified and likely shortcomings anticipated in advance. We consider four known systematic failures of modern DFT: dispersion, charge transfer, extended pi conjugation, and bond cleavage. Their ramifications for molecular electronics applications are outlined and we suggest that great care is required when using modern DFT to partition charge flow across electrode-molecule junctions, screen applied electric fields, position molecular orbitals with respect to electrode Fermi energies, and in evaluating the distance dependence of through-molecule conductivity. The causes of these difficulties are traced to errors inherent in the types of density functionals in common use, associated with their inability to treat very long-range electron correlation effects. Heuristic enhancements of modern DFT designed to eliminate individual problems are outlined, as are three new schemes that each represent significant departures from modern DFT implementations designed to provide a priori improvements in at least one and possible all problem areas. Finally, fully semiempirical schemes based on both Hartree-Fock and Kohn-Sham theory are described that, in the short term, offer the means to avoid the inherent problems of modern DFT and, in the long term, offer competitive accuracy at dramatically reduced computational costs.

  13. Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules.

    Science.gov (United States)

    Hubert, Mickaël; Hedegård, Erik D; Jensen, Hans Jørgen Aa

    2016-05-10

    Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn-Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become inadequate when the molecule has near-degeneracies and/or low-lying double-excited states. To address these issues we have recently proposed multiconfiguration short-range density-functional theory-MC-srDFT-as a new tool in the toolbox. While initial applications for systems with multireference character and double excitations have been promising, it is nevertheless important that the accuracy of MC-srDFT is at least comparable to the best KS-DFT methods also for organic molecules that are typically of single-reference character. In this paper we therefore systematically investigate the performance of MC-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2, NEVPT2, and the coupled cluster based CC2 and CC3.

  14. Density functional perturbational orbital theory of spin polarization in electronic systems. II. Transition metal dimer complexes.

    Science.gov (United States)

    Seo, Dong-Kyun

    2007-11-14

    We present a theoretical scheme for a semiquantitative analysis of electronic structures of magnetic transition metal dimer complexes within spin density functional theory (DFT). Based on the spin polarization perturbational orbital theory [D.-K. Seo, J. Chem. Phys. 125, 154105 (2006)], explicit spin-dependent expressions of the spin orbital energies and coefficients are derived, which allows to understand how spin orbitals form and change their energies and shapes when two magnetic sites are coupled either ferromagnetically or antiferromagnetically. Upon employment of the concept of magnetic orbitals in the active-electron approximation, a general mathematical formula is obtained for the magnetic coupling constant J from the analytical expression for the electronic energy difference between low-spin broken-symmetry and high-spin states. The origin of the potential exchange and kinetic exchange terms based on the one-electron picture is also elucidated. In addition, we provide a general account of the DFT analysis of the magnetic exchange interactions in compounds for which the active-electron approximation is not appropriate.

  15. Ab initio density functional theory investigation of structural and electronic properties of silicon carbide nanotube bundles

    Energy Technology Data Exchange (ETDEWEB)

    Moradian, Rostam [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Science and Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Department of Nano Science, Computational Physical Science Research Laboratory, Institute for Studies in Theoretical Physics and Mathematics (IPM), P.O. Box 19395-5531, Tehran (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)

    2008-10-01

    By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius.

  16. Ground and low-lying excited electronic states of graphene flakes: a density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Tachikawa, Hiroto; Kawabata, Hiroshi, E-mail: hiroto@eng.hokudai.ac.jp [Division of Materials Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628 (Japan)

    2011-10-28

    Structures and electronic states of graphene flakes (finite and small sized graphenes) have been investigated by means of the density functional theory method. Sizes of graphene flakes examined in this study were n = 7, 10, 14, 19, 29 and 44, where n is the number of benzene rings in the graphene flake. The excitation energies of graphene flakes decreased gradually as a function of the number of the ring (n). The orbitals of the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) are localized in the edge region of the graphene flake. It was found that the edge region can react with a water molecule and H{sub 2}O is dissociated into OH radical and hydrogen atom (H) without an activation barrier. A lithium ion can bind strongly to the edge region. The ability of the edge region in the graphene flakes was discussed on the basis of theoretical results.

  17. Large-scale all-electron density functional theory calculations using an enriched finite element basis

    CERN Document Server

    Kanungo, Bikash

    2016-01-01

    We present a computationally efficient approach to perform large-scale all-electron density functional theory calculations by enriching the classical finite element basis with compactly supported atom-centered numerical basis functions that are constructed from the solution of the Kohn-Sham (KS) problem for single atoms. We term these numerical basis functions as enrichment functions, and the resultant basis as the enriched finite element basis. The enrichment functions are compactly supported through the use of smooth cutoff functions, which enhances the conditioning and maintains the locality of the basis. The integrals involved in the evaluation of the discrete KS Hamiltonian and overlap matrix in the enriched finite element basis are computed using an adaptive quadrature grid based on the characteristics of enrichment functions. Further, we propose an efficient scheme to invert the overlap matrix by using a block-wise matrix inversion in conjunction with special reduced-order quadrature rules to transform...

  18. 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 ...

  19. 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 ...

  20. Quantum electrodynamical time-dependent density functional theory for many-electron systems on a lattice

    Science.gov (United States)

    Farzanehpour, Mehdi; Tokatly, Ilya; Nano-Bio Spectroscopy Group; ETSF Scientific Development Centre Team

    2015-03-01

    We present a rigorous formulation of the time-dependent density functional theory for interacting lattice electrons strongly coupled to cavity photons. We start with an example of one particle on a Hubbard dimer coupled to a single photonic mode, which is equivalent to the single mode spin-boson model or the quantum Rabi model. For this system we prove that the electron-photon wave function is a unique functional of the electronic density and the expectation value of the photonic coordinate, provided the initial state and the density satisfy a set of well defined conditions. Then we generalize the formalism to many interacting electrons on a lattice coupled to multiple photonic modes and prove the general mapping theorem. We also show that for a system evolving from the ground state of a lattice Hamiltonian any density with a continuous second time derivative is locally v-representable. Spanish Ministry of Economy and Competitiveness (Grant No. FIS2013-46159-C3-1-P), Grupos Consolidados UPV/EHU del Gobierno Vasco (Grant No. IT578-13), COST Actions CM1204 (XLIC) and MP1306 (EUSpec).

  1. Kinetic energies to analyze the experimental auger electron spectra by density functional theory calculations

    Science.gov (United States)

    Endo, Kazunaka

    2016-02-01

    In the Auger electron spectra (AES) simulations, we define theoretical modified kinetic energies of AES in the density functional theory (DFT) calculations. The modified kinetic energies correspond to two final-state holes at the ground state and at the transition-state in DFT calculations, respectively. This method is applied to simulate Auger electron spectra (AES) of 2nd periodic atom (Li, Be, B, C, N, O, F)-involving substances (LiF, beryllium, boron, graphite, GaN, SiO2, PTFE) by deMon DFT calculations using the model molecules of the unit cell. Experimental KVV (valence band electrons can fill K-shell core holes or be emitted during KVV-type transitions) AES of the (Li, O) atoms in the substances agree considerably well with simulation of AES obtained with the maximum kinetic energies of the atoms, while, for AES of LiF, and PTFE substance, the experimental F KVV AES is almost in accordance with the spectra from the transitionstate kinetic energy calculations.

  2. Density functional theory study of mixed-phase TiO₂: heterostructures and electronic properties.

    Science.gov (United States)

    Li, Wei-Kun; Hu, Peijun; Lu, Guanzhong; Gong, Xue-Qing

    2014-04-01

    In this work, density functional theory calculations have been performed to study the geometric, electronic, and energetic properties of two-phase TiO₂ composites built by joining two single-phase TiO₂ slabs, aiming at verifying possible improvement of the photo-activities of the composites through phase separation of excitons. We find that such desired electronic properties can be determined by several factors. When both the HOMO and LUMO levels of one of the two single-phase TiO₂ slabs are higher than the corresponding ones of the other, the composite may have native electronic structures with phase-separated HOMO-LUMO states, especially when the two slabs exhibit highly matched surface lattices. For those pairs of TiO₂ slabs with the HOMO and LUMO levels of one phase being within the range of those of the other, though the energetically favored composite give HOMO-LUMO states within one phase, one may still be able to separate them and move the HOMO state to the interface region by destabilizing the interactions between the two slabs.

  3. A revised electronic Hessian for approximate time-dependent density functional theory.

    Science.gov (United States)

    Ziegler, Tom; Seth, Michael; Krykunov, Mykhaylo; Autschbach, Jochen

    2008-11-14

    Time-dependent density functional theory (TD-DFT) at the generalized gradient level of approximation (GGA) has shown systematic errors in the calculated excitation energies. This is especially the case for energies representing electron transitions between two separated regions of space or between orbitals of different spatial extents. It will be shown that these limitations can be attributed to the electronic ground state Hessian G(GGA). Specifically, we shall demonstrate that the Hessian G(GGA) can be used to describe changes in energy due to small perturbations of the electron density (Deltarho), but it should not be applied to one-electron excitations involving the density rearrangement (Deltarho) of a full electron charge. This is in contrast to Hartree-Fock theory where G(HF) has a trust region that is accurate for both small perturbations and one-electron excitations. The large trust radius of G(HF) can be traced back to the complete cancellation of Coulomb and exchange terms in Hartree-Fock (HF) theory representing self-interaction (complete self-interaction cancellation, CSIC). On the other hand, it is shown that the small trust radius for G(GGA) can be attributed to the fact that CSIC is assumed for GGA in the derivation of G(GGA) although GGA (and many other approximate DFT schemes) exhibits incomplete self-interaction cancellation (ISIC). It is further shown that one can derive a new matrix G(R-DFT) with the same trust region as G(HF) by taking terms due to ISIC properly into account. Further, with TD-DFT based on G(R-DFT), energies for state-to-state transitions represented by a one-electron excitation (psi(i)-->psi(a)) are approximately calculated as DeltaE(ai). Here DeltaE(ai) is the energy difference between the ground state Kohn-Sham Slater determinant and the energy of a Kohn-Sham Slater determinant where psi(i) has been replaced by psi(a). We make use of the new Hessian in two numerical applications involving charge-transfer excitations. It is

  4. Correlated electron dynamics and memory in time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, Mark

    2009-07-28

    Time-dependent density functional theory (TDDFT) is an exact reformulation of the time-dependent many-electron Schroedinger equation, where the problem of many interacting electrons is mapped onto the Kohn-Sham system of noninteracting particles which reproduces the exact electronic density. In the Kohn-Sham system all non-classical many-body effects are incorporated in the exchange-correlation potential which is in general unknown and needs to be approximated. It is the goal of this thesis to investigate the connection between memory effects and correlated electron dynamics in strong and weak fields. To this end one-dimensional two-electron singlet systems are studied. At the same time these systems include the onedimensional helium atom model, which is an established system to investigate the crucial effects of correlated electron dynamics in external fields. The studies presented in this thesis show that memory effects are negligible for typical strong field processes. Here the approximation of the spatial nonlocality is of primary importance. For the photoabsorption spectra on the other hand the neglect of memory effects leads to qualitative and quantitative errors, which are shown to be connected to transitions of double excitation character. To develop a better understanding of the conditions under which memory effects become important quantum fluid dynamics has been found to be especially suitable. It represents a further exact reformulation of the quantum mechanic many-body problem which is based on hydrodynamic quantities such as density and velocity. Memory effects are shown to be important whenever the velocity field develops strong gradients and dissipative effects contribute. (orig.)

  5. Factors Influencing Mean Inner Potentials As Studied Using Electron Holography and Density Functional Theory

    DEFF Research Database (Denmark)

    Pennington, Robert S.

    to analyze diffraction effects on the amplitude and the phase. There is relatively good comparison between image simulation and experimental data, but the experimental absorption parameter is found to differ between strongly and weakly diffracting conditions. Density functional theory simulations of the mean...

  6. A density functional theory investigation of the electronic structure and spin moments of magnetite

    KAUST Repository

    Noh, Junghyun

    2014-08-01

    We present the results of density functional theory (DFT) calculations on magnetite, Fe3O4, which has been recently considered as electrode in the emerging field of organic spintronics. Given the nature of the potential applications, we evaluated the magnetite room-temperature cubic phase in terms of structural, electronic, and magnetic properties. We considered GGA (PBE), GGA + U (PBE + U), and range-separated hybrid (HSE06 and HSE(15%)) functionals. Calculations using HSE06 and HSE(15%) functionals underline the impact that inclusion of exact exchange has on the electronic structure. While the modulation of the band gap with exact exchange has been seen in numerous situations, the dramatic change in the valence band nature and states near the Fermi level has major implications for even a qualitative interpretation of the DFT results. We find that HSE06 leads to highly localized states below the Fermi level while HSE(15%) and PBE + U result in delocalized states around the Fermi level. The significant differences in local magnetic moments and atomic charges indicate that describing room-temperature bulk materials, surfaces and interfaces may require different functionals than their low-temperature counterparts.

  7. A density functional theory investigation of the electronic structure and spin moments of magnetite

    Science.gov (United States)

    Noh, Junghyun; Osman, Osman I; Aziz, Saadullah G; Winget, Paul; Brédas, Jean-Luc

    2014-01-01

    We present the results of density functional theory (DFT) calculations on magnetite, Fe3O4, which has been recently considered as electrode in the emerging field of organic spintronics. Given the nature of the potential applications, we evaluated the magnetite room-temperature cubic phase in terms of structural, electronic, and magnetic properties. We considered GGA (PBE), GGA + U (PBE + U), and range-separated hybrid (HSE06 and HSE(15%)) functionals. Calculations using HSE06 and HSE(15%) functionals underline the impact that inclusion of exact exchange has on the electronic structure. While the modulation of the band gap with exact exchange has been seen in numerous situations, the dramatic change in the valence band nature and states near the Fermi level has major implications for even a qualitative interpretation of the DFT results. We find that HSE06 leads to highly localized states below the Fermi level while HSE(15%) and PBE + U result in delocalized states around the Fermi level. The significant differences in local magnetic moments and atomic charges indicate that describing room-temperature bulk materials, surfaces and interfaces may require different functionals than their low-temperature counterparts. PMID:27877697

  8. Geometries, stabilities and electronic properties of copper and selenium doped copper clusters: Density functional theory study

    Science.gov (United States)

    Li, Cheng-Gang; Zhang, Jie; Yuan, Yu-Quan; Tang, Ya-Nan; Ren, Bao-Zeng; Chen, Wei-Guang

    2017-02-01

    The structures properties of Cun+1 and CunSe clusters have been investigated using an unbiased CALYPSO structure searching method. Firstly, an unbiased search relying on several structurally different initial clusters have been undertaken. Subsequently, geometry optimization by means of density functional theory is carried out to determine the relative stability of various candidates for low lying clusters obtained from the unconstrained search. The results shown that the ground state Cu9 cluster is found to prefer a unique and previously unrecognized structure, with the total energies much lower than all structures proposed in the literature so far. The Cu2Se cluster is the most stable geometries for CunSe clusters. Additionally, the calculated HOMO-LUMO gaps ranges from 1.27 to 2.85 eV, which make CunSe clusters suitable candidates in photocatalyst materials. Lastly, the molecular orbital energy and density of states; the adaptive natural density partitioning; the electron localization function, localized orbital locator and Mayer Bond order are also studied for the ground state to develop a deeper understanding on the electronic properties.

  9. Electronic structures of one-dimensional poly-fused selenophene radical cations: density functional theory study

    Directory of Open Access Journals (Sweden)

    Hiroshi Kawabata et al

    2008-01-01

    Full Text Available Hybrid density functional theory (DFT calculations have been carried out for neutral and radical cation species of a fused selenophene oligomer, denoted by Se(n, where n represents the number of selenophene rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused selenophene was also investigated using one-dimensional periodic boundary conditions (PBC for comparison. It was found that the reorganization energy of a radical cation of Se(n from a vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that Se(n has an effective intramolecular hole transport property. It was found that the radical cation species of Se(n has a low-energy band in the near-IR region, which is strongly correlated to hole conductivity. The relationship between the electronic states and intramolecular hole conductivity was discussed on the basis of theoretical calculations.

  10. Electronic density functional theory in the grand canonical ensemble, electrochemistry, and the underpotential deposition of Cu/Pt(111)

    Science.gov (United States)

    Sundararaman, Ravishankar; Weaver, Kendra; Arias, Tomas

    2012-02-01

    The study of electrochemical systems within electronic density functional theory requires the handling of non-neutral electronic systems in the plane-wave basis in order to accurately describe charged metallic surfaces; this can be accomplished in joint density functional theory by adding an electrolyte with Debye screening ootnotetextK. L. Weaver and T. A. Arias (under preparation). This capability opens up the opportunity to work in the grand canonical ensemble at fixed chemical potential μ for the electrons, which corresponds directly to the experimental setting in electrochemistry. We present efficient techniques for electronic density functional calculations at fixed μ, and demonstrate the improvement in predictive power over conventional neutral calculations using the underpotential deposition of Cu/Pt(111) as an example: for the first time, we calculate absolute voltages for electrochemical processes in excellent agreement with experiment, instead of voltage shifts alone.

  11. Electronic structure and optical properties of TbPO4: Experiment and density functional theory calculations

    Science.gov (United States)

    Khadraoui, Z.; Horchani-Naifer, K.; Ferhi, M.; Ferid, M.

    2015-09-01

    Single crystals of TbPO4 were grown by high temperature solid-state reaction and identified by means of X-ray diffraction, infrared and Raman spectroscopies analysis. The electronic properties of TbPO4 such as the energy band structures, density of states were carried out using density functional theory (DFT). We have employed the LDA+U functional to treat the exchange correlation potential by solving Kohn-Sham equation. The calculated total and partial density of states indicate that the top of valance band is mainly built upon O-2p states and the bottom of the conduction band mostly originates from Tb-5d states. The population analysis indicates that the P-O bond was mainly covalent and Tb-O bond was mainly ionic. The emission spectrum, color coordinates and decay curve were employed to reveal the luminescence properties of TbPO4. Moreover, the optical properties including the dielectric function, absorption spectrum, refractive index, extinction coefficient, reflectivity and energy-loss spectrum are investigated and analyzed. The results are discussed and compared with the available experimental data.

  12. Structural, elastic, electronic, and thermodynamic properties of MgAgSb investigated by density functional theory

    Science.gov (United States)

    Wang, Jun-Fei; Fu, Xiao-Nan; Zhang, Xiao-Dong; Wang, Jun-Tao; Li, Xiao-Dong; Jiang, Zhen-Yi

    2016-08-01

    The structural, elastic, electronic, and thermodynamic properties of thermoelectric material MgAgSb in γ,β,α phases are studied with first-principles calculations based on density functional theory. The optimized lattice constants accord well with the experimental data. According to the calculated total energy of the three phases, the phase transition order is determined from α to γ phase with cooling, which is in agreement with the experimental result. The physical properties such as elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, and anisotropy factor are also discussed and analyzed, which indicates that the three structures are mechanically stable and each has a ductile feature. The Debye temperature is deduced from the elastic properties. The total density of states (TDOS) and partial density of states (PDOS) of the three phases are investigated. The TDOS results show that the γ phase is most stable with a pseudogap near the Fermi level, and the PDOS analysis indicates that the conduction band of the three phases is composed mostly of Mg-3s, Ag-4d, and Sb-5p. In addition, the changes of the free energy, entropy, specific heat, thermal expansion of γ-MgAgSb with temperature are obtained successfully. The obtained results above are important parameters for further experimental and theoretical tuning of doped MgAgSb as a thermoelectric material at high temperature. Project supported by the National Natural Science Foundation of China (Grant No. 11504088), the Fund from Henan University of Technology, China (Grant Nos. 2014YWQN08 and 2013JCYJ12), the Natural Science Fund from the Henan Provincial Education Department, China (Grant No. 16A140027), the Natural Science Foundation of Shaanxi Province of China (Grant Nos. 2013JQ1018 and 15JK1759), and the Science Foundation of Northwest University of China (Grant No. 14NW23).

  13. Electronic band structure of Cu(2)O by spin density functional theory.

    Science.gov (United States)

    French, M; Schwartz, R; Stolz, H; Redmer, R

    2009-01-07

    The band structure of Cu(2)O is calculated using density functional theory in the generalized gradient approximation. By taking spin-orbit coupling into account the split between the Γ(7)(+) and the Γ(8)(+) valence band states is obtained as 128 meV. The highest valence band shows a noticeable nonparabolicity close to the Γ point. This is important for the quantitative description of excitons in this material, which is considered to be the best candidate for the confirmation that Bose-Einstein condensation also occurs in excitonic systems.

  14. Time-dependent density-functional theory for open electronic systems

    Institute of Scientific and Technical Information of China (English)

    ZHENG Xiao; WANG RuLin

    2014-01-01

    Time-dependent density-functional theory(TDDFT)has been successfully applied to predict excited-state properties of isolated and periodic systems.However,it cannot address a system coupled to an environment or whose number of electrons is not conserved.To tackle these problems,TDDFT needs to be extended to accommodate open systems.This paper provides a comprehensive account of the recent developments of TDDFT for open systems(TDDFT-OS),including both theoretical and practical aspects.The practicality and accuracy of a latest TDDFT-OS method is demonstrated with two numerical examples:the time-dependent electron transport through a series of quasi-one-dimensional atomic chains,and the real-time electronic dynamics on a two-dimensional graphene surface.The advancement of TDDFT-OS may lead to promising applications in various fields of chemistry,including energy conversion and heterogeneous catalysis.

  15. Electronic structure modeling of InAs/GaSb superlattices with hybrid density functional theory

    Science.gov (United States)

    Garwood, T.; Modine, N. A.; Krishna, S.

    2017-03-01

    The application of first-principles calculations holds promise for greatly improving our understanding of semiconductor superlattices. Developing a procedure to accurately predict band gaps using hybrid density functional theory lays the groundwork for future studies investigating more nuanced properties of these structures. Our approach allows a priori prediction of the properties of SLS structures using only the band gaps of the constituent materials. Furthermore, it should enable direct investigation of the effects of interface structure, e.g., intermixing or ordering at the interface, on SLS properties. In this paper, we present band gap data for various InAs/GaSb type-II superlattice structures calculated using the generalized Kohn-Sham formulation of density functional theory. A PBE0-type hybrid functional was used, and the portion of the exact exchange was tuned to fit the band gaps of the binary compounds InAs and GaSb with the best agreement to bulk experimental values obtained with 18% of the exact exchange. The heterostructures considered in this study are 6 monolayer (ML) InAs/6 ML GaSb, 8 ML InAs/8 ML GaSb and 10 ML InAs/10 ML GaSb with deviations from the experimental band gaps ranging from 3% to 11%.

  16. Semiclassics in Density Functional Theory

    Science.gov (United States)

    Lee, Donghyung; Cangi, Attila; Elliott, Peter; Burke, Kieron

    2009-03-01

    Recently, we published an article [1] about the semiclassical origin of density functional theory. We showed that the density and the kinetic energy density of one dimensional finite systems with hard walls can be expressed in terms of the external potential using the semiclassical Green's function method. Here, we show a uniformization scheme for the semiclassical density and the kinetic energy density for turning-point problems.[1] P. Elliott, D. Lee, A. Cangi, and K. Burke, Phys. Rev. Lett. 100, 256406 (2008).

  17. Magnetic properties of f-electron systems in spin-polarized relativistic density functional theory

    Science.gov (United States)

    Yamagami, H.; Mavromaras, A.; Kübler, J.

    1997-12-01

    The magnetic ground state of the series of lanthanide and actinide trivalent ions is investigated by means of spin-polarized relativistic spin-density functional theory. In the local density functional approximation (LDA) an internal effective magnetic field due to exchange and correlation couples to the spin degrees of freedom. The resulting set of coupled Dirac equations yields ground-state multiplets that obey the well-known Hund's rules. This remarkable result comes about by the coupling of the j = l + 1/2 with the j = l - 1/2 states due to the exchange - correlation potential that is, as usual, the functional derivative of the exchange - correlation energy with respect to the spin magnetic moment. The effect of the coupling is shown to depend on the varying relative strengths of spin - orbit coupling and exchange splitting within the f series. Since in the f levels the internal exchange splitting dominates rather than the spin - orbit splitting, the energy level scheme is that of the Paschen - Back effect, and thus features of the Russell - Saunders coupling persist in spite of relativistic effects.

  18. Electronic and vibrational properties of graphene monolayers with iron adatoms: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Dimakis, Nicholas, E-mail: dimakis@utpa.edu [Department of Physics and Geology, University of Texas-Pan American, Edinburg, TX (United States); Navarro, Nestor E. [Department of Chemistry, University of Texas-Pan American, Edinburg, TX (United States); Velazquez, Julian; Salgado, Andres [Department of Physics and Geology, University of Texas-Pan American, Edinburg, TX (United States)

    2015-04-15

    Highlights: • Periodic density functional calculations were performed on graphene monolayers with and without an iron adatom. • Densities of states, charge transfers, and overlap populations were used to elucidate the effects of weak iron adsorption on graphene compared to CO adsorption on Pt. • Infrared intensities and normal mode analysis verify weak iron adsorption on graphene by studying the shift in prominent vibrational modes and changes in lattice dynamics. - Abstract: Periodic density functional calculations on graphene monolayers with and without an iron adatom have been used to elucidate iron-graphene adsorption and its effects on graphene electronic and vibrational properties. Density-of-states calculations and charge density contour plots reveal charge transfer from the iron s orbitals to the d orbitals, in agreement with past reports. Adsorbed iron atoms covalently bind to the graphene substrate, verified by the strong hybridization of iron d-states with the graphene bands in the energy region just below the Fermi level. This adsorption is weak and compared to the well-analyzed CO adsorption on Pt: It is indicated by its small adsorption energy and the minimal change of the substrate geometry due to the presence of the iron adatoms. Graphene vibrational spectra are analyzed though a systematic variation of the graphene supercell size. The shifts of graphene most prominent infrared active vibrational modes due to iron adsorption are explored using normal mode eigenvectors.

  19. Geometries, stabilities, and electronic properties of Be-doped gold clusters: a density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Chen Dong-Dong; Kuang Xiao-Yu; Zhao Ya-Ru; Shao Peng; Li Yan-Fang

    2011-01-01

    We have systematically investigated the geometrical structures, relative stabilities and electronic properties of small bimetallic AunBe (n = 1, 2, ..., 8) clusters using a density functional method at BP86 level. The optimized geometries reveal that the impurity beryllium atom dramatically affects the structures of the Aun clusters. The averaged binding energies, fragmentation energies, second-order difference of energies, the highest occupied-lowest unoccupied molecular orbital energy gaps and chemical hardness are investigated. All of them exhibit a pronounced odd-even alternation,manifesting that the clusters with even number of gold atoms possess relatively higher stabilities. Especially, the linear Au2Be cluster is magic cluster with the most stable chemical stability. According to the natural population analysis, it is found that charge-transferring direction between Au atom and Be atom changes at the size of n = 4.

  20. A multiconfigurational hybrid density-functional theory

    CERN Document Server

    Sharkas, Kamal; Jensen, Hans Jørgen Aa; Toulouse, Julien; 10.1063/1.4733672

    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 of the usual hybrid approximations by essentially adding a fraction \\lambda of exact static correlation in addition to the fraction \\lambda of exact exchange. Test calculations on the cycloaddition reactions of ozone with ethylene or acetylene and the dissociation of diatomic molecules with the Perdew-Burke-Ernzerhof (PBE) and Becke-Lee-Yang-Parr (BLYP) density functionals show that a good value of \\lambda is 0.25, as in the usual hybrid approximations. The results suggest that the proposed multiconfigurational hybrid approximations can improve over usual density-functional calculations for situations with strong static correlation effects.

  1. Multiconfiguration Pair-Density Functional Theory.

    Science.gov (United States)

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

    2014-09-09

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

  2. Assessment of oscillator strengths with multiconfigurational short-range density functional theory for electronic excitations in organic molecules

    DEFF Research Database (Denmark)

    Hedegård, Erik Donovan

    2017-01-01

    considered the large collection of organic molecules whose excited states were investigated with a range of electronic structure methods by Thiel et al. As a by-product of our calculations of oscillator strengths, we also obtain electronic excitation energies, which enable us to compare the performance......We have in a series of recent papers investigated electronic excited states with a hybrid between a complete active space self-consistent field (CASSCF) wave function and density functional theory (DFT). This method has been dubbed the CAS short-range DFT method (CAS–srDFT). The previous papers...

  3. Connection formula for thermal density functional theory

    CERN Document Server

    Pribram-Jones, Aurora

    2015-01-01

    The adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upwards from the system's physical temperature to infinite temperatures. Several formulas yield one component of the thermal correlation free energy in terms of another, many of which can be expressed either in terms of temperature- or coupling-constant integration. We illustrate with the uniform electron gas.

  4. Electronic structure and physical properties of ScN in pressure: density-functional theory calculations

    Institute of Scientific and Technical Information of China (English)

    Guan Peng-Fei; Wang Chong-Yu; Yu Tao

    2008-01-01

    Local density functional is investigated by using the full-potential linearized augmented plane wave (FP-LAPW) method for ScN in the hexagonal structure and the rocksalt structure and for hexagonal structures linking a layered hexagonal phase with wurtzite structure along a homogeneous strain transition path. It is found that the wurtzite ScN is unstable and the layered hexagonal phase, labelled as ho, in which atoms are approximately fivefold coordinated,is metastable, and the rocksalt ScN is stable. The electronic structure, the physical properties of the intermediate structures and the energy band structure along the transition are presented. It is found that the band gaps change from 4.0 to 1.0eV continuously when c/a value varies from 1.68 to 1.26. It is noticeable that the study of ScN provides an opportunity to apply this kind of material (in wurtzite[h]-derived phase).

  5. exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory

    Science.gov (United States)

    Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian; Nabok, Dmitrii; Pavone, Pasquale; Rigamonti, Santiago; Sagmeister, Stephan; Werner, Ute; Draxl, Claudia

    2014-09-01

    Linearized augmented planewave methods are known as the most precise numerical schemes for solving the Kohn-Sham equations of density-functional theory (DFT). In this review, we describe how this method is realized in the all-electron full-potential computer package, exciting. We emphasize the variety of different related basis sets, subsumed as (linearized) augmented planewave plus local orbital methods, discussing their pros and cons and we show that extremely high accuracy (microhartrees) can be achieved if the basis is chosen carefully. As the name of the code suggests, exciting is not restricted to ground-state calculations, but has a major focus on excited-state properties. It includes time-dependent DFT in the linear-response regime with various static and dynamical exchange-correlation kernels. These are preferably used to compute optical and electron-loss spectra for metals, molecules and semiconductors with weak electron-hole interactions. exciting makes use of many-body perturbation theory for charged and neutral excitations. To obtain the quasi-particle band structure, the GW approach is implemented in the single-shot approximation, known as G0W0. Optical absorption spectra for valence and core excitations are handled by the solution of the Bethe-Salpeter equation, which allows for the description of strongly bound excitons. Besides these aspects concerning methodology, we demonstrate the broad range of possible applications by prototypical examples, comprising elastic properties, phonons, thermal-expansion coefficients, dielectric tensors and loss functions, magneto-optical Kerr effect, core-level spectra and more.

  6. Electronic structures of one-dimensional metal-molecule hybrid chains studied using scanning tunneling microscopy and density functional theory.

    Science.gov (United States)

    Chung, Kyung-Hoon; Koo, Bon-Gil; Kim, Howon; Yoon, Jong Keon; Kim, Ji-Hoon; Kwon, Young-Kyun; Kahng, Se-Jong

    2012-05-28

    The electronic structures of self-assembled hybrid chains comprising Ag atoms and organic molecules were studied using scanning tunneling microscopy (STM) and spectroscopy (STS) in parallel with density functional theory (DFT). Hybrid chains were prepared by catalytic breaking of Br-C bonds in 4,4″-dibromo-p-terphenyl molecules, followed by spontaneous formation of Ag-C bonds on Ag(111). An atomic model was proposed for the observed hybrid chain structures. Four electronic states were resolved using STS measurements, and strong energy dependence was observed in STM images. These results were explained using first-principles calculations based on DFT.

  7. On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation

    CERN Document Server

    Fromager, Emmanuel

    2014-01-01

    The exact formulation of multi-configuration density-functional theory (DFT) is discussed in this work. As an alternative to range-separated methods, where electron correlation effects are split in the coordinate space, the combination of Configuration Interaction methods with orbital occupation functionals is explored at the formal level through the separation of correlation effects in the orbital space. When applied to model Hamiltonians, this approach leads to an exact Site-Occupation Embedding Theory (SOET). An adiabatic connection expression is derived for the complementary bath functional and a comparison with Density Matrix Embedding Theory (DMET) is made. Illustrative results are given for the simple two-site Hubbard model. SOET is then applied to a quantum chemical Hamiltonian, thus leading to an exact Complete Active Space Site-Occupation Functional Theory (CASSOFT) where active electrons are correlated explicitly within the CAS and the remaining contributions to the correlation energy are described...

  8. 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.

  9. Search for the ground-state electronic configurations of correlated organometallic metallocenes from constraint density functional theory

    Science.gov (United States)

    Nawa, Kenji; Kitaoka, Yukie; Nakamura, Kohji; Imamura, Hiroshi; Akiyama, Toru; Ito, Tomonori; Weinert, M.

    2016-07-01

    The ground-state electronic configurations of the correlated organometallic metallocenes, M Cp2,M =V , Cr, Mn, Fe, Co, and Ni, are investigated using constraint density functional theory combined with nonempirical Ueff parameters determined from linear-response theory. The relative stability of the various d -orbital electronic configurations of these organometallic molecules is found to be sensitive to the amount of correlation. Using nonempirical values of Ueff, the calculated electronic configurations are in agreement with the experiments: 4A2 g ,3E2 g ,6A1 g ,1A1 g ,2E1 g , and 3A2 g for the VCp2,CrCp2,MnCp2,FeCp2,CoCp2 , and NiCp2, respectively.

  10. Electron-Ion Dynamics with Time-Dependent Density Functional Theory: Towards Predictive Solar Cell Modeling: Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Maitra, Neepa [Hunter College City University of New York, New York, NY (United States)

    2016-07-14

    This project investigates the accuracy of currently-used functionals in time-dependent density functional theory, which is today routinely used to predict and design materials and computationally model processes in solar energy conversion. The rigorously-based electron-ion dynamics method developed here sheds light on traditional methods and overcomes challenges those methods have. The fundamental research undertaken here is important for building reliable and practical methods for materials discovery. The ultimate goal is to use these tools for the computational design of new materials for solar cell devices of high efficiency.

  11. Electronic coupling matrix elements from charge constrained density functional theory calculations using a plane wave basis set

    Science.gov (United States)

    Oberhofer, Harald; Blumberger, Jochen

    2010-12-01

    We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT). Following the work of Wu and Van Voorhis [J. Chem. Phys. 125, 164105 (2006)], the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q-) anion. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The thermal average, ( { } )^{1/2} = 6.7 {mH}, is significantly higher than the value obtained for the minimum energy structure, | {H_ab } | = 3.8 {mH}. While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q- in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.

  12. 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

  13. Density Functional Theory Study on the Electronic Structures of Oxadiazole Based Dyes as Photosensitizer for Dye Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Umer Mehmood

    2015-01-01

    Full Text Available The molecular structures and UV-visible absorption spectra of complex photosensitizers comprising oxadiazole isomers as the π-bridges were analyzed by density functional theory (DFT and time-dependent DFT. The ground state and excited state oxidation potentials, HOMOs and LUMOs energy levels, and electron injection from the dyes to semiconductor TiO2 have been computed in vacuum here. The results show that all of the dyes may potentially be good photosensitizers in DSSC. To justify the simulation basis, N3 dye was also simulated under the similar conditions. Simulated absorption spectrum, HOMO, LUMO, and band gap values of N3 were compared with the experimental values. We also computed the electronic structure properties and absorption spectra of dye/(TiO28 systems to elucidate the electron injection efficiency at the interface. This work is expected to give proper orientation for experimental synthesis.

  14. Examining real-time time-dependent density functional theory nonequilibrium simulations for the calculation of electronic stopping power

    Science.gov (United States)

    Yost, Dillon C.; Yao, Yi; Kanai, Yosuke

    2017-09-01

    In ion irradiation processes, electronic stopping power describes the energy transfer rate from the irradiating ion to the target material's electrons. Due to the scarcity and significant uncertainties in experimental electronic stopping power data for materials beyond simple solids, there has been growing interest in the use of first-principles theory for calculating electronic stopping power. In recent years, advances in high-performance computing have opened the door to fully first-principles nonequilibrium simulations based on real-time time-dependent density functional theory (RT-TDDFT). While it has been demonstrated that the RT-TDDFT approach is capable of predicting electronic stopping power for a wide range of condensed matter systems, there has yet to be an exhaustive examination of the physical and numerical approximations involved and their effects on the calculated stopping power. We discuss the results of such a study for crystalline silicon with protons as irradiating ions. We examine the influences of key approximations in RT-TDDFT nonequilibrium simulations on the calculated electronic stopping power, including approximations related to basis sets, finite size effects, exchange-correlation approximation, pseudopotentials, and more. Finally, we propose a simple and efficient correction scheme to account for the contribution from core-electron excitations to the stopping power, as it was found to be significant for large proton velocities.

  15. Electronic structure and optical properties of Nb-doped Sr2TiO4 by density function theory calculation

    Institute of Scientific and Technical Information of China (English)

    Yun Jiang-Ni; Zhang Zhi-Yong

    2009-01-01

    This paper investigates the effect of Nb doping on the electronic structure and optical properties of by the first-principles calculation of plane wave ultra-soft pseudo-potential based on density functional theory (DFT).The calculated results reveal that due to the electron doping, the Fermi level shifts into conduction bands(CBs) for Sr2NbxTi1-xO4 with x = 0.125 and the system shows n-type degenerate semiconductor features. Sr2TiO4 exhibits optical anisotropy in its main crystal axes, and the c-axis shows the most suitable crystal growth direction for obtaining a wide transparent region. The optical transmittance is higher than 90% in the visible range for Sr2Nb0.125Ti0.875O4.

  16. Electronic and thermoelectric properties of InN studied using ab initio density functional theory and Boltzmann transport calculations

    Energy Technology Data Exchange (ETDEWEB)

    Borges, P. D., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu; Scolfaro, L., E-mail: pdborges@gmail.com, E-mail: lscolfaro@txstate.edu [Department of Physics, Texas State University, San Marcos, Texas 78666 (United States)

    2014-12-14

    The thermoelectric properties of indium nitride in the most stable wurtzite phase (w-InN) as a function of electron and hole concentrations and temperature were studied by solving the semiclassical Boltzmann transport equations in conjunction with ab initio electronic structure calculations, within Density Functional Theory. Based on maximally localized Wannier function basis set and the ab initio band energies, results for the Seebeck coefficient are presented and compared with available experimental data for n-type as well as p-type systems. Also, theoretical results for electric conductivity and power factor are presented. Most cases showed good agreement between the calculated properties and experimental data for w-InN unintentionally and p-type doped with magnesium. Our predictions for temperature and concentration dependences of electrical conductivity and power factor revealed a promising use of InN for intermediate and high temperature thermoelectric applications. The rigid band approach and constant scattering time approximation were utilized in the calculations.

  17. Density functional theory study on the structural and electronic properties of Ag-adsorbed (MgO)n clusters

    Institute of Scientific and Technical Information of China (English)

    GE GuiXian; JING Qun; LUO YouHua

    2009-01-01

    Equilibrium geometries, charge distributions, stabilities and electronic properties of the Ag-adsorbed (MgO)n(n=1-8) clusters have been investigated by density functional theory (DFT)with generalized gradient approximation (GGA) for exchange-correlation functional. The results show that hollow site is energetically preferred for n≥4, and the incoming Ag atoms tend to cluster on the existing Ag cluster.The Mulliken populations indicate that the interaction between the Ag atom and Magnesia clusters is mainly induced by a weak atomic polarization. The adsorbed Ag atom only causes charge redistributions of the atoms near itself. The effect of the adsorbed Ag atom on the bonding natures and structural features of Magnesia clusters is minor. Furthermore, the investigations on the first energy difference,fragmentation energies and electron affinities show that the Ag(MgO)4 and Ag(MgO)6 are the most stable among studied clusters.

  18. Density functional theory study on the structural and electronic properties of Ag-adsorbed (MgO)_n clusters

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Equilibrium geometries, charge distributions, stabilities and electronic properties of the Ag-adsorbed (MgO)n (n = 1-8) clusters have been investigated by density functional theory (DFT) with generalized gradient approximation (GGA) for exchange-correlation functional. The results show that hollow site is energetically preferred for n≥4, and the incoming Ag atoms tend to cluster on the existing Ag cluster. The Mulliken populations indicate that the interaction between the Ag atom and Magnesia clusters is mainly induced by a weak atomic polarization. The adsorbed Ag atom only causes charge redistributions of the atoms near itself. The effect of the adsorbed Ag atom on the bonding natures and structural features of Magnesia clusters is minor. Furthermore, the investigations on the first energy difference, fragmentation energies and electron affinities show that the Ag(MgO)4 and Ag(MgO)6 are the most stable among studied clusters.

  19. 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.

  20. Integer Discontinuity of Density Functional Theory

    CERN Document Server

    Mosquera, Martin A

    2014-01-01

    Density functional approximations to the exchange-correlation energy of Kohn-Sham theory, such as the local density approximation and generalized gradient approximations, lack the well-known integer discontinuity, a feature that is critical to describe molecular dissociation correctly. Moreover, standard approximations to the exchange-correlation energy also fail to yield the correct linear dependence of the ground-state energy on the number of electrons when this is a non-integer number obtained from the grand canonical ensemble statistics. We present a formal framework to restore the integer discontinuity of any density functional approximation. Our formalism derives from a formula for the exact energy functional and a new constrained search functional that recovers the linear dependence of the energy on the number of electrons.

  1. Multicomponent density functional theory embedding formulation.

    Science.gov (United States)

    Culpitt, Tanner; Brorsen, Kurt R; Pak, Michael V; Hammes-Schiffer, Sharon

    2016-07-28

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

  2. Multicomponent density functional theory embedding formulation

    Science.gov (United States)

    Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.; Hammes-Schiffer, Sharon

    2016-07-01

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

  3. 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

  4. Study of adiabatic connection in density functional theory with an accurate wavefunction for 2-electron atoms

    CERN Document Server

    Chauhan, Rabeet Singh

    2016-01-01

    Using an accurate semi-analytic wavefunction for two electron atoms, we construct the external potential for varying strength of electron-electron (e-e) interaction. Using this potential we explicitly calculate the energy of their positive ion and show that the ionization-potential of these systems remains unchanged with respect to the strength parameter for e-e interaction. Furthermore, using total energies of these systems as a function of strength parameter, we provide a new perspective into a variety of hybrid functionals.

  5. The Structure of Hydrated Electron. Part 1. Magnetic Resonance of Internally Trapping Water Anions: A Density Functional Theory Study

    CERN Document Server

    Shkrob, I A

    2006-01-01

    Density functional theory (DFT) is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using Electron Paramagnetic Resonance (EPR) and Electron Spin Echo Envelope Modulation (ESEEM) spectroscopies. To this end, model water cluster anions (n=4-8 and n=20,24) that localize the electron internally are examined. It is shown that EPR parameters of such water anions (such as hyperfine coupling tensors of H/D nuclei in the water molecules) are defined mainly by the cavity size and the coordination number of the electron; the water molecules in the second solvation shell play a relatively minor role. An idealized model of hydrated electron (that is usually attributed to L. Kevan) in which six hydroxyl groups arranged in an octahedral pattern point towards the common center is shown to provide the closest match to the experimental parameters, such as isotropic and anisotropic hyperfine coupling constants for the protons (estimated from ESEEM), the second moment of the E...

  6. Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs

    Science.gov (United States)

    Filatov, Michael; Liu, Fang; Kim, Kwang S.; Martínez, Todd J.

    2016-12-01

    The spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociation of several chemical bonds takes place, as well as to the singlet ground states of organic tetraradicals 2,4-didehydrometaxylylene and 1,4,6,9-spiro[4.4]nonatetrayl.

  7. Near and Above Ionization Electronic Excitations with Non-Hermitian Real-Time Time-Dependent Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Lopata, Kenneth A.; Govind, Niranjan

    2013-11-12

    We present a real-time time-dependent density functional theory (RT-TDDFT) prescription for capturing near and post-ionization excitations based on non-Hermitian von Neumann density matrix propagation with atom-centered basis sets, tuned range-separated DFT, and a phenomenological imaginary molecular orbital-based absorbing potential to mimic coupling to the continuum. The computed extreme ultraviolet absorption spectra for acetylene (C2H2), water (H2O), and Freon 12 (CF2Cl2) agree well with electron energy loss spectroscopy (EELS) data over the range 0 to 50 eV. The absorbing potential removes spurious high energy finite basis artifacts, yielding correct bound to bound transitions, metastable (autoionizing) resonance states, and consistent overall absorption shapes.

  8. Near and Above Ionization Electronic Excitations with Non-Hermitian Real-Time Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Lopata, Kenneth; Govind, Niranjan

    2013-11-12

    We present a real-time time-dependent density functional theory (RT-TDDFT) prescription for capturing near and post-ionization excitations based on non-Hermitian von Neumann density matrix propagation with atom-centered basis sets, tuned range-separated DFT, and a phenomenological imaginary molecular orbital-based absorbing potential to mimic coupling to the continuum. The computed extreme ultraviolet absorption spectra for acetylene (C2H2), water (H2O), and Freon 12 (CF2Cl2) agree well with electron energy loss spectroscopy (EELS) data over the range of 0-50 eV. The absorbing potential removes spurious high-energy finite basis artifacts, yielding correct bound-to-bound transitions, metastable (autoionizing) resonance states, and consistent overall absorption shapes.

  9. Consistent Atomic Geometries and Electronic Structure of Five Phases of Potassium Niobate from Density-Functional Theory

    Directory of Open Access Journals (Sweden)

    Falko Schmidt

    2017-01-01

    Full Text Available We perform a comprehensive theoretical study of the structural and electronic properties of potassium niobate (KNbO3 in the cubic, tetragonal, orthorhombic, monoclinic, and rhombohedral phase, based on density-functional theory. The influence of different parametrizations of the exchange-correlation functional on the investigated properties is analyzed in detail, and the results are compared to available experimental data. We argue that the PBEsol and AM05 generalized gradient approximations as well as the RTPSS meta-generalized gradient approximation yield consistently accurate structural data for both the external and internal degrees of freedom and are overall superior to the local-density approximation or other conventional generalized gradient approximations for the structural characterization of KNbO3. Band-structure calculations using a HSE-type hybrid functional further indicate significant near degeneracies of band-edge states in all phases which are expected to be relevant for the optical response of the material.

  10. Electronic structure of novel charge transfer compounds: application of Fermi orbital self-interaction corrected density functional theory

    Science.gov (United States)

    Hahn, Torsten; Rückerl, Florian; Liebing, Simon; Pederson, Mark

    We present our experimental and theoretical results on novel Picene/F4TCNQ and Manganese-Phthalocyanine/F4TCNQ donor / acceptor systems. We apply the recently developed Fermi-orbital based approach for self-interaction corrected density functional theory (FO-SIC DFT) to these materials and compare the results to standard DFT calculations and to experimental data obtained by photoemission spectroscopy. We focus our analysis on the description of the magnitude of the ground state charge transfer and on the details of the formed hybrid orbitals. Further, we show that for weakly bound donor / acceptor systems the FO-SIC approach delivers a more realistic description of the electronic structure compared to standard DFT calculations Support by DFG FOR1154 is greatly acknowledged.

  11. Structural and electronic properties of V-doped cubic BN: A density functional theory study

    Science.gov (United States)

    Espitia R, Miguel J.; Díaz F, John H.; Rodríguez Martínez, Jairo Arbey

    2016-10-01

    The structural, electronic, and magnetic properties of c-BN compound doped with V atoms were calculated by means of the pseudopotential method, employed exactly as implemented in computational Quantum ESPRESSO code. For the description of the electron-electron interaction, generalized gradient approximation (GGA) was used. A half-metallic behavior is predicted for the concentrations B0.9375V0.0625N and B0.875V0.125N, because of the fact that the majority spins are metallic and the minority spins are semiconducting. We found magnetic moments of 2.0 and 4.0 μβ per supercell, respectively. The main contribution to the magnetic moment comes from the V atom, with local moments of 1.61 μβ/V-atom. These compounds are good candidates for potential applications in spintronics and as spin injectors.

  12. Electronic structure effects in liquid water studied by photoelectron spectroscopy and density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Nordlund, Dennis; Odelius, Michael; Bluhm, Hendrik; Ogasawara, Hirohito; Pettersson, Lars G.M.; Nilsson, Anders

    2008-04-29

    We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a{sub 1} orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction.

  13. Periodic density functional theory study of structural and electronic properties of single-walled zinc oxide and carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Marana, Naiara L. [Modeling and Molecular Simulations Group, São Paulo State University, UNESP, 17033-360 Bauru, SP (Brazil); Albuquerque, Anderson R. [Federal Institute of Education, Science and Technology of Sertão Pernambucano, 56400-000 Floresta, PE (Brazil); La Porta, Felipe A. [Chemistry Department, Federal Technological University of Paraná, 86036-370 Londrina, PR (Brazil); Longo, Elson [São Paulo State University, Chemistry Institute, UNESP, 14801-907 Araraquara, SP (Brazil); Sambrano, Julio R. [Modeling and Molecular Simulations Group, São Paulo State University, UNESP, 17033-360 Bauru, SP (Brazil)

    2016-05-15

    Periodic density functional theory calculations with the B3LYP hybrid functional and all-electron Gaussian basis set were performed to simulate the structural and electronic properties as well as the strain and formation energies of single-walled ZnO nanotubes (SWZnONTs) and Carbon nanotubes (SWCNTs) with different chiralities as functions of their diameters. For all SWZnONTs, the band gap, strain energy, and formation energy converge to ~4.5 eV, 0.0 eV/atom, and 0.40 eV/atom, respectively. This result suggests that the nanotubes are formed more easily from the surface than from the bulk. For SWCNTs, the strain energy is always positive, while the formation energy is negative for armchair and zigzag nanotubes, therefore suggesting that these types of nanotubes can be preferentially formed from the bulk. The electronic properties of SWCNTs depend on the chirality; all armchair nanotubes are metallic, while zigzag and chiral nanotubes can be metallic or semiconducting, depending on the n and m vectors. - Graphical abstract: DFT/B3LYP were performed to simulate the structural and electronic properties as well as the strain and formation energies of SWZnONTs and SWCNTs with different chiralities as functions of their diameters. - Highlights: • The energies of SWZnONTs converge for chirality with diameters up 20 Å. • SWCNTs electronic properties depend on the chirality. • The properties of SWZnONTs are very similar to those of monolayer surface.

  14. Structural and electronic properties of poly(vinyl alcohol) using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Dabhi, Shweta, E-mail: shwetadabhi1190@gmail.com; Jha, Prafulla K., E-mail: shwetadabhi1190@gmail.com [Department of Physics, Maharaja Krishnakumasinhji Bhavnagar University, Bhavnagar-364001 (India)

    2014-04-24

    The first principles calculations have been carried out to investigate the structural, electronic band structure density of states along with the projected density of states for poly(vinyl alcohol). Our structural calculation suggests that the poly(vinyl alcohol) exhibits monoclinic structure. The calculated structural lattice parameters are in excellent agreement with available experimental values. The band structure calculations reveal that the direct and indirect band gaps are 5.55 eV and 5.363 eV respectively in accordance with experimental values.

  15. Structural and electronic properties of BeH2 polymorphs: a study by density functional theory

    Science.gov (United States)

    Trivedi, D. K.; Galav, K. L.; Jaaffrey, S. N. A.; Joshi, K. B.

    2016-11-01

    Structural and electronic properties of α, β, δ and ɛ polymorphs of BeH2 are studied. The effect of pressure on these properties is also seen. Investigations are carried out using the linear combination of atomic orbitals method. The lattice parameters, computed by coupling total energy calculations with the Murnaghan equation of state for the four crystals, are overall in agreement with the experimental data and other calculations. Enthalpy-pressure diagram indicates structural phase transitions α → β, α → δ, α → ɛ, β → δ, β → ɛ, and δ → ɛ to occur at 8.75, 12.75, 18.34, 39.53, 55.57 and 76.60 GPa respectively. Electronic band structure and density of states from PBE-GGA show that all polymorphs have wide bandgap. However, quantitative and qualitative agreement of the bandgap from hybrid calculations is observed with available GW data in α-BeH2. Therefore bandgaps from hybrid calculations are also proposed. In the three polymorphs the bandgap decreases slowly with pressure. Beyond 100 GPa, the β structure exhibits overlap of bands at the Γ point.

  16. Electronic and optical properties of families of polycyclic aromatic hydrocarbons: A systematic (time-dependent) density functional theory study

    Science.gov (United States)

    Malloci, G.; Cappellini, G.; Mulas, G.; Mattoni, A.

    2011-06-01

    Homologous classes of polycyclic aromatic hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and time-dependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies and (iv) electronic absorption spectra of neutral and ±1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.

  17. Time-dependent density functional theory study on direction-dependent electron and hole transfer processes in molecular systems.

    Science.gov (United States)

    Partovi-Azar, Pouya; Kaghazchi, Payam

    2017-04-15

    We report on real-time time-dependent density functional theory calculations on direction-dependent electron and hole transfer processes in molecular systems. As a model system, we focus on α-sulfur. It is shown that time scale of the electron transfer process from a negatively charged S8 molecule to a neighboring neutral monomer is comparable to that of a strong infrared-active molecular vibrations of the dimer with one negatively charged monomer. This results in a strong coupling between the electrons and the nuclei motion which eventually leads to S8 ring opening before the electron transfer process is completed. The open-ring structure is found to be stable. The similar infrared-active peak in the case of hole transfer, however, is shown to be very weak and hence no significant scattering by the nuclei is possible. The presented approach to study the charge transfer processes in sulfur has direct applications in the increasingly growing research field of charge transport in molecular systems. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  18. All-electron Kohn–Sham density functional theory on hierarchic finite element spaces

    Energy Technology Data Exchange (ETDEWEB)

    Schauer, Volker [Institute of Applied Mechanics (CE) Chair I, University of Stuttgart, 70550 Stuttgart, Pfaffenwaldring 7 (Germany); Linder, Christian, E-mail: linder@stanford.edu [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305 (United States)

    2013-10-01

    In this work, a real space formulation of the Kohn–Sham equations is developed, making use of the hierarchy of finite element spaces from different polynomial order. The focus is laid on all-electron calculations, having the highest requirement onto the basis set, which must be able to represent the orthogonal eigenfunctions as well as the electrostatic potential. A careful numerical analysis is performed, which points out the numerical intricacies originating from the singularity of the nuclei and the necessity for approximations in the numerical setting, with the ambition to enable solutions within a predefined accuracy. In this context the influence of counter-charges in the Poisson equation, the requirement of a finite domain size, numerical quadratures and the mesh refinement are examined as well as the representation of the electrostatic potential in a high order finite element space. The performance and accuracy of the method is demonstrated in computations on noble gases. In addition the finite element basis proves its flexibility in the calculation of the bond-length as well as the dipole moment of the carbon monoxide molecule.

  19. Insight and progress in density functional theory

    Science.gov (United States)

    Yang, Weitao; Mori-Sanchez, Paula; Cohen, Aron J.

    2012-12-01

    Density functional theory of electronic structure is widely and successfully applied in simulations throughout engineering and sciences. However, there are spectacular failures for many predicted properties. The errors include underestimation of the barriers of chemical reactions, the band gaps of materials, the energies of dissociating molecular ions and charge transfer excitation energies. Typical DFT calculations also fail to describe degenerate or near degenerate systems, as arise in the breaking of chemical bonds, and strongly correlated materials. These errors can all be characterized and understood through the perspective of fractional charges and fractional spins introduced recently.

  20. Using the electron localization function to correct for confinement physics in semi-local density functional theory.

    Science.gov (United States)

    Hao, Feng; Armiento, Rickard; Mattsson, Ann E

    2014-05-14

    We have previously proposed that further improved functionals for density functional theory can be constructed based on the Armiento-Mattsson subsystem functional scheme if, in addition to the uniform electron gas and surface models used in the Armiento-Mattsson 2005 functional, a model for the strongly confined electron gas is also added. However, of central importance for this scheme is an index that identifies regions in space where the correction provided by the confined electron gas should be applied. The electron localization function (ELF) is a well-known indicator of strongly localized electrons. We use a model of a confined electron gas based on the harmonic oscillator to show that regions with high ELF directly coincide with regions where common exchange energy functionals have large errors. This suggests that the harmonic oscillator model together with an index based on the ELF provides the crucial ingredients for future improved semi-local functionals. For a practical illustration of how the proposed scheme is intended to work for a physical system we discuss monoclinic cupric oxide, CuO. A thorough discussion of this system leads us to promote the cell geometry of CuO as a useful benchmark for future semi-local functionals. Very high ELF values are found in a shell around the O ions, and take its maximum value along the Cu-O directions. An estimate of the exchange functional error from the effect of electron confinement in these regions suggests a magnitude and sign that could account for the error in cell geometry.

  1. Determination of structures, stabilities, and electronic properties for bimetallic cesium-doped gold clusters: a density functional theory study.

    Science.gov (United States)

    Cheng, Lu; Xiao-Yu, Kuang; Zhi-Wen, Lu; Ai-Jie, Mao; Yan-Ming, Ma

    2011-08-25

    The equilibrium geometric structures, stabilities, and electronic properties of bimetallic Au(n)Cs (n = 1-10) and pure gold Au(n) (n ≤ 11) clusters have been systematically investigated by using density functional theory with meta-generalized gradient approximation. The optimized geometries show that one Au atom capped on Au(n-1)Cs structures and Cs atom capped Au(n) structures for different sized Au(n)Cs (n = 1-10) clusters are two dominant growth patterns. Theoretical calculated results indicate that the most stable isomers have three-dimensional structures at n = 4 and 6-10. Averaged atomic binding energies, fragmentation energies, and second-order difference of energies exhibit a pronounced even-odd alternations phenomenon. The same even-odd alternations are found in the highest occupied-lowest unoccupied molecular orbital gaps, vertical ionization potential, vertical electron affinity, and hardnesses. In addition, it is found that the charge in corresponding Au(n)Cs clusters transfers from the Cs atom to the Au(n) host in the range of 0.851-1.036 electrons.

  2. Chemical bonding and electronic-structure in MAX phases as viewed by X-ray spectroscopy and density functional theory

    Science.gov (United States)

    Magnuson, Martin; Mattesini, Maurizio

    2017-01-01

    This is a critical review of MAX-phase carbides and nitrides from an electronic-structure and chemical bonding perspective. This large group of nanolaminated materials is of great scientific and technological interest and exhibit a combination of metallic and ceramic features. These properties are related to the special crystal structure and bonding characteristics with alternating strong M-C bonds in high-density MC slabs, and relatively weak M-A bonds between the slabs. Here, we review the trend and relationship between the chemical bonding, conductivity, elastic and magnetic properties of the MAX phases in comparison to the parent binary MX compounds with the underlying electronic structure probed by polarized X-ray spectroscopy. Spectroscopic studies constitute important tests of the results of state-of-the-art electronic structure density functional theory that is extensively discussed and are generally consistent. By replacing the elements on the M, A, or X-sites in the crystal structure, the corresponding changes in the conductivity, elasticity, magnetism and other materials properties makes it possible to tailor the characteristics of this class of materials by controlling the strengths of their chemical bonds.

  3. Evaluation of optical and electronic properties of silicon nano-agglomerates embedded in SRO: applying density functional theory.

    Science.gov (United States)

    Espinosa-Torres, Néstor D; la Luz, David Hernández-de; Flores-Gracia, José Francisco J; Luna-López, José A; Martínez-Juárez, Javier; Vázquez-Valerdi, Diana E

    2014-01-01

    In systems in atomic scale and nanoscale such as clusters or agglomerates constituted by particles from a few to less than 100 atoms, quantum confinement effects are very important. Their optical and electronic properties are often dependent on the size of the systems and the way in which the atoms in these clusters are bonded. Generally, these nanostructures display optical and electronic properties significantly different to those found in corresponding bulk materials. Silicon agglomerates embedded in silicon rich oxide (SRO) films have optical properties, which have been reported to be directly dependent on silicon nanocrystal size. Furthermore, the room temperature photoluminescence (PL) of SRO has repeatedly generated a huge interest due to its possible applications in optoelectronic devices. However, a plausible emission mechanism has not been widely accepted in the scientific community. In this work, we present a short review about the experimental results on silicon nanoclusters in SRO considering different techniques of growth. We focus mainly on their size, Raman spectra, and photoluminescence spectra. With this as background, we employed the density functional theory with a functional B3LYP and a basis set 6-31G* to calculate the optical and electronic properties of clusters of silicon (constituted by 15 to 20 silicon atoms). With the theoretical calculation of the structural and optical properties of silicon clusters, it is possible to evaluate the contribution of silicon agglomerates in the luminescent emission mechanism, experimentally found in thin SRO films.

  4. Electronic and optical properties of families of polycyclic aromatic hydrocarbons: A systematic (time-dependent) density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Malloci, G., E-mail: giuliano.malloci@dsf.unica.it [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy); Cappellini, G. [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy); INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Localita Poggio dei Pini, I-09012 Capoterra (Italy); Mulas, G. [INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Localita Poggio dei Pini, I-09012 Capoterra (Italy); Mattoni, A. [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy)

    2011-06-16

    Graphical abstract: Electronic absorption spectra of the neutral molecules of the four PAH classes considered, as computed using the real-time real-space TD-DFT. Highlights: {yields}We present a systematic comparative study of families of PAHs. {yields} We computed electronic, optical, and transport properties as a function of size. {yields} We considered oligoacenes, phenacenes, circumacenes, and oligorylenes. {yields} Circumacenes have the best transport properties compared to the other classes. {yields} Oligorylenes are much more efficient in absorbing low-energy photons. - Abstract: Homologous classes of polycyclic aromatic hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and time-dependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies and (iv) electronic absorption spectra of neutral and {+-}1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.

  5. A Density Functional Theory Study of the Ionic and Electronic Transport Mechanisms in LiFeBO3 Battery Electrodes

    DEFF Research Database (Denmark)

    Loftager, Simon; García Lastra, Juan Maria; Vegge, Tejs

    2016-01-01

    to large overvoltages at the beginning of charge. Using a convex-hull analysis, based on Hubbard-corrected density functional theory (DFT+U), we identify this intermediate phase as Li0.5FeBO3. Moreover, we show by means of the nudged elastic band (NEB) method, that the origin of these adverse...

  6. Structural and Electronic Properties of Folic Acid Adsorption on the Carbon Nanotubes: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Shahla Hamedani

    2015-03-01

    Full Text Available In this study, we studied the adsorption behavior of folic acid on the (5,0 zigzag and (5,5 armchair single-walled carbon nanotube (SWCNT by Density Functional Theory (DFT. Geometry optimizations were carried out at the B3LYP/6-31 G* level of theory using the Gaussian 09 suite of programs. The adsorption energies, the quantum molecular descriptors analysis and the structural changes at the adsorption site are indicative of chemisorption (adsorption energy -31.673 kcal/mol on the zigzag SWCNT surface, while the adsorption is physical (adsorption energy -9.70 kcal/mol in nature on the armchair SWCNT surface. The density of the states (DOS Plots, Natural bond orbital (NBO analysis, and HOMO and LUMO are witness to the substantial changes in the electronic properties of the SWCNT systems after the attachment adsorbed species with the tube surface. These results are extremely relevant in order to diagnosis the potential applications of carbon nanotubes as drug delivery systems.

  7. Density-functional theory of thermoelectric phenomena.

    Science.gov (United States)

    Eich, F G; Di Ventra, M; Vignale, G

    2014-05-16

    We introduce a nonequilibrium density-functional theory of local temperature and associated local energy density that is suited for the study of thermoelectric phenomena. The theory rests on a local temperature field coupled to the energy-density operator. We identify the excess-energy density, in addition to the particle density, as the basic variable, which is reproduced by an effective noninteracting Kohn-Sham system. A novel Kohn-Sham equation emerges featuring a time-dependent and spatially varying mass which represents local temperature variations. The adiabatic contribution to the Kohn-Sham potentials is related to the entropy viewed as a functional of the particle and energy density. Dissipation can be taken into account by employing linear response theory and the thermoelectric transport coefficients of the electron gas.

  8. Modeling Fast Electron Dynamics with Real-Time Time-Dependent Density Functional Theory: Application to Small Molecules and Chromophores.

    Science.gov (United States)

    Lopata, Kenneth; Govind, Niranjan

    2011-05-10

    The response of matter to external fields forms the basis for a vast wealth of fundamental physical processes ranging from light harvesting to nanoscale electron transport. Accurately modeling ultrafast electron dynamics in excited systems thus offers unparalleled insight but requires an inherently nonlinear time-resolved approach. To this end, an efficient and massively parallel real-time real-space time-dependent density functional theory (RT-TDDFT) implementation in NWChem is presented. The implementation is first validated against linear-response TDDFT and experimental results for a series of molecules subjected to small electric field perturbations. Second, nonlinear excitation of green fluorescent protein is studied, which shows a blue-shift in the spectrum with increasing perturbation, as well as a saturation in absorption. Next, the charge dynamics of optically excited zinc porphyrin is presented in real time and real space, with relevance to charge injection in photovoltaic devices. Finally, intermolecular excitation in an adenine-thymine base pair is studied using the BNL range separated functional [ Baer , R. ; Neuhauser , D. Phys. Rev. Lett. 2005 , 94 , 043002 ], demonstrating the utility of a real-time approach in capturing charge transfer processes.

  9. Electronic structure of LiCoO2 thin films: A combined photoemission spectroscopy and density functional theory study

    Science.gov (United States)

    Ensling, David; Thissen, Andreas; Laubach, Stefan; Schmidt, Peter C.; Jaegermann, Wolfram

    2010-11-01

    The electronic properties of LiCoO2 have been studied by theoretical band-structure calculations (using density functional theory) and experimental methods (photoemission). Synchrotron-induced photoelectron spectroscopy, resonant photoemission spectroscopy (ResPES), and soft x-ray absorption (XAS) have been applied to investigate the electronic structure of both occupied and unoccupied states. High-quality PES spectra were obtained from stoichiometric and highly crystalline LiCoO2 thin films deposited “in situ” by rf magnetron sputtering. An experimental approach of separating oxygen- and cobalt-derived (final) states by ResPES in the valence-band region is presented. The procedure takes advantage of an antiresonant behavior of cobalt-derived states at the 3p-3d excitation threshold. Information about the unoccupied density of states has been obtained by OK XAS. The structure of the CoL absorption edge is compared to semiempirical charge-transfer multiplet calculations. The experimental results are furthermore compared with band-structure calculations considering three different exchange potentials [generalized gradient approximation (GGA), using a nonlocal Hubbard U (GGA+U) and using a hybrid functional (Becke, three-parameter, Lee-Yang-Parr [B3LYP])]. For these different approaches total density of states and partial valence-band density of states have been investigated. The best qualitative agreement with experimental results has been obtained by using a GGA+U functional with U=2.9eV .

  10. Electronic, structural, and thermodynamic properties of mixed actinide dioxides (U, Pu, Am) O2 from hybrid density functional theory

    Science.gov (United States)

    Ma, Li; Ray, Asok K.

    2010-03-01

    As a continuation of our studies of pure actinide metals using hybrid density functional theory,footnotetextR. Atta-Fynn and A. K. Ray, Europhysics Letters, 85, 27008-p1- p6 (2009); Chemical Physics Letters, 482, 223-227 (2009). we present here a systematic study of the electronic and geometric structure properties of mixed actinide dioxides, U0.5Pu0.5O2, U0.5Am0.5O2, Pu0.5Am0.5 O2 and U0.8Pu0.2O2. The fraction of exact Hartree-Fock exchange used was 40%. To investigate the effect of spin-orbit coupling on the ground state electronic and geometric structure properties, computations have been carried out at two theoretical levels, one at the scalar-relativistic level with no spin-orbit coupling and one at the fully relativistic level with spin-orbit coupling. Thermodynamic properties have been calculated by a coupling of first-principles calculation and lattice dynamics.

  11. 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.

  12. Electronic structure and optical properties of In-doped SrTiO3 by density function theory

    Institute of Scientific and Technical Information of China (English)

    Zhang Zhi-Yong; Yun Jiang-Ni; Zhang Fu-Chun

    2007-01-01

    The effect of In doping on the electronic structure and optical properties of SrTiO3 is investigated by the firstprinciples calculation of plane wave ultra-soft pseudo-potential based on the density function theory (DFT). The calculated results reveal that due to the hole doping, the Fermi level shifts into valence bands (VBs) for SrTi1-xInxO3 with x = 0.125 and the system exhibits p-type degenerate semiconductor features. It is suggested according to the density of states (DOS) of SrTi0.s75In0.125O3 that the band structure of p-type SrTiO3 can be described by a rigid band model.At the same time, the DOS shifts towards high energies and the optical band gap is broadened. The wide band gap,small transition probability and weak absorption due to the low partial density of states (PDOS) of impurity in the Fermi level result in the optical transparency of the film. The optical transmittance of In doped SrTiO3 is higher than 85% in a visible region, and the transmittance improves greatly. And the cut-off wavelength shifts into a blue-light region with the increase of In doping concentration.

  13. Electronic Structure of Semiconducting and Metallic Tubes in TiO2/Carbon Nanotube Heterojunctions: Density Functional Theory Calculations.

    Science.gov (United States)

    Long, Run

    2013-04-18

    The electronic structure of the TiO2(110) surface interfaced with both a semiconducting and metallic carbon nanotube (CNT) was investigated by density functional theory. Our simulations rationalized visible light photocatalytic activity of CNT/TiO2 hybrid materials higher than that under ultraviolent irradiation and showed that the photoactivity of a semiconducting CNT decorating TiO2 is better than that of the metallic CNT/TiO2 system due to efficient charge separation across the interface. This suggests that semiconducting CNT/TiO2 could be a potential photovoltaic material. In contrast, strong interaction between a metallic CNT and TiO2 leads to large charge transfer. Such charge transfer reduces the built-in potential, in turn resulting in inefficient charge separation. Functionalizing the metallic CNT with a small platinum cluster can increase the built-in potential and drive charge separation. These observations indicate that the CNT/TiO2 interface can be a potential photovoltaic material by a metal cluster decorating a CNT despite a real tube being composed of the mixture of metallic and semiconducting CNTs.

  14. An atomic orbital based real-time time-dependent density functional theory for computing electronic circular dichroism band spectra.

    Science.gov (United States)

    Goings, Joshua J; Li, Xiaosong

    2016-06-21

    One of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entire ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.

  15. Electronic and Optical Properties of Small Hydrogenated Silicon Quantum Dots Using Time-Dependent Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Muhammad Mus-’ab Anas

    2015-01-01

    Full Text Available This paper presents a systematic study of the absorption spectrum of various sizes of small hydrogenated silicon quantum dots of quasi-spherical symmetry using the time-dependent density functional theory (TDDFT. In this study, real-time and real-space implementation of TDDFT involving full propagation of the time-dependent Kohn-Sham equations were used. The experimental results for SiH4 and Si5H12 showed good agreement with other earlier calculations and experimental data. Then these calculations were extended to study larger hydrogenated silicon quantum dots with diameter up to 1.6 nm. It was found that, for small quantum dots, the absorption spectrum is atomic-like while, for relatively larger (1.6 nm structure, it shows bulk-like behavior with continuous plateau with noticeable peak. This paper also studied the absorption coefficient of silicon quantum dots as a function of their size. Precisely, the dependence of dot size on the absorption threshold is elucidated. It was found that the silicon quantum dots exhibit direct transition of electron from HOMO to LUMO states; hence this theoretical contribution can be very valuable in discerning the microscopic processes for the future realization of optoelectronic devices.

  16. Coupled-cluster and density functional theory studies of the electronic 0-0 transitions of the DNA bases.

    Science.gov (United States)

    Ovchinnikov, Vasily A; Sundholm, Dage

    2014-04-21

    The 0-0 transitions of the electronic excitation spectra of the lowest tautomers of the four nucleotide (DNA) bases have been studied using linear-response approximate coupled-cluster singles and doubles (CC2) calculations. Excitation energies have also been calculated at the linear-response time-dependent density functional theory (TDDFT) level using the B3LYP functional. Large basis sets have been employed for ensuring that the obtained excitation energies are close to the basis-set limit. Zero-point vibrational energy corrections have been calculated at the B3LYP and CC2 levels for the ground and excited states rendering direct comparisons with high-precision spectroscopy measurements feasible. The obtained excitation energies for the 0-0 transitions of the first excited states of guanine tautomers are in good agreement with experimental values confirming the experimental assignment of the energetic order of the tautomers of the DNA bases. For the experimentally detected guanine tautomers, the first excited state corresponds to a π→π* transition, whereas for the tautomers of adenine, thymine, and the lowest tautomer of cytosine the transition to the first excited state has n →π* character. The calculations suggest that the 0-0 transitions of adenine, thymine, and cytosine are not observed in the absorption spectrum due to the weak oscillator strength of the formally symmetry-forbidden transitions, while 0-0 transitions of thymine have been detected in fluorescence excitation spectra.

  17. The Density Functional Theory Study of Electronical Properties of (ZnO12 Clusters During Gas Adsorption

    Directory of Open Access Journals (Sweden)

    O.V. Bovgyra

    2015-12-01

    Full Text Available A density functional theory study of the adsorption of molecules of different gases (O2, H2O, CO, NO2, NH3, CH3OH, C3H6O and C2H5OH on the surface of nanoclusters Zn12O12 were performed. For each cluster an optimization (relaxation of structures geometry were performed and then the molecules of O2, H2O, CO, NO2, NH3, methanol, acetone and ethanol had been added to the surface. It was determined that the molecules of H2O, CO, NO2, NH3, CH3OH, C3H6O and C2H5OH increase the concentration of the main charge carriers (electrons in sensor systems, whereas molecule O2, reduce their concentration. Adsorption of molecules causes the reducing of the band gap of nanoclusters. The sharpest decrease is observed for O2 molecules, and among donor molecules the greatest impact was observed with CO and NH3 molecules.

  18. Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework

    Energy Technology Data Exchange (ETDEWEB)

    Morzan, Uriel N.; Ramírez, Francisco F.; Scherlis, Damián A., E-mail: damian@qi.fcen.uba.ar, E-mail: mcgl@qb.ffyb.uba.ar [Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. II, Buenos Aires (C1428EHA) (Argentina); Oviedo, M. Belén; Sánchez, Cristián G. [Departamento de Matemática y Física, Facultad de Ciencias Químicas, INFIQC, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Lebrero, Mariano C. González, E-mail: damian@qi.fcen.uba.ar, E-mail: mcgl@qb.ffyb.uba.ar [Instituto de Química y Fisicoquímica Biológicas, IQUIFIB, CONICET (Argentina)

    2014-04-28

    This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.

  19. Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework.

    Science.gov (United States)

    Morzan, Uriel N; Ramírez, Francisco F; Oviedo, M Belén; Sánchez, Cristián G; Scherlis, Damián A; Lebrero, Mariano C González

    2014-04-28

    This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix-required to propagate the electron dynamics-, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.

  20. Investigating the electronic structure of the Atox1 copper(I) transfer mechanism with density functional theory.

    Science.gov (United States)

    Pitts, Amanda L; Hall, Michael B

    2013-09-16

    To maintain correct copper homeostasis, the body relies on ion binding metallochaperones, cuprophilic ligands, and proteins to move copper around as a complexed metal. The most common binding site for Cu(I) proteins is the CX1X2C motif, where X1 and X2 are nonconserved residues. Although this binding site motif is well established, the mechanistic and electronic details for the transfer of Cu(I) between two binding sites have not been fully established, in particular, whether the transfer is dissociative or associative or if the electron-rich Cu(I)-Cys interactions influence the transfer. In this work, we investigated the electronic structure of the Cu(I)-S interactions during the copper transfer between Atox1 and a metal binding domain on the ATP7A or ATP7B protein. Initially, three Cu(I) methylthiolate complexes, [Cu(SCH3)2](-1), [Cu(SCH3)3](-2), [Cu(SCH3)4](-3), were investigated with density functional theory (DFT) to fully elucidate the electronic structure and bonding between Cu(I) and thiolate species. The two-coordinate, linear species with a C-S-S-C dihedral angle of ∼90° is the lowest energy conformation because the filled π antibonding orbitals are stabilized in this geometry. The importance of π-overlap is also seen with the trigonal planar, three-coordinate Cu(I) complex, which is similarly stabilized. A corresponding four-coordinate species could not be consistently optimized, so it was concluded that tetrahedral coordination was not likely to be stable. The transfer of Cu(I) from the Atox1 metallochaperone to a metal binding domain of the ATP7A or ATP7B protein was then modeled by using the CGGC Atox1 binding site for the donor model and the dithiotreitol ligand (DTT) for the acceptor model. The two- and three-coordinate intermediates calculated along the five-step transfer mechanism converged to near optimal Cu-S π-overlap for the respective geometries, which demonstrates that the electronic structure in this electron-rich environment

  1. Combining Molecular Dynamics and Density Functional Theory

    Science.gov (United States)

    Kaxiras, Efthimios

    2015-03-01

    The time evolution of a system consisting of electrons and ions is often treated in the Born-Oppenheimer approximation, with electrons in their instantaneous ground state. This approach cannot capture many interesting processes that involved excitation of electrons and its effects on the coupled electron-ion dynamics. The time scale needed to accurately resolve the evolution of electron dynamics is atto-seconds. This poses a challenge to the simulation of important chemical processes that typically take place on time scales of pico-seconds and beyond, such as reactions at surfaces and charge transport in macromolecules. We will present a methodology based on time-dependent density functional theory for electrons, and classical (Ehrenfest) dynamics for the ions, that successfully captures such processes. We will give a review of key features of the method and several applications. These illustrate how the atomic and electronic structure evolution unravels the elementary steps that constitute a chemical reaction. In collaboration with: G. Kolesov, D. Vinichenko, G. Tritsaris, C.M. Friend, Departments of Physics and of Chemistry and Chemical Biology.

  2. Pressure Correction in Density Functional Theory Calculations

    CERN Document Server

    Lee, S H

    2008-01-01

    First-principles calculations based on density functional theory have been widely used in studies of the structural, thermoelastic, rheological, and electronic properties of earth-forming materials. The exchange-correlation term, however, is implemented based on various approximations, and this is believed to be the main reason for discrepancies between experiments and theoretical predictions. In this work, by using periclase MgO as a prototype system we examine the discrepancies in pressure and Kohn-Sham energy that are due to the choice of the exchange-correlation functional. For instance, we choose local density approximation and generalized gradient approximation. We perform extensive first-principles calculations at various temperatures and volumes and find that the exchange-correlation-based discrepancies in Kohn-Sham energy and pressure should be independent of temperature. This implies that the physical quantities, such as the equation of states, heat capacity, and the Gr\\"{u}neisen parameter, estimat...

  3. Density Functional Theory Modeling of Low-Loss Electron Energy-Loss Spectroscopy in Wurtzite III-Nitride Ternary Alloys.

    Science.gov (United States)

    Eljarrat, Alberto; Sastre, Xavier; Peiró, Francesca; Estradé, Sónia

    2016-06-01

    In the present work, the dielectric response of III-nitride semiconductors is studied using density functional theory (DFT) band structure calculations. The aim of this study is to improve our understanding of the features in the low-loss electron energy-loss spectra of ternary alloys, but the results are also relevant to optical and UV spectroscopy results. In addition, the dependence of the most remarkable features with composition is tested, i.e. applying Vegard's law to band gap and plasmon energy. For this purpose, three wurtzite ternary alloys, from the combination of binaries AlN, GaN, and InN, were simulated through a wide compositional range (i.e., Al x Ga1-x N, In x Al1-x N, and In x Ga1-x N, with x=[0,1]). For this DFT calculations, the standard tools found in Wien2k software were used. In order to improve the band structure description of these semiconductor compounds, the modified Becke-Johnson exchange-correlation potential was also used. Results from these calculations are presented, including band structure, density of states, and complex dielectric function for the whole compositional range. Larger, closer to experimental values, band gap energies are predicted using the novel potential, when compared with standard generalized gradient approximation. Moreover, a detailed analysis of the collective excitation features in the dielectric response reveals their compositional dependence, which sometimes departs from a linear behavior (bowing). Finally, an advantageous method for measuring the plasmon energy dependence from these calculations is explained.

  4. Structural and electronic properties of the adsorbed and defected Cu nanowires: A density-functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Ying-Ni [College of Physics and Information Technology, Shaanxi Normal University, Xian 710062, Shaanxi (China); Department of Medical Engineering and Technology, Xinjiang Medical University, Urumqi 830011, Xinjiang (China); Zhang, Jian-Min, E-mail: jianm_zhang@yahoo.com [College of Physics and Information Technology, Shaanxi Normal University, Xian 710062, Shaanxi (China); Fan, Xiao-Xi [Department of Medical Engineering and Technology, Xinjiang Medical University, Urumqi 830011, Xinjiang (China); Xu, Ke-Wei [College of Physics and Mechanical and Electronic Engineering, Xian University of Arts and Science, Xian 710065, Shaanxi (China)

    2014-12-01

    Using first-principles calculations based on density-functional theory, we systematically investigate the influence of adsorbates (CO molecule and O atom) and defects (adsorb one extra Cu atom and monovacancy) on the structural and electronic properties of Cu{sub 5-1}NW and Cu{sub 6-1}NW. For both nanowires, CO molecule prefers to adsorb on the top site, while O atom prefers to adsorb on the center site. The hybridization between the CO and Cu states is dominated by the donation–backdonation process, which leads to the formation of bonding/antibonding pairs, 5σ{sub b}/5σ{sub a} and 2π{sub b}{sup ⁎}/2π{sub a}{sup ⁎}. The larger adsorption energies, larger charge transfers to O adatom and larger decrease in quantum conductance 3G{sub 0} for an O atom adsorbed on the Cu{sub 5-1}NW and Cu{sub 6-1}NW show both Cu{sub 5-1}NW and Cu{sub 6-1}NW can be used as an O sensor. Furthermore, the decrease in quantum conductance 1G{sub 0} for a CO molecule adsorbed on the Cu{sub 6-1}NW also shows the Cu{sub 6-1}NW can be used to detect CO molecule. So we expect these results may have implications for CuNW based chemical sensing. High adsorption energy of one extra Cu atom and relatively low formation energy of a monovacancy suggest that these two types of defects are likely to occur in the fabrication of CuNWs. One extra Cu atom does not decrease the quantum conductance, while a Cu monovacancy leads to a drop of the quantum conductance.

  5. Electronic structures and phonon free energies of LaCoO3 using hybrid-exchange density functional theory

    Science.gov (United States)

    Mukhopadhyay, S.; Finnis, M. W.; Harrison, N. M.

    2013-03-01

    Hybrid-exchange density functional theory has been used to model the electronic structure of LaCoO3. Based on a rhombohedral unit cell of R3¯c symmetry containing two Co atoms we find a mixed spin phase, comprising alternating low and high spin Co+3 ions, with a total energy at 0 K just 57 meV per formula unit above that of a nonmagnetic semiconducting ground state. In the mixed spin phase the high-spin Co+3 ions have spin moments of 3.1μB and the state is insulating with a band gap of 2.2 eV. Our calculations suggest that the effective on-site Coulomb repulsion energy Ueff on Co+3 ions is spin dependent. The Ueff on Co+3 ions is 7.1 eV and 8.5 eV for the nonmagnetic ground state and for the magnetic high spin state, respectively. For the mixed spin state, two different Ueff are estimated for two Co+3 ions in the unit cell having different spin states, 8.0 eV for the high-spin Co+3 ion and 7.0 eV for the low-spin Co+3 ion. An estimate of the harmonic phonon free energy suggests that this mixed spin phase would become the more stable phase as the temperature increases, which is consistent with experimental evidence. An alternative intermediate spin state is higher in energy at all temperatures.

  6. Density functional theory on phase space

    CERN Document Server

    Blanchard, Philippe; Várilly, Joseph C

    2010-01-01

    Forty-five years after the point de d\\'epart [1] of density functional theory, its applications in chemistry and the study of electronic structures keep steadily growing. However, the precise form of the "divine" energy functional in terms of the electron density [2] still eludes us --and possibly will do so forever [3]. In what follows we examine a formulation in the same spirit with phase-space variables. The validity of Hohenberg-Kohn-Levy-type theorems on phase space is recalled. We study the representability problem for reduced Wigner functions, and proceed to analyze properties of the new functional. Along the way, new results on states in the phase-space formalism of quantum mechanics are established. Natural Wigner orbital theory is developed in depth, with the final aim of constructing accurate correlation-exchange functionals on phase space. A new proof of the overbinding property of the Mueller functional is given. This exact theory supplies its home at long last to that illustrious ancestor, the T...

  7. Density functional theory studies on the structures and electronic communication of meso-ferrocenylporphyrins: long range orbital coupling via porphyrin core.

    Science.gov (United States)

    Zhang, Lijuan; Qi, Dongdong; Zhang, Yuexing; Bian, Yongzhong; Jiang, Jianzhuang

    2011-02-01

    The molecular and electronic structures together with the electronic absorption spectra of a series of metal free meso-ferrocenylporphyrins, namely 5-ferrocenylporphyrin (1), 5,10-diferrocenylporphyrin (2), 5,15-diferrocenylporphyrin (3), 5,10,15-triferrocenylporphyrin (4), and 5,10,15,20-tetraferrocenylporphyrin (5) have been studied with the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. For the purpose of comparative studies, metal free porphyrin without any ferrocenyl group (0) and isolated ferrocene (6) were also calculated. The effects of the number and position of meso-attached ferrocenyl substituents on their molecular and electronic structures, atomic charges, molecular orbitals, and electronic absorption spectra of 1-5 were systematically investigated. The orbital coupling is investigated in detail, explaining well the long range coupling of ferrocenyl substituents connected via porphyrin core and the systematic change in the electronic absorption spectra of porphyrin compounds.

  8. Noncovalent Interactions in Density-Functional Theory

    CERN Document Server

    DiLabio, Gino A

    2014-01-01

    Non-covalent interactions are essential in the description of soft matter, including materials of technological importance and biological molecules. In density-functional theory, common approaches fail to describe dispersion forces, an essential component in noncovalent binding interactions. In the last decade, great progress has been made in the development of accurate and computationally-efficient methods to describe noncovalently bound systems within the framework of density-functional theory. In this review, we give an account of the field from a chemical and didactic perspective, describing different approaches to the calculation of dispersion energies and comparing their accuracy, complexity, popularity, and general availability. This review should be useful to the newcomer who wants to learn more about noncovalent interactions and the different methods available at present to describe them using density-functional theory.

  9. Tight-Binding Approximations to Time-Dependent Density Functional Theory - a fast approach for the calculation of electronically excited states

    CERN Document Server

    Rüger, Robert; Heine, Thomas; Visscher, Lucas

    2016-01-01

    We propose a new method of calculating electronically excited states that combines a density functional theory (DFT) 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 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 time-dependent density functional theory (TD-DFT) calculations. Errors in vertical excitation energies are reduced by a factor of two compared to TD-DFTB.

  10. Large-scale all-electron density functional theory calculations using an enriched finite-element basis

    Science.gov (United States)

    Kanungo, Bikash; Gavini, Vikram

    2017-01-01

    We present a computationally efficient approach to perform large-scale all-electron density functional theory calculations by enriching the classical finite element basis with compactly supported atom-centered numerical basis functions that are constructed from the solution of the Kohn-Sham (KS) problem for single atoms. We term these numerical basis functions as enrichment functions, and the resultant basis as the enriched finite element basis. The compact support for the enrichment functions is obtained by using smooth cutoff functions, which enhances the conditioning and maintains the locality of the enriched finite element basis. The integrals involved in the evaluation of the discrete KS Hamiltonian and overlap matrix in the enriched finite element basis are computed using an adaptive quadrature grid that is constructed based on the characteristics of enrichment functions. Further, we propose an efficient scheme to invert the overlap matrix by using a blockwise matrix inversion in conjunction with special reduced-order quadrature rules, which is required to transform the discrete Kohn-Sham problem to a standard eigenvalue problem. Finally, we solve the resulting standard eigenvalue problem, in each self-consistent field iteration, by using a Chebyshev polynomial based filtering technique to compute the relevant eigenspectrum. We demonstrate the accuracy, efficiency, and parallel scalability of the proposed method on semiconducting and heavy-metallic systems of various sizes, with the largest system containing 8694 electrons. We obtain accuracies in the ground-state energies that are ˜1 mHa with reference ground-state energies employing classical finite element as well as Gaussian basis sets. Using the proposed formulation based on enriched finite element basis, for accuracies commensurate with chemical accuracy, we observe a staggering 50 -300 -fold reduction in the overall computational time when compared to classical finite element basis. Further, we find a

  11. General degeneracy in density functional perturbation theory

    CERN Document Server

    Palenik, Mark C

    2016-01-01

    Degenerate perturbation theory from quantum mechanics is inadequate in density functional theory (DFT) because of nonlinearity in the Kohn-Sham potential. We develop the fully general degenerate perturbation theory for DFT without assuming that the degeneracy is required by symmetry. The resulting methodology is applied to the iron atom ground state in order to demonstrate the effects of degeneracy that appears both due to symmetry requirements and accidentally, between different representations of the symmetry group.

  12. Electrons as probes of dynamics in molecules and clusters: A contribution from Time Dependent Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Wopperer, P. [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Dinh, P.M., E-mail: dinh@irsamc.ups-tlse.fr [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Reinhard, P.-G. [Institut für Theoretische Physik, Universität Erlangen, Staudtstrasse 7, D-91058 Erlangen (Germany); Suraud, E. [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Physics Department, University at Buffalo, The State University New York, Buffalo, NY 14260 (United States)

    2015-02-28

    There are various ways to analyze the dynamical response of clusters and molecules to electromagnetic perturbations. Particularly rich information can be obtained from measuring the properties of electrons emitted in the course of the excitation dynamics. Such an analysis of electron signals covers observables such as total ionization, Photo-Electron Spectra (PES), Photoelectron Angular Distributions (PAD), and ideally combined PES/PAD. It has a long history in molecular physics and was increasingly used in cluster physics as well. Recent progress in the design of new light sources (high intensity, high frequency, ultra short pulses) opens new possibilities for measurements and thus has renewed the interest on these observables, especially for the analysis of various dynamical scenarios, well beyond a simple access to electronic density of states. This, in turn, has motivated many theoretical investigations of the dynamics of electronic emission for molecules and clusters up to such a complex and interesting system as C{sub 60}. A theoretical tool of choice is here Time-Dependent Density Functional Theory (TDDFT) propagated in real time and on a spatial grid, and augmented by a Self-Interaction Correction (SIC). This provides a pertinent, robust, and efficient description of electronic emission including the detailed pattern of PES and PAD. A direct comparison between experiments and well founded elaborate microscopic theories is thus readily possible, at variance with more demanding observables such as for example fragmentation or dissociation cross sections. The purpose of this paper is to describe the theoretical tools developed on the basis of real-time and real-space TDDFT and to address in a realistic manner the analysis of electronic emission following irradiation of clusters and molecules by various laser pulses. After a general introduction, we shall present in a second part the available experimental results motivating such studies, starting from the

  13. Electrons as probes of dynamics in molecules and clusters: A contribution from Time Dependent Density Functional Theory

    Science.gov (United States)

    Wopperer, P.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.

    2015-02-01

    There are various ways to analyze the dynamical response of clusters and molecules to electromagnetic perturbations. Particularly rich information can be obtained from measuring the properties of electrons emitted in the course of the excitation dynamics. Such an analysis of electron signals covers observables such as total ionization, Photo-Electron Spectra (PES), Photoelectron Angular Distributions (PAD), and ideally combined PES/PAD. It has a long history in molecular physics and was increasingly used in cluster physics as well. Recent progress in the design of new light sources (high intensity, high frequency, ultra short pulses) opens new possibilities for measurements and thus has renewed the interest on these observables, especially for the analysis of various dynamical scenarios, well beyond a simple access to electronic density of states. This, in turn, has motivated many theoretical investigations of the dynamics of electronic emission for molecules and clusters up to such a complex and interesting system as C60. A theoretical tool of choice is here Time-Dependent Density Functional Theory (TDDFT) propagated in real time and on a spatial grid, and augmented by a Self-Interaction Correction (SIC). This provides a pertinent, robust, and efficient description of electronic emission including the detailed pattern of PES and PAD. A direct comparison between experiments and well founded elaborate microscopic theories is thus readily possible, at variance with more demanding observables such as for example fragmentation or dissociation cross sections. The purpose of this paper is to describe the theoretical tools developed on the basis of real-time and real-space TDDFT and to address in a realistic manner the analysis of electronic emission following irradiation of clusters and molecules by various laser pulses. After a general introduction, we shall present in a second part the available experimental results motivating such studies, starting from the simplest

  14. Density Functional Theory with Dissipation: Transport through Single Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kieron Burke

    2012-04-30

    A huge amount of fundamental research was performed on this grant. Most of it focussed on fundamental issues of electronic structure calculations of transport through single molecules, using density functional theory. Achievements were: (1) First density functional theory with dissipation; (2) Pseudopotential plane wave calculations with master equation; (3) Weak bias limit; (4) Long-chain conductance; and (5) Self-interaction effects in tunneling.

  15. Electronic structure of CeRu4Sn6: a density functional plus dynamical mean field theory study

    Science.gov (United States)

    Wissgott, Philipp; Held, Karsten

    2016-01-01

    The Kondo system CeRu4Sn6 shows a strong anisotropy in its electric, optic and magnetic properties. We employ density functional theory plus dynamical mean field theory and show that the predominant Ce-f state has total angular moment J = 5 / 2 and z-component mJ = ± 1 / 2 in agreement with recent X-ray absorption experiments. There is also an admixture of mJ = ± 3 / 2 which is reduced in favor of mJ = ± 1 / 2 with the onset of the Kondo effect. Even though CeRu4Sn6 has the direct gap of a Kondo insulator through most of the Brillouin zone it remains weakly metallic. This is because of (i) a band crossing in the z-direction and (ii) a negative indirect gap.

  16. Density functional theory and multiscale materials modeling

    Indian Academy of Sciences (India)

    Swapan K Ghosh

    2003-01-01

    One of the vital ingredients in the theoretical tools useful in materials modeling at all the length scales of interest is the concept of density. In the microscopic length scale, it is the electron density that has played a major role in providing a deeper understanding of chemical binding in atoms, molecules and solids. In the intermediate mesoscopic length scale, an appropriate picture of the equilibrium and dynamical processes has been obtained through the single particle number density of the constituent atoms or molecules. A wide class of problems involving nanomaterials, interfacial science and soft condensed matter has been addressed using the density based theoretical formalism as well as atomistic simulation in this regime. 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 density functions has been found to be quite appropriate. A unique single unified theoretical framework that emerges through the density concept at these diverse length scales and is applicable to both quantum and classical systems is the so called density functional theory (DFT) which essentially provides a vehicle to project the many-particle picture to a single particle one. Thus, the central equation for quantum DFT is a one-particle Schrödinger-like Kohn–Sham equation, while the same for classical DFT consists of Boltzmann type distributions, both corresponding to a system of noninteracting particles in the field of a density-dependent effective potential. Selected illustrative applications of quantum DFT to microscopic modeling of intermolecular interaction and that of classical DFT to a mesoscopic modeling of soft condensed matter systems are presented.

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

    Science.gov (United States)

    Pribram-Jones, Aurora

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

  18. Density functional theory: Fixing Jacob's ladder

    Science.gov (United States)

    Car, Roberto

    2016-09-01

    Density functional theory calculations can be carried out with different levels of accuracy, forming a hierarchy that is often represented by the rungs of a ladder. Now a new method has been developed that significantly improves the accuracy of the 'third rung' when calculating the properties of diversely bonded systems.

  19. 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 ou

  20. Basis convergence of range-separated density-functional theory

    CERN Document Server

    Franck, Odile; Luppi, Eleonora; Toulouse, Julien

    2014-01-01

    Range-separated density-functional theory is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components, and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whe...

  1. Teaching Density Functional Theory Through Experiential Learning

    Science.gov (United States)

    Narasimhan, Shobhana

    2015-09-01

    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.

  2. Density functional theory in the solid state.

    Science.gov (United States)

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

    2014-03-13

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

  3. 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

  4. Particle conservation in dynamical density functional theory.

    Science.gov (United States)

    de Las Heras, Daniel; Brader, Joseph M; Fortini, Andrea; Schmidt, Matthias

    2016-06-22

    We present the exact adiabatic theory for the dynamics of the inhomogeneous density distribution of a classical fluid. Erroneous particle number fluctuations of dynamical density functional theory are absent, both for canonical and grand canonical initial conditions. We obtain the canonical free energy functional, which yields the adiabatic interparticle forces of overdamped Brownian motion. Using an exact and one of the most advanced approximate hard core free energy functionals, we obtain excellent agreement with simulations. The theory applies to finite systems in and out of equilibrium.

  5. 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...

  6. The benchmark of gutzwiller density functional theory in hydrogen systems

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Y.; Wang, Cai-Zhuang; Ho, Kai-Ming

    2012-02-23

    We propose an approximate form of the exchange-correlation energy functional for the Gutzwiller density functional theory. It satisfies certain physical constraints in both weak and strong electron correlation limits. We benchmark the Gutzwiller density functional approximation in the hydrogen systems, where the static correlation error is shown to be negligible. The good transferability is demonstrated by applications to the hydrogen molecule and some crystal structures.

  7. The Benchmark of Gutzwiller Density Functional Theory in Hydrogen Systems

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yongxin; Wang, Cai-Zhuang; Ho, Kai-Ming

    2011-01-13

    We propose an approximate form of the exchange-correlation energy functional for the Gutzwiller density functional theory. It satisfies certain physical constraints in both weak and strong electron correlation limits. We benchmark the Gutzwiller density functional approximation in the hydrogen systems, where the static correlation error is shown to be negligible. The good transferability is demonstrated by applications to the hydrogen molecule and some crystal structures. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

  8. Density functional theory studies of etoricoxib

    Science.gov (United States)

    Sachdeva, Ritika; Kaur, Prabhjot; Singh, V. P.; Saini, G. S. S.

    2016-05-01

    Etoricoxib is a COX-2 selective inhibitor drug with molecular formula C18H15ClN2O2S. It is primarily used for the treatment of arthritis(rheumatoid, psoriatic, osteoarthritis), ankylosing spondylitis, gout and chronic low back pain. Theoretical studies of the molecule including geometry optimization and vibrational frequency calculations were carried out with the help of density functional theory calculations using 6-311++ g (d, p) basis set and B3LYP functional.

  9. Studies on structures and electron affinities of the simplest alkyl dithio radicals and their anions with gaussian-3 theory and density functional theory.

    Science.gov (United States)

    Gao, Aifang; Du, Hongli; Li, Aiguo; Pei, Huiyi

    2013-06-01

    The equilibrium geometries and electron affinities of the R-SS/R-SS(-)(R=CH₃, C₂H₅, n-C₃H7, i-C₃H₇, n-C₄H₉, t-C₄H₉, n-C₅H₁₁) species have been studied using the higher level of the Gaussian-3(G3) theory and 21 carefully calibrated pure and hybrid density functionals (five generalized gradient approximation (GGA) methods, seven hybrid GGAs, three meta GGA methods, and six hybrid meta GGAs) in conjunction with diffuse function augmented double-ζ plus polarization (DZP++) basis sets. The geometries are fully optimized with each method and discussed. The reliable adiabatic electron affinity has been presented by means of the high level of G3 technique. With the DZP++ DFT method, three measures of neutral/anion energy differences reported in this work are the adiabatic electron affinity, the vertical electron affinity, and the vertical detachment energy. The adiabatic electron affinities, obtained at the BP86, M05-2X, B3LYP, M06, B98, M06-2X, mPW1PW91, HCTH, B97-1, M05, PBE1PBE, and VSXC methods, are in agreement with the G3 results. These methods perform better for EA prediction and are considered to be reliable.

  10. Generalized density-functional theory: Conquering the -representability problem with exact functionals for the electron pair density and the second-order reduced density matrix

    Indian Academy of Sciences (India)

    Paul W Ayers; Mel Levy

    2005-09-01

    Using the constrained search and Legendre-transform formalisms, one can derive ``generalized” density-functional theories, in which the fundamental variable is either the electron pair density or the second-order reduced density matrix. In both approaches, the -representability problem is solved by the functional, and the variational principle is with respect to all pair densities (density matrices) that are nonnegative and appropriately normalized. The Legendre-transform formulation provides a lower bound on the constrained-search functional. Noting that experience in density-functional and density-matrix theories suggests that it is easier to approximate functionals than it is to approximate the set of -representable densities sheds some light on the significance of this work.

  11. Extraction of state-resolved information from systems with a fractional number of electrons within the framework of time-dependent density functional theory

    Science.gov (United States)

    Wang, Feng; Yao, Yugui; Calvayrac, Florent; Zhang, Fengshou

    2016-09-01

    The determination of the state-resolved physical information within the framework of time-dependent density functional theory has remained a widely open question. We demonstrated the ability to extract the state-resolved probability from the knowledge of only the time-dependent density, which has been used as the basic variable within the time-dependent density functional theory, with the help of state-resolved single-electron capture experiments for collisions of protons on helium in the energy range of 2-100 keV/amu. The present theoretical results for capture into states of H(1s), H(2s), and H(2p) are in good agreement with the most sophisticated experimental results of H+ + He(1s2) system, validating our approach and numerical implementation.

  12. Computing dispersion interactions in density functional theory

    Science.gov (United States)

    Cooper, V. R.; Kong, L.; Langreth, D. C.

    2010-02-01

    In this article techniques for including dispersion interactions within density functional theory are examined. In particular comparisons are made between four popular methods: dispersion corrected DFT, pseudopotential correction schemes, symmetry adapted perturbation theory, and a non-local density functional - the so called Rutgers-Chalmers van der Waals density functional (vdW-DF). The S22 benchmark data set is used to evaluate the relative accuracy of these methods and factors such as scalability and transferability are also discussed. We demonstrate that vdW-DF presents an excellent compromise between computational speed and accuracy and lends most easily to full scale application in solid materials. This claim is supported through a brief discussion of a recent large scale application to H2 in a prototype metal organic framework material (MOF), Zn2BDC2TED. The vdW-DF shows overwhelming promise for first-principles studies of physisorbed molecules in porous extended systems; thereby having broad applicability for studies as diverse as molecular adsorption and storage, battery technology, catalysis and gas separations.

  13. Basis convergence of range-separated density-functional theory.

    Science.gov (United States)

    Franck, Odile; Mussard, Bastien; Luppi, Eleonora; Toulouse, Julien

    2015-02-21

    Range-separated density-functional theory (DFT) is an alternative approach to Kohn-Sham density-functional theory. The strategy of range-separated density-functional theory consists in separating the Coulomb electron-electron interaction into long-range and short-range components and treating the long-range part by an explicit many-body wave-function method and the short-range part by a density-functional approximation. Among the advantages of using many-body methods for the long-range part of the electron-electron interaction is that they are much less sensitive to the one-electron atomic basis compared to the case of the standard Coulomb interaction. Here, we provide a detailed study of the basis convergence of range-separated density-functional theory. We study the convergence of the partial-wave expansion of the long-range wave function near the electron-electron coalescence. We show that the rate of convergence is exponential with respect to the maximal angular momentum L for the long-range wave function, whereas it is polynomial for the case of the Coulomb interaction. We also study the convergence of the long-range second-order Møller-Plesset correlation energy of four systems (He, Ne, N2, and H2O) with cardinal number X of the Dunning basis sets cc - p(C)V XZ and find that the error in the correlation energy is best fitted by an exponential in X. This leads us to propose a three-point complete-basis-set extrapolation scheme for range-separated density-functional theory based on an exponential formula.

  14. General degeneracy in density functional perturbation theory

    Science.gov (United States)

    Palenik, Mark C.; Dunlap, Brett I.

    2017-07-01

    Degenerate perturbation theory from quantum mechanics is inadequate in density functional theory (DFT) because of nonlinearity in the Kohn-Sham potential. Herein, we develop the fully general perturbation theory for open-shell, degenerate systems in Kohn-Sham DFT, without assuming the presence of symmetry or equal occupation of degenerate orbitals. To demonstrate the resulting methodology, we apply it to the iron atom in the central field approximation, perturbed by an electric quadrupole. This system was chosen because it displays both symmetry required degeneracy, between the five 3 d orbitals, as well as accidental degeneracy, between the 3 d and 4 s orbitals. The quadrupole potential couples the degenerate 3 d and 4 s states, serving as an example of the most general perturbation.

  15. Spin in Density-Functional Theory

    CERN Document Server

    Jacob, Christoph R; 10.1002/qua.24309

    2012-01-01

    The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. While density-functional theory (DFT) is widely applied in this area, the sometimes severe limitations of its currently available approximate realizations often preclude its application as a predictive theory. Here, we review the foundations of DFT applied to open-shell systems, both within the nonrelativistic and the relativistic framework. In particular, we provide an in-depth discussion of the exact theory, with a focus on the role of the spin density and possibilities for targeting specific spin states. It turns out that different options exist for setting up Kohn-Sham DFT schemes for open-shell systems, which imply different definitions of the exchange-correlation energy functional and lead to different exact conditions on this functional. Finally, we suggest some possible directions for future developments.

  16. Effective Maxwell Equations from Time-dependent Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    Weinan E; Jianfeng LU; Xu YANG

    2011-01-01

    The behavior of interacting electrons in a perfect crystal under macroscopic external electric and magnetic fields is studied. Effective Maxwell equations for the macroscopic electric and magnetic fields are derived starting from time-dependent density functional theory. Effective permittivity and permeability coefficients are obtained.

  17. Density functional resonance theory: complex density functions, convergence, orbital energies, and functionals.

    Science.gov (United States)

    Whitenack, Daniel L; Wasserman, Adam

    2012-04-28

    Aspects of density functional resonance theory (DFRT) [D. L. Whitenack and A. Wasserman, Phys. Rev. Lett. 107, 163002 (2011)], a recently developed complex-scaled version of ground-state density functional theory (DFT), are studied in detail. The asymptotic behavior of the complex density function is related to the complex resonance energy and system's threshold energy, and the function's local oscillatory behavior is connected with preferential directions of electron decay. Practical considerations for implementation of the theory are addressed including sensitivity to the complex-scaling parameter, θ. In Kohn-Sham DFRT, it is shown that almost all θ-dependence in the calculated energies and lifetimes can be extinguished via use of a proper basis set or fine grid. The highest occupied Kohn-Sham orbital energy and lifetime are related to physical affinity and width, and the threshold energy of the Kohn-Sham system is shown to be equal to the threshold energy of the interacting system shifted by a well-defined functional. Finally, various complex-scaling conditions are derived which relate the functionals of ground-state DFT to those of DFRT via proper scaling factors and a non-Hermitian coupling-constant system.

  18. Molecular Density Functional Theory of Water

    CERN Document Server

    Jeanmairet, Guillaume; Vuilleumier, Rodolphe; Borgis, Daniel; 10.1021/jz301956b

    2013-01-01

    Three dimensional implementations of liquid state theories offer an efficient alternative to computer simulations for the atomic-level description of aqueous solutions in complex environments. In this context, we present a (classical) molecular density functional theory (MDFT) of water that is derived from first principles and is based on two classical density fields, a scalar one, the particle density, and a vectorial one, the multipolar polarization density. Its implementation requires as input the partial charge distribution of a water molecule and three measurable bulk properties, namely the structure factor and the k-dependent longitudinal and transverse dielectric constants. It has to be complemented by a solute-solvent three-body term that reinforces tetrahedral order at short range. The approach is shown to provide the correct three-dimensional microscopic solvation profile around various molecular solutes, possibly possessing H-bonding sites, at a computer cost two-three orders of magnitude lower tha...

  19. Effect Of Non-metal Elements (C, N, S) As Anionic Dopants On Electronic Structure Of Tio2-Anatase By Density-Functional Theory Approach

    OpenAIRE

    Hari Sutrisno

    2016-01-01

    This article is a theoritical approach to calculate the electronic structure of undoped- and non-metal anions doped-TiO2-anatase. The objective of the research is to calculate abinitio the band structure and the density of states (DOS) of undoped-, C-, N-, and S-doped TiO2-anatase. Kohn-Sham equations are performed with the density functional theory (DFT) using the local density approximation (LDA) for exchange-correlation functional. The first-principle calculations were done using supercell...

  20. Theoretical Study on Structure and Electronic Properties of 2, 5-Bis [4-N, N-Diethylaminostyryl] Thiophene and Its Furan and Pyrrole Derivatives Using Density Functional Theory (Dft

    Directory of Open Access Journals (Sweden)

    *B. Semire

    2012-12-01

    Full Text Available Theoretical calculations using Density Functional Theory (DFT were performed on 2,5-bis[4-N,N-diethylaminostyryl]thiophene and its furan and pyrrole derivatives The energy band gaps calculated at B3LYP/6-31G(d level for thiophene derivatives are lower than that of furan and pyrrole analogues. The absorption λmax calculated using DFT was shifted to longer wavelength by replacement of R = CH3 by C2H5 for all studied molecules. The geometries and electronic properties of the compounds were also studied.

  1. A Density Functional Theory Study on Electronic Structure and Second—order Nonlinear Optical Properties of Some Push—Pull Molecules

    Institute of Scientific and Technical Information of China (English)

    洒荣建; 吴克琛; 林晨升; 刘萍; 莽朝永

    2003-01-01

    Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches.

  2. Longest-Wavelength Electronic Excitations of Linear Cyanines: The Role of Electron Delocalization and of Approximations in Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Ii, Barry Moore; Autschbach, Jochen

    2013-11-12

    The lowest-energy/longest-wavelength electronic singlet excitation energies of linear cyanine dyes are examined, using time-dependent density functional theory (TDDFT) and selected wave function methods in comparison with literature data. Variations of the bond-length alternation obtained with different optimized structures produce small differences of the excitation energy in the limit of an infinite chain. Hybrid functionals with range-separated exchange are optimally 'tuned', which is shown to minimize the delocalization error (DE) in the cyanine π systems. Much unlike the case of charge-transfer excitations, small DEs are not strongly correlated with better performance. A representative cyanine is analyzed in detail. Compared with accurate benchmark data, TDDFT with 'pure' local functionals gives too high singlet excitation energies for all systems, but DFT-based ΔSCF calculations with a local functional severely underestimates the energies. TDDFT strongly overestimates the difference between singlet and triplet excitation energies. An analysis points to systematically much too small magnitudes of integrals from the DFT components of the exchange-correlation response kernel as the likely culprit. The findings support previous suggestions that the differential correlation energy between the ground and excited state is not correctly produced by TDDFT with most functionals.

  3. Quasi-Low-Dimensional Electron Gas with One Populated Band as a Testing Ground for Time-Dependent Density-Functional Theory of Mesoscopic Systems.

    Science.gov (United States)

    Nazarov, Vladimir U

    2017-06-09

    We find an exact analytical solution to the exchange-only time-dependent density-functional theory (TDDFT) problem for a significant class of quasi-low-dimensional (QLD) materials: QLD electron gas with only one band filled in the direction perpendicular to the layer or wire. The theory yields the TD exchange potential as an explicit nonlocal operator of the TD spin density. The dressed interband (image states) excitation spectra of quasi-two-dimensional electron gas are obtained, while the comparison with the Kohn-Sham transitions provides insights into the qualitative and quantitative role of the many-body interactions. Important cancellations between the Hartree f_{H} and the exchange f_{x} kernels of TDDFT are found in the low-density regime, elucidating the interrelations between the Kohn-Sham and the many-body dynamics in mesoscopic systems.

  4. Quasi-Low-Dimensional Electron Gas with One Populated Band as a Testing Ground for Time-Dependent Density-Functional Theory of Mesoscopic Systems

    Science.gov (United States)

    Nazarov, Vladimir U.

    2017-06-01

    We find an exact analytical solution to the exchange-only time-dependent density-functional theory (TDDFT) problem for a significant class of quasi-low-dimensional (QLD) materials: QLD electron gas with only one band filled in the direction perpendicular to the layer or wire. The theory yields the TD exchange potential as an explicit nonlocal operator of the TD spin density. The dressed interband (image states) excitation spectra of quasi-two-dimensional electron gas are obtained, while the comparison with the Kohn-Sham transitions provides insights into the qualitative and quantitative role of the many-body interactions. Important cancellations between the Hartree fH and the exchange fx kernels of TDDFT are found in the low-density regime, elucidating the interrelations between the Kohn-Sham and the many-body dynamics in mesoscopic systems.

  5. Phases of Polonium via Density Functional Theory

    Science.gov (United States)

    Verstraete, Matthieu J.

    2010-01-01

    The thermodynamical properties of the main phases of metallic polonium are examined using density functional theory. The exceptional nature of the solid-solid phase transition of α to β Po is underlined: it induces a lowering in symmetry, from cubic to rhombohedral, with increasing temperature. This is explained as the result of a delicate balance between bonding and entropic effects. Overall agreement with existing experimental data is good by state-of-the-art standards. The phonons of Po present Kohn anomalies, and it is shown that the effect of spin-orbit interactions is the inverse of that in normal metals: due to the nonspherical nature of the Fermi Surface, spin-orbit effects reduce nesting and harden most phonon frequencies.

  6. Density Functional Theory An Advanced Course

    CERN Document Server

    Dreizler, Reiner M

    2011-01-01

    Density Functional Theory (DFT) has firmly established itself as the workhorse for the atomic-level simulation of condensed matter phases, pure or composite materials and quantum chemical systems. The present book is a rigorous and detailed introduction to the foundations up to and including such advanced topics as orbital-dependent functionals and both time-dependent and relativistic DFT. Given the many ramifications of contemporary DFT, this text concentrates on the self-contained presentation of the basics of the most widely used DFT variants. This implies a thorough discussion of the corresponding existence theorems and effective single particle equations, as well as of key approximations utilized in implementations. The formal results are complemented by selected quantitative results, which primarily aim at illustrating strengths and weaknesses of a particular approach or functional. DFT for superconducting or nuclear and hadronic systems are not addressed in this work. The structure and material contain...

  7. Adiabatic density-functional perturbation theory

    Science.gov (United States)

    Gonze, Xavier

    1995-08-01

    The treatment of adiabatic perturbations within density-functional theory is examined, at arbitrary order of the perturbation expansion. Due to the extremal property of the energy functional, standard variation-perturbation theorems can be used. The different methods (Sternheimer equation, extremal principle, Green's function, and sum over state) for obtaining the perturbation expansion of the wave functions are presented. The invariance of the Hilbert space of occupied wave functions with respect to a unitary transformation leads to the definition of a ``parallel-transport-gauge'' and a ``diagonal-gauge'' perturbation expansion. Then, the general expressions are specialized for the second, third, and fourth derivative of the energy, with an example of application of the method up to third order.

  8. 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.)

  9. Energy Continuity in Degenerate Density Functional Perturbation Theory

    CERN Document Server

    Palenik, Mark C

    2016-01-01

    Fractional occupation numbers can produce open-shell degeneracy in density functional theory. We develop the corresponding perturbation theory by requiring that a differentiable map connects the initial and perturbed states. The degenerate state connects to a single perturbed state which extremizes, but does not necessarily minimize or maximize, the energy with respect to occupation numbers. Using a system of three electrons in a harmonic oscillator potential, we relate the counterintuitive sign of first-order occupation numbers to eigenvalues of the electron-electron interaction Hessian.

  10. Prediction of the electronic structures, thermodynamic and mechanical properties in manganese doped magnesium-based alloys and their saturated hydrides based on density functional theory

    Science.gov (United States)

    Zhang, Ziying; Zhang, Huizhen; Zhao, Hui; Yu, Zhishui; He, Liang; Li, Jin

    2015-04-01

    The crystal structures, electronic structures, thermodynamic and mechanical properties of Mg2Ni alloy and its saturated hydride with different Mn-doping contents are investigated using first-principles density functional theory. The lattice parameters for the Mn-doped Mg2Ni alloys and their saturated hydrides decreased with an increasing Mn-doping content because of the smaller atomic size of Mn compared with that of Mg. Analysis of the formation enthalpies and electronic structures reveal that the partial substitution of Mg with Mn reduces the stability of Mg2Ni alloy and its saturated hydride. The calculated elastic constants indicate that, although the partial substitution of Mg with Mn lowers the toughness of the hexagonal Mg2Ni alloy, the charge/discharge cycles are elevated when the Mn-doping content is high enough to form the predicted intermetallic compound Mg3MnNi2.

  11. Atomic and molecular adsorption on transition-metal carbide (111) surfaces from density-functional theory: a trend study of surface electronic factors

    DEFF Research Database (Denmark)

    Vojvodic, Aleksandra; Ruberto, C.; Lundqvist, Bengt

    2010-01-01

    This study explores atomic and molecular adsorption on a number of early transition-metal carbides (TMCs) in NaCl structure by means of density-functional theory calculations. The investigated substrates are the TM-terminated TMC(111) surfaces, of interest because of the presence of different types......, surface relaxations, Bader charges, and surface-localized densities of states (DOSs). Detailed comparisons between surface and bulk DOSs reveal the existence of transition-metal localized SRs (TMSRs) in the pseudogap and of several C-localized SRs (CSRs) in the upper valence band on all considered TMC(111......C, delta-MoC, TaC, and WC (in NaCl structure) and the adsorbates H, B, C, N, O, F, NH, NH2, and NH3. Trends in adsorption strength are explained in terms of surface electronic factors, by correlating the calculated adsorption-energy values with the calculated surface electronic structures. The results...

  12. Structures and properties of electronically excited chromophores in solution from the polarizable continuum model coupled to the time-dependent density functional theory.

    Science.gov (United States)

    Mennucci, Benedetta; Cappelli, Chiara; Guido, Ciro Achille; Cammi, Roberto; Tomasi, Jacopo

    2009-04-02

    This paper provides an overview of recent research activities concerning the quantum-mechanical description of structures and properties of electronically excited chromophores in solution. The focus of the paper is on a specific approach to include solvent effects, namely the polarizable continuum model (PCM). Such a method represents an efficient strategy if coupled to proper quantum-mechanical descriptions such as the time-dependent density functional theory (TDDFT). As a result, the description of molecules in the condensed phase can be extended to excited states still maintaining the computational efficiency and the physical reliability of the ground-state calculations. The most important theoretical and computational aspects of the coupling between PCM and TDDFT are presented and discussed together with an example of application to the study of the low-lying electronic excited states of push-pull chromophores in different solvents.

  13. Ab initio density functional theory investigation of the structural, electronic and optical properties of Ca3Sb2 in hexagonal and cubic phases

    Science.gov (United States)

    Arghavani Nia, Borhan; Sedighi, Matin; Shahrokhi, Masoud; Moradian, Rostam

    2013-11-01

    A density functional theory study of structural, electronical and optical properties of Ca3Sb2 compound in hexagonal and cubic phases is presented. In the exchange-correlation potential, generalized gradient approximation (PBE-GGA) has been used to calculate lattice parameters, bulk modulus, cohesive energy, dielectric function and energy loss spectra. The electronic band structure of this compound has been calculated using the above two approximations as well as another form of PBE-GGA, proposed by Engle and Vosko (EV-GGA). It is found that the hexagonal phase of Ca3Sb2 has an indirect gap in the Γ→N direction; while in the cubic phase there is a direct-gap at the Γ point in the PBE-GGA and EV-GGA. Effects of applying pressure on the band structure of the system studied and optical properties of these systems were calculated.

  14. Influence of alkali metal superoxides on structure, electronic, and optical properties of Be12O12 nanocage: Density functional theory study

    Science.gov (United States)

    Raoof Toosi, Ali; Shamlouei, Hamid Reza; Hesari, Asghar Mohammadi

    2016-09-01

    The effect of alkali metal superoxides M3O (M = Li, Na, K) on the electronic and optical properties of a Be12O12 nanocage was studied by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The energy gaps (Eg) of all configurations were calculated. Generally, the adsorption of alkali metal superoxides on the Be12O12 nanocage causes a decrease of Eg. Electric dipole moment μ, polarizability α, and static first hyperpolarizability β were calculated and it was shown that the adsorption of alkali metal superoxides on Be12O12 increases its polarizability. It was found that the absorption of M3O on Be12O12 nanocluster improves its nonlinear optical properties. The highest first hyperpolarizability (β ≈ 214000 a.u.) is obtained in the K3O-Be12O12 nanocluster. The TD-DFT calculations were performed to investigate the origin of the first hyperpolarizabilities and it was shown that a higher first hyperpolarizability belongs to the structure that has a lower transition energy.

  15. Influence on electron energy loss spectroscopy of the niobium-substituted uranium atom: A density functional theory study

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    We present the electronic structure and electron energy loss spectroscopy (EELS) for uranium, niobium and U3Nb in which uranium is substituted by niobium. Comparing the electronic structures and optical properties for uranium, niobium and U3Nb, we found that when niobium atom replaces uranium atom in the center lattice, density of state (DOS) of U3Nb shifts downward to low energy. Niobium affects DOS forfand d electrons more than that for p and s electrons. U3Nb is similar to uranium for the electronic energy loss spectra.

  16. Chemistry by Way of Density Functional Theory

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.; Ricca, Alessandra; Partridge, Harry; Langohff, Stephen R.; Arnold, James O. (Technical Monitor)

    1996-01-01

    In this work we demonstrate that density functional theory (DFT) methods make an important contribution to understanding chemical systems and are an important additional method for the computational chemist. We report calibration calculations obtained with different functionals for the 55 G2 molecules to justify our selection of the B3LYP functional. We show that accurate geometries and vibrational frequencies obtained at the B3LYP level can be combined with traditional methods to simplify the calculation of accurate heats of formation. We illustrate the application of the B3LYP approach to a variety of chemical problems from the vibrational frequencies of polycyclic aromatic hydrocarbons to transition metal systems. We show that the B3LYP method typically performs better than the MP2 method at a significantly lower computational cost. Thus the B3LYP method allows us to extend our studies to much larger systems while maintaining a high degree of accuracy. We show that for transition metal systems, the B3LYP bond energies are typically of sufficient accuracy that they can be used to explain experimental trends and even differentiate between different experimental values. We show that for boron clusters the B3LYP energetics are not as good as for many of the other systems presented, but even in this case the B3LYP approach is able to help understand the experimental trends.

  17. Scaled density functional theory correlation functionals.

    Science.gov (United States)

    Ghouri, Mohammed M; Singh, Saurabh; Ramachandran, B

    2007-10-18

    We show that a simple one-parameter scaling of the dynamical correlation energy estimated by the density functional theory (DFT) correlation functionals helps increase the overall accuracy for several local and nonlocal functionals. The approach taken here has been described as the "scaled dynamical correlation" (SDC) method [Ramachandran, J. Phys. Chem. A 2006, 110, 396], and its justification is the same as that of the scaled external correlation (SEC) method of Brown and Truhlar. We examine five local and five nonlocal (hybrid) DFT functionals, the latter group including three functionals developed specifically for kinetics by the Truhlar group. The optimum scale factors are obtained by use of a set of 98 data values consisting of molecules, ions, and transition states. The optimum scale factors, found with a linear regression relationship, are found to differ from unity with a high degree of correlation in nearly every case, indicating that the deviation of calculated results from the experimental values are systematic and proportional to the dynamic correlation energy. As a consequence, the SDC scaling of dynamical correlation decreases the mean errors (signed and unsigned) by significant amounts in an overwhelming majority of cases. These results indicate that there are gains to be realized from further parametrization of several popular exchange-correlation functionals.

  18. Periphery-Hydrogenating Effects on the Unordinary 14 w-Electron Delocalized Circuits and Related Electronic Properties of Subporphyrazine Analogs: A Density Functional Theory Investigation%Periphery-Hydrogenating Effects on the Unordinary 14 w-Electron Delocalized Circuits and Related Electronic Properties of Subporphyrazine Analogs: A Density Functional Theory Investigation

    Institute of Scientific and Technical Information of China (English)

    赵鲁阳; 齐冬冬; 蔡雪; 姜建壮

    2012-01-01

    Density functional theory method was employed to investigate the electronic properties of two series of sub- porphyrazine and subphthalocyanine derivatives, namely SubPz, SubPz-1H, SubPz-2H, SubPz-3H, SubPc, SubPc-1H, SubPc-2H, and SubPc-3H. Calculated results show that peripheral hydrogenation essentially changes the delocalized pattern from the common π14^14 to limited π13^14 or π12^14 for SubPz series, and substantially weakens the aromaticity for both SubPz and SubPc compounds. The unordinary delocalized circuit owns an unstable energy level, and thus gives rise to a notable transformation of geometric configuration, frontier molecular orbital topology, and absorption spectral bands.

  19. 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

  20. Ab initio density functional theory investigation of the structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases

    Energy Technology Data Exchange (ETDEWEB)

    Arghavani Nia, Borhan, E-mail: b.arghavani@gmail.com [Department of Physics, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Sedighi, Matin [Department of Physics, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Shahrokhi, Masoud [Young Researchers and Elite Club, Kermanshah Branch, Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Moradian, Rostam [Nano-Science and Nano-Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Computational Physics Science Research Laboratory, Department of Nano-Science, Institute for Studies in Theoretical Physics and Mathematics (IPM), P.O. Box 19395-1795, Tehran (Iran, Islamic Republic of)

    2013-11-15

    A density functional theory study of structural, electronical and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. In the exchange–correlation potential, generalized gradient approximation (PBE-GGA) has been used to calculate lattice parameters, bulk modulus, cohesive energy, dielectric function and energy loss spectra. The electronic band structure of this compound has been calculated using the above two approximations as well as another form of PBE-GGA, proposed by Engle and Vosko (EV-GGA). It is found that the hexagonal phase of Ca{sub 3}Sb{sub 2} has an indirect gap in the Γ→N direction; while in the cubic phase there is a direct-gap at the Γ point in the PBE-GGA and EV-GGA. Effects of applying pressure on the band structure of the system studied and optical properties of these systems were calculated. - Graphical abstract: A density functional theory study of structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. Display Omitted - Highlights: • Physical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases are investigated. • It is found that the hexagonal phase is an indirect gap semiconductor. • Ca{sub 3}Sb{sub 2} is a direct-gap semiconductor at the Γ point in the cubic phase. • By increasing pressure the semiconducting band gap and anti-symmetry gap are decreased.

  1. Electronic reconstruction of hexagonal FeS: a view from density functional dynamical mean-field theory

    Science.gov (United States)

    Craco, L.; Faria, J. L. B.; Leoni, S.

    2017-03-01

    We present a detailed study of correlation- and pressure-induced electronic reconstruction in hexagonal iron monosulfide, a system which is widely found in meteorites and one of the components of Earth’s core. Based on a perusal of experimental data, we stress the importance of multi-orbital electron-electron interactions in concert with first-principles band structure calculations for a consistent understanding of its intrinsic Mott–Hubbard insulating state. We explain the anomalous nature of pressure-induced insulator-metal-insulator transition seen in experiment, showing that it is driven by dynamical spectral weight transfer in response to changes in the crystal-field splittings under pressure. As a byproduct of this analysis, we confirm that the electronic transitions observed in pristine FeS at moderated pressures are triggered by changes in the spin state which causes orbital-selective Kondo quasiparticle electronic reconstruction at low energies.

  2. Semilocal density functional theory with correct surface asymptotics

    Science.gov (United States)

    Constantin, Lucian A.; Fabiano, Eduardo; Pitarke, J. M.; Della Sala, Fabio

    2016-03-01

    Semilocal density functional theory is the most used computational method for electronic structure calculations in theoretical solid-state physics and quantum chemistry of large systems, providing good accuracy with a very attractive computational cost. Nevertheless, because of the nonlocality of the exchange-correlation hole outside a metal surface, it was always considered inappropriate to describe the correct surface asymptotics. Here, we derive, within the semilocal density functional theory formalism, an exact condition for the imagelike surface asymptotics of both the exchange-correlation energy per particle and potential. We show that this condition can be easily incorporated into a practical computational tool, at the simple meta-generalized-gradient approximation level of theory. Using this tool, we also show that the Airy-gas model exhibits asymptotic properties that are closely related to those at metal surfaces. This result highlights the relevance of the linear effective potential model to the metal surface asymptotics.

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

    KAUST Repository

    Khan, Mohammad A.

    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.

  4. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...

  5. Is Density Functional Theory adequate for quantum transport?

    Science.gov (United States)

    Burke, Kieron

    2007-03-01

    Density functional calculations for the electronic conductance of single molecules attached to leads are now common. I'll examine the methodology from a rigorous point of view, discussing where it can be expected to work, and where it should fail. When molecules are weakly coupled to leads, local and gradient-corrected approximations fail, as the Kohn-Sham levels are misaligned. In the weak bias regime, XC corrections to the current are missed by the standard methodology. Finally, I will compare and contrast several new methodologies that go beyond the present standard approach of applying the Landauer formula to ground-state DFT. Self-interaction errors in density functional calculations of electronictransport, C. Toher, A. Filippetti, S. Sanvito, and K. Burke, Phys. Rev. Lett. 95, 146402 (2005) The Dramatic Role of the Exchange-Correlation Potential in ab initio Electron Transport Calculations, S-H. Ke, H.U. Baranger, and W. Yang, cond-mat/0609367. Zero-bias molecular electronics: Exchange-correlation corrections to Landauer's formula, M. Koentopp, K. Burke, and F. Evers, Phys. Rev. B Rapid Comm., 73, 121403 (2006). Density Functional Theory of the Electrical Conductivity of Molecular Devices, K. Burke, Roberto Car, and Ralph Gebauer, Phys. Rev. Lett. 94, 146803 (2005). Density functional calculations of nanoscale conductance, Connie Chang, Max Koentopp, Kieron Burke, and Roberto Car, in prep.

  6. Density Functional Theory Investigations on the Geometric and Electronic Structures of 4–Azidomethyl–6–Isopropyl–2H–Chromen–2–One

    Directory of Open Access Journals (Sweden)

    Toh Pek–Lan

    2015-01-01

    Full Text Available We have employed first principle Density Functional Theory (DFT investigations to study the physical and electronic properties of 4–Azidomethyl–6–isopropyl–2H–chromen–2–one, C13H13N3O2. Complete geometry optimization calculations were carried out to find local energy minimum of the molecular system using the B3LYP approach with a variety of basis sets. The optimized geometries were then used to determine the HOMO–LUMO gaps, Mulliken atomic charges, and others. Our calculation results show that the computed geometrical properties of C13H13N3O2 cluster model are in good agreement with the corresponding measured experimental value. The calculated energies obtained are close to each other using the B3LYP density functional method combined with a variety of basis sets. Furthermore, using B3LYP/6–31G** method, the oxygen–attached carbon, C2 atom has the highest positively charge, with the corresponding value of +0.59. For both oxygen atoms (O1 and O2, the calculated charge values obtained are about –0.52 and –0.46, respectively.

  7. The stability and electronic structures of Si/O/Al/P atom doped (5,0)boron nitrogen nanotubes with Stone-Wales defects: Density functional theory studies

    Science.gov (United States)

    Li, KeJing; Ye, JinQian; Zhang, Juan; Wang, XiYuan; Shao, QingYi

    2017-03-01

    Using density functional theory, we have investigated Si/O/Al/P atoms doped (5,0)BNNTs with SW defects. We have mainly found that Si/O/Al/P have improved the stability of (5,0)BNNTs with SW defects. In view of Mulliken charge, we have thought Si/O/Al/P atoms have donated electrons (charge +e state or charge -e state) to nanotubes, contributing BNNTs with SW defects to stable. Meanwhile, from the aspect of energy band structure and DOS, we have further explained the reason. We have considerred that stability of doped structures has related to hybridization between doped atom and BNNTs. The stability has changed with changing the degree of hybridization. Moreover, B atom can play a crucial role in the insertion of Si/O/Al/P atom into (5,0)BNNTs with SW defects.

  8. Impact of electron delocalization on the nature of the charge-transfer states in model pentacene/C60 Interfaces: A density functional theory study

    KAUST Repository

    Yang, Bing

    2014-12-04

    Electronic delocalization effects have been proposed to play a key role in photocurrent generation in organic photovoltaic devices. Here, we study the role of charge delocalization on the nature of the charge-transfer (CT) states in the case of model complexes consisting of several pentacene molecules and one fullerene (C60) molecule, which are representative of donor/acceptor heterojunctions. The energies of the CT states are examined by means of time-dependent density functional theory (TD-DFT) using the long-range-corrected functional, ωB97X, with an optimized range-separation parameter, ω. We provide a general description of how the nature of the CT states is impacted by molecular packing (i.e., interfacial donor/acceptor orientations), system size, and intermolecular interactions, features of importance in the understanding of the charge-separation mechanism.

  9. Electronic structures of AlMoO(y)(-) (y = 1-4) determined by photoelectron spectroscopy and density functional theory calculations.

    Science.gov (United States)

    Waller, Sarah E; Mann, Jennifer E; Hossain, Ekram; Troyer, Mary; Jarrold, Caroline C

    2012-07-14

    Vibrationally-resolved photoelectron spectra of AlMoO(y)(-) (y = 1-4) are presented and analyzed in conjunction with density functional theory computational results. The structures determined for the AlMoO(y) anion and neutral clusters suggest ionic bonding between Al(+) and a MoO(y)(-) or MoO(y)(-2) moiety, and point to the relative stability of Mo=O versus Al=O bonds. The highest occupied and partially occupied orbitals in the anions and neutrals can be described as Mo atomic-like orbitals, so while the Mo is in a higher oxidation state than Al, the most energetically accessible electrons are localized on the molybdenum center.

  10. Perspective: Fundamental aspects of time-dependent density functional theory

    Science.gov (United States)

    Maitra, Neepa T.

    2016-06-01

    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.

  11. Electronic structure of ScN and YN:density-functional theory LDA and GW approximation calculations

    Institute of Scientific and Technical Information of China (English)

    Lü Tie-Yu; Huang Mei-Chun

    2007-01-01

    The desirable physical properties of hardness, high temperature stability, and conductivity make the early transition metal nitrides important materials for various technological applications. To learn more about the nature of these materials, the local-density approximation(LDA) and GW approximation i.e. combination of the Green function G and the screened Coulomb interaction W, have been performed. This paper investigates the bulk electronic and physical properties of early transition metal mononitrides, ScN and YN in the rocksalt structure. In this paper, the semicore electrons are regarded as valance electrons. ScN appears to be a semimetal, and YN is semiconductor with band gap of0.142 eV within the LDA, but are in fact semiconductors with indirect band gaps of 1.244 and 0.544 eV respectively, as revealed by calculations performed using GW approximation.

  12. Electronic and Elastic Properties of CaMg2 Alloy Phase under Various Pressures by Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Fu Jia

    2017-01-01

    Full Text Available The influencing effect of pressure on structural, elastic and electronic properties of CaMg2 Laves phase is mainly investigated. The optimized structural parameters at zero pressure are a = b = 6.250Å, c = 10.101Å, which has good agreement with the experimental and theoretical values. The elastic constants are calculated, and then the bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and anisotropy factor are determined. The results show that the applied pressure is beneficial to the elastic properties of CaMg2. The analysis of electronic density of states (DOS and Mulliken electron population reveal the bonding characteristics in CaMg2 crystal. Finally, the Debye temperatures under different pressures are obtained from the average sound velocity.

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

    Science.gov (United States)

    Sato, Shunsuke A.; Taniguchi, Yasutaka; Shinohara, Yasushi; Yabana, Kazuhiro

    2015-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Shunsuke A. [Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Taniguchi, Yasutaka [Center for Computational Science, University of Tsukuba, Tsukuba 305-8571 (Japan); Department of Medical and General Sciences, Nihon Institute of Medical Science, 1276 Shimogawara, Moroyama-Machi, Iruma-Gun, Saitama 350-0435 (Japan); Shinohara, Yasushi [Max Planck Institute of Microstructure Physics, 06120 Halle (Germany); Yabana, Kazuhiro [Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Center for Computational Science, University of Tsukuba, Tsukuba 305-8571 (Japan)

    2015-12-14

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

  15. The one-electron description of excited states: Natural excitation orbitals of density matrix theory and Kohn-Sham orbitals of density functional theory as ideal orbitals

    Science.gov (United States)

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

    2015-10-01

    Linear response density matrix functional theory has been shown to solve the main problems of time-dependent density functional theory (deficient in case of double, charge transfer and bond breaking excitations). However, the natural orbitals preclude the description of excitations as (approximately) simple orbital-to-orbital transitions: many weakly occupied 'virtual' natural orbitals are required to describe the excitations. Kohn-Sham orbitals on the other hand afford for many excitations such a simple orbital description. In this communication we show that a transformation of the set of weakly occupied NOs can be defined such that the resulting natural excitation orbitals (NEOs) restore the single orbital transition structure for excitations generated by the linear response DMFT formalism.

  16. A density functional theory study of electronic and magnetic properties of rare earth doped monolayered molybdenum disulphide

    Science.gov (United States)

    Majid, Abdul; Imtiaz, Anum; Yoshiya, Masato

    2016-10-01

    The effects of Rare Earth (RE) atoms Sm, Eu, Gd, Tb, and Dy doping on structural, electronic, and magnetic properties of single layer MoS2 were investigated using first principles calculations. The analysis of electronic properties pointed out the appearance of host-impurity hybrid states on the edges of principal bands of the material, which appeared to cause narrowing of its bandgap. The values of total magnetic moment were calculated as 3.3 μB, 8.1 μB, 8.5 μB, 6.8 μB, and 6.4 μB for Sm-, Eu-, Gd-, Tb-, and Dy-doped MoS2, respectively. The underestimation of magnetic moment in the case of Sm doping is found which is assigned to shielding of 4f moments and quenching of angular momentum caused by Sm 4f-S 3p hybridization. On the other hand, the observed overestimation of magnetic moments for Eu and Gd cases is likely to be due to increase in angular momentum due to indirect exchange interaction of highly localized 4f states via 5d or 6s conduction electrons. The findings of this work point out the possibilities of tuning the band gap and magnetic properties of monolayer MoS2 upon RE doping for realization of p-type ferromagnetic semiconductors.

  17. Density functional theory analysis of structural and electronic properties of orthorhombic perovskite CH3NH3PbI3.

    Science.gov (United States)

    Wang, Yun; Gould, Tim; Dobson, John F; Zhang, Haimin; Yang, Huagui; Yao, Xiangdong; Zhao, Huijun

    2014-01-28

    The organic-inorganic hybrid perovskite CH3NH3PbI3 is a novel light harvester, which can greatly improve the solar-conversion efficiency of dye-sensitized solar cells. In this article, a first-principle theoretical study is performed using local, semi-local and non-local exchange-correlation approximations to find a suitable method for this material. Our results, using the non-local optB86b + vdWDF functional, excellently agree with the experimental data. Thus, consideration of weak van der Waals interactions is demonstrated to be important for the accurate description of the properties of this type of organic-inorganic hybrid materials. Further analysis of the electronic properties reveals that I 5p electrons can be photo-excited to Pb 6p empty states. The main interaction between the organic cations and the inorganic framework is through the ionic bonding between CH3 and I ions. Furthermore, I atoms in the Pb-I framework are found to be chemically inequivalent because of their different chemical environments.

  18. The structure of the hydrated electron. Part 2. A mixed quantum/classical molecular dynamics embedded cluster density functional theory: single-excitation configuration interaction study.

    Science.gov (United States)

    Shkrob, Ilya A; Glover, William J; Larsen, Ross E; Schwartz, Benjamin J

    2007-06-21

    Adiabatic mixed quantum/classical (MQC) molecular dynamics (MD) simulations were used to generate snapshots of the hydrated electron in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the hydrated electron were extracted from the MQC MD simulations and embedded in a roughly 18 Ax18 Ax18 A matrix of fractional point charges designed to represent the rest of the solvent. Density functional theory (DFT) with the Becke-Lee-Yang-Parr functional and single-excitation configuration interaction (CIS) methods were then applied to these embedded clusters. The salient feature of these hybrid DFT(CIS)/MQC MD calculations is significant transfer (approximately 18%) of the excess electron's charge density into the 2p orbitals of oxygen atoms in OH groups forming the solvation cavity. We used the results of these calculations to examine the structure of the singly occupied and the lower unoccupied molecular orbitals, the density of states, the absorption spectra in the visible and ultraviolet, the hyperfine coupling (hfcc) tensors, and the infrared (IR) and Raman spectra of these embedded water cluster anions. The calculated hfcc tensors were used to compute electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectra for the hydrated electron that compared favorably to the experimental spectra of trapped electrons in alkaline ice. The calculated vibrational spectra of the hydrated electron are consistent with the red-shifted bending and stretching frequencies observed in resonance Raman experiments. In addition to reproducing the visible/near IR absorption spectrum, the hybrid DFT model also accounts for the hydrated electron's 190-nm absorption band in the ultraviolet. Thus, our study suggests that to explain several important experimentally observed properties of the hydrated electron, many-electron effects must be accounted for: one-electron models that do not allow for mixing of the excess

  19. The structure of the hydrated electron. Part 2. A mixed quantum/classical molecular dynamics embedded cluster density functional theory : single-excitation configuration interaction study.

    Energy Technology Data Exchange (ETDEWEB)

    Shkrob, I. A.; Glover, W. J.; Larsen, R. E.; Schwartz, B. J.; Chemistry; Univ. of California at Los Angeles

    2007-06-21

    Adiabatic mixed quantum/classical (MQC) molecular dynamics (MD) simulations were used to generate snapshots of the hydrated electron in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the hydrated electron were extracted from the MQC MD simulations and embedded in a roughly 18 Angstrom x 18 Angstrom x 18 Angstrom matrix of fractional point charges designed to represent the rest of the solvent. Density functional theory (DFT) with the Becke-Lee-Yang-Parr functional and single-excitation configuration interaction (CIS) methods were then applied to these embedded clusters. The salient feature of these hybrid DFT(CIS)/MQC MD calculations is significant transfer ({approx}18%) of the excess electron's charge density into the 2p orbitals of oxygen atoms in OH groups forming the solvation cavity. We used the results of these calculations to examine the structure of the singly occupied and the lower unoccupied molecular orbitals, the density of states, the absorption spectra in the visible and ultraviolet, the hyperfine coupling (hfcc) tensors, and the infrared (IR) and Raman spectra of these embedded water cluster anions. The calculated hfcc tensors were used to compute electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectra for the hydrated electron that compared favorably to the experimental spectra of trapped electrons in alkaline ice. The calculated vibrational spectra of the hydrated electron are consistent with the red-shifted bending and stretching frequencies observed in resonance Raman experiments. In addition to reproducing the visible/near IR absorption spectrum, the hybrid DFT model also accounts for the hydrated electron's 190-nm absorption band in the ultraviolet. Thus, our study suggests that to explain several important experimentally observed properties of the hydrated electron, many-electron effects must be accounted for: one-electron models that do not

  20. Universality principle and the development of classical density functional theory

    Institute of Scientific and Technical Information of China (English)

    周世琦; 张晓琪

    2002-01-01

    The universality principle of the free energy density functional and the ‘test particle' trick by Percus are combined to construct the approximate free energy density functional or its functional derivative. Information about the bulk fluid ralial distribution function is integrated into the density functional approximation directly for the first time in the present methodology. The physical foundation of the present methodology also applies to the quantum density functional theory.

  1. Role of substituents on the reactivity and electron density profile of diimine ligands: A density functional theory based study

    Indian Academy of Sciences (India)

    Bhakti S Kulkarni; Deepti Mishra; Sourav Pal

    2013-09-01

    In this paper, we study the reactivity of diimines like 2, 2'-bipyridine, 1, l0-phenanthroline and 1, 2, 4-triazines using density-based reactivity descriptors. We discuss the enhancement or diminution in the reactivity of these ligands as a function of two substituent groups, namely methyl (-CH3) group and phenyl (-C6H5) group. The global reactivity descriptors explain the global affinity and philicity of these ligands, whereas the local softness depicts the particular site selectivity. The inter-molecular reactivity trends for the same systems are analysed through the philicity and group philicity indices. The -donor character of these ligands is quantified with the help of electron density profile. In addition, the possible strength of interaction of these ligands with metal ions is supported with actual reaction energies of Ru-L complexes.

  2. Time-dependent density functional theory study on the electronic excited-state geometric structure, infrared spectra, and hydrogen bonding of a doubly hydrogen-bonded complex.

    Science.gov (United States)

    Liu, Yufang; Ding, Junxia; Liu, Ruiqiong; Shi, Deheng; Sun, Jinfeng

    2009-12-01

    The geometric structures and infrared (IR) spectra in the electronically excited state of a novel doubly hydrogen-bonded complex formed by fluorenone and alcohols, which has been observed by IR spectra in experimental study, are investigated by the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in both ground state and the S(1) state of this doubly hydrogen-bonded FN-2MeOH complex are calculated using the DFT and TDDFT methods, respectively. Two intermolecular hydrogen bonds are formed between FN and methanol molecules in the doubly hydrogen-bonded FN-2MeOH complex. Moreover, the formation of the second intermolecular hydrogen bond can make the first intermolecular hydrogen bond become slightly weak. Furthermore, it is confirmed that the spectral shoulder at around 1700 cm(-1) observed in the IR spectra should be assigned as the doubly hydrogen-bonded FN-2MeOH complex from our calculated results. The electronic excited-state hydrogen bonding dynamics is also studied by monitoring some vibraitonal modes related to the formation of hydrogen bonds in different electronic states. As a result, both the two intermolecular hydrogen bonds are significantly strengthened in the S(1) state of the doubly hydrogen-bonded FN-2MeOH complex. The hydrogen bond strengthening in the electronically excited state is similar to the previous study on the singly hydrogen-bonded FN-MeOH complex and play important role on the photophysics of fluorenone in solutions.

  3. Electron dynamics and optical properties modulation of monolayer MoS2 by femtosecond laser pulse: a simulation using time-dependent density functional theory

    Science.gov (United States)

    Su, Xiaoxing; Jiang, Lan; Wang, Feng; Su, Gaoshi; Qu, Liangti; Lu, Yongfeng

    2017-07-01

    In this study, we adopted time-dependent density functional theory to investigate the optical properties of monolayer MoS2 and the effect of intense few-cycle femtosecond laser pulses on these properties. The electron dynamics of monolayer MoS2 under few-cycle and multi-cycle laser irradiation were described. The polarization direction of the laser had a marked effect on the energy absorption and electronic excitation of monolayer MoS2 because of anisotropy. Change in the polarization direction of few-cycle pulse changed the absorbed energy by a factor over 4000. Few-cycle pulse showed a higher sensitivity to the electronic property of material than multi-cycle pulse. The modulation of the dielectric properties of the material was observed on the femtosecond time scale. The negative divergence appeared in the real part of the function at low frequencies and photoinduced blue shift occurred due to Burstein-Moss effect. The irradiation of femtosecond laser caused the dielectric response within the infrared region and introduced anisotropy to the in-plane optical properties. Laser-based engineering of optical properties through controlling transient electron dynamics expands the functionality of MoS2 and has potential applications in direction-dependent optoelectronic devices.

  4. Locality of correlation in density functional theory.

    Science.gov (United States)

    Burke, Kieron; Cancio, Antonio; Gould, Tim; Pittalis, Stefano

    2016-08-07

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

  5. Combining density functional and density matrix theory: Optical excitation and electron relaxation at the Si(001)2 x 1 surface

    Energy Technology Data Exchange (ETDEWEB)

    Buecking, Norbert [Institut fuer Theoretische Physik, Technische Universitaet Berlin (Germany); Fritz-Haber-Institut der MPG, Berlin (Germany); Kratzer, Peter [Fachbereich Physik, Duisburg (Germany); Scheffler, Matthias [Fritz-Haber-Institut der MPG, Berlin (Germany); Knorr, Andreas [Institut fuer Theoretische Physik, Technische Universitaet Berlin (Germany)

    2008-07-01

    A theoretical two-step approach to investigate the optical excitation and subsequent phonon-assisted relaxation dynamics at semiconductor surfaces is presented and applied to the Si(001)2 x 1-surface: In the first step, the electronic band structure and the Kohn-Sham wave functions are calculated by density-functional-theory (DFT) within the LDA. In the second step, dynamical equations are derived from density-matrix theory (DMT), whereby an optical field is considered via A.p-coupling and phonon induced relaxation by a deformation potential coupling term. Into these equations, the numerical results of the DFT calculation (Kohn-Sham eigenvalues and wave functions) enter as coupling matrix elements. By numerically solving the dynamical equations, the time-resolved population of the excited states can be evaluated. The results for the Si(001) surface correspond to the findings of recent experiments, in particular a short (intra-surface-band scattering) and a long (bulk-surface band scattering) timescale are dominating the relaxation process. The value of the experimental short timescale is reproduced by our calculations, whereas the long timescale cannot be accurately described by our theory.

  6. Structural, bonding, and electronic properties of the hexagonal ferroelectric and paraelectric phases of LuMnO3 compound: A density functional theory study

    Science.gov (United States)

    Sousa, A. M.; Coutinho, W. S.; Lima, A. F.; Lalic, M. V.

    2015-02-01

    We have investigated the structural, bonding, and electronic properties of both ferroelectric (FE) and paraelectric (PE) phases of the hexagonal LuMnO3 compound using calculations based on density functional theory. The structural properties have been determined by employing the generalized gradient approximation with Perdew-Burke-Ernzerhof and Wu-Cohen parameterization. The bonding and electronic properties have been treated by recently developed modified Becke-Johnson exchange potential, which succeeded to open a band gap for both PE and FE phases, in agreement with experimental predictions. The Bader's topological analysis of electronic density showed that the character of the Lu-O axial bonds changes when the crystal exhibits the PE → FE structural transition. This fact is in agreement with experimental findings. The covalent character of the Lu-O bond significantly increases due to orbital hybridization between the Lu 5dz2 and O 2pz-states. This bonding mechanism causes the ferroelectricity in the hexagonal LuMnO3 compound.

  7. Electronically Excited States of Vitamin B12: Benchmark Calculations Including Time-Dependent Density Functional Theory and Correlated Ab Initio Methods

    CERN Document Server

    Kornobis, Karina; Wong, Bryan M; Lodowski, Piotr; Jaworska, Maria; Andruniów, Tadeusz; Rudd, Kenneth; Kozlowski, Pawel M; 10.1021/jp110914y

    2011-01-01

    Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to the electronically excited states of vitamin B12 (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to predict the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B12 was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e. B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of relative contributions of DFT and HF to the exchange-correlation functional ...

  8. Dispersion-Corrected Density Functional Theory Investigations of Structural and Electronic Properties of Bulk MoS2: Effect of Uniaxial Strain.

    Science.gov (United States)

    Nguyen, Chuong V; Hieu, Nguyen N; Nguyen, Duong T

    2015-12-01

    Strain-dependent structural and electronic properties of MoS2 materials are investigated using first principles calculations. The structural and electronic band structures of the MoS2 with relaxed unit cells are optimized and calculated by the dispersion-corrected density functional theory (DFT-D2). Calculations within the local density approximation (LDA) and GGA using PAW potentials were also performed for specific cases for the purpose of comparison. The effect of strain on the band gap and the dependence of formation energy on strain of MoS2 are also studied and discussed using the DFT-D2 method. In bulk MoS2, the orbitals shift towards the higher/lower energy area when strain is applied along the z/x direction, respectively. The energy splitting of Mo4d states is in the range from 0 to 2 eV, which is due to the reduction of the electronic band gap of MoS2.

  9. Investigating the effect of acene-fusion and trifluoroacetyl substitution on the electronic and charge transport properties by density functional theory

    Directory of Open Access Journals (Sweden)

    Ahmad Irfan

    2016-05-01

    Full Text Available We designed novel derivatives of 4,6-di(thiophen-2-ylpyrimidine (DTP. Two benchmark strategies including mesomerically deactivating group, as well as the extension of π-conjugation bridge (acene-fusion have been employed to enhance the electrical and charge transport properties. The density functional theory (DFT and time dependent DFT methods have been used to get optimized geometries in ground and first excited state, respectively. The structural properties (geometric parameters, electronic properties (frontier molecular orbitals; highest occupied and lowest unoccupied molecular orbitals, photophysical properties (absorption, fluorescence and phosphorescence, and important charge transport properties are discussed to establish a molecular level structure–property relationship among these derivatives. Our calculated electronic spectra i.e., absorption, fluorescence and phosphorescence have been found in good semi-quantitative agreement with available experimental data. All the newly designed derivatives displayed significantly improved electron injection ability than those of the parent molecule. The values of reorganization energy and transfer integral elucidate that DTP is a potential hole transport material. Based on our present investigation, it is expected that the naphtho and anthra derivatives of DTP are better hole transporters than those of some well-known charge transporter materials like naphthalene, anthracene, tetracene and pentacene.

  10. Photo-induced reactions from efficient molecular dynamics with electronic transitions using the FIREBALL local-orbital density functional theory formalism.

    Science.gov (United States)

    Zobač, Vladimír; Lewis, James P; Abad, Enrique; Mendieta-Moreno, Jesús I; Hapala, Prokop; Jelínek, Pavel; Ortega, José

    2015-05-08

    The computational simulation of photo-induced processes in large molecular systems is a very challenging problem. Firstly, to properly simulate photo-induced reactions the potential energy surfaces corresponding to excited states must be appropriately accessed; secondly, understanding the mechanisms of these processes requires the exploration of complex configurational spaces and the localization of conical intersections; finally, photo-induced reactions are probability events, that require the simulation of hundreds of trajectories to obtain the statistical information for the analysis of the reaction profiles. Here, we present a detailed description of our implementation of a molecular dynamics with electronic transitions algorithm within the local-orbital density functional theory code FIREBALL, suitable for the computational study of these problems. As an example of the application of this approach, we also report results on the [2 + 2] cycloaddition of ethylene with maleic anhydride and on the [2 + 2] photo-induced polymerization reaction of two C60 molecules. We identify different deactivation channels of the initial electron excitation, depending on the time of the electronic transition from LUMO to HOMO, and the character of the HOMO after the transition.

  11. Investigation of pure and Co{sup 2+}-doped ZnO quantum dot electronic structures using the density functional theory: choosing the right functional

    Energy Technology Data Exchange (ETDEWEB)

    Badaeva, Ekaterina; Feng Yong; Gamelin, Daniel R; Li Xiaosong [Department of Chemistry, University of Washington, Seattle, WA 98195-1700 (United States)], E-mail: li@chem.washington.edu

    2008-05-15

    The electronic structures of pure and Co{sup 2+}-doped ZnO quantum dots (QDs) with sizes up to 300 atoms were investigated using three different density functional theory approximations: local spin density approximation (LSDA), gradient-corrected Perdew-Burke-Ernzerhof (PBE) and the hybrid PBE1 functionals with LANL2DZ pseudo-potential and associated basis set. Qualitative agreement among the three methods is found for the pure ZnO nanostructures, but only the hybrid functional reproduces the correct bandgap energies quantitatively. For Co{sup 2+}-doped ZnO QDs, both LSDA and PBE incorrectly model interactions between Co{sup 2+} d levels and the valence band of ZnO, which will strongly impair predictions of dopant-carrier magnetic exchange interactions based on such computational results. Experimental observations are reproduced well in calculations at the hybrid PBE1 level of theory, making this the method of choice for exploring the magnetism of transition metal ions in ZnO QDs computationally. The qualitative features of the Co{sup 2+} 3d levels do not change appreciably with changes in cluster size over the range examined, leading to size-dependent dopant-band edge energy differences. The results presented here thus provide an experimentally calibrated framework for future ab initio descriptions of dopant-carrier and dopant-dopant magnetic exchange interactions in diluted magnetic semiconductors (DMS) nanocrystals.

  12. The structure of the hydrated electron. Part 2. A mixed quantum classical molecular dynamics - embedded cluster density functional theory: single-excitation configuration interaction study

    CERN Document Server

    Shkrob, I A; Larsen, R E; Schwartz, B J; Glover, William J.; Larsen, Ross E.; Schwartz, Benjamin J.; Shkrob, Ilya A.

    2006-01-01

    Adiabatic mixed quantum/classical molecular dynamics simulations were used to generate snapshots of the hydrated electron (e-) in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the e- were extracted from these simulations and embedded in a matrix of fractional point charges designed to represent the rest of the solvent. Density functional theory and single-excitation configuration interaction methods were then applied to these embedded clusters. The salient feature of these hybrid calculations is significant transfer (ca. 0.18) of the excess electron's charge density into the O 2p orbitals in OH groups forming the solvation cavity. We used the results of these calculations to examine the structure of the molecular orbitals, the density of states, the absorption spectra in the visible and ultraviolet, the hyperfine coupling (hfc) tensors, and the IR and Raman spectra of the e-. The calculated hfc tensors were used to compute the EPR and ESEEM spectra for the ...

  13. Density functional theory analysis of the structural and electronic properties of TiO2 rutile and anatase polytypes: performances of different exchange-correlation functionals.

    Science.gov (United States)

    Labat, Frédéric; Baranek, Philippe; Domain, Christophe; Minot, Christian; Adamo, Carlo

    2007-04-21

    The two polymorphs of TiO2, rutile and anatase, have been investigated at the ab initio level using different Hamiltonians with all-electron Gaussian and projector augmented plane wave basis sets. Their equilibrium lattice parameters, relative stabilities, binding energies, and band structures have been evaluated. The calculations have been performed at the Hartree-Fock, density functional theory (DFT), and hybrid (B3LYP and PBE0) levels. As regards DFT, the local density and generalized gradient (PBE) approximations have been used. Our results show an excellent agreement with the experimental band structures and binding energies for the B3LYP and PBE0 functionals, while the best structural descriptions are obtained at the PBE0 level. However, no matter which Hamiltonian and method are used, anatase is found more stable than rutile, in contrast with recent experimental reports, although the relative stabilities of the two phases are very close to each other. Nevertheless, based on the overall results, the hybrid PBE0 functional appears as a good compromise to obtain an accurate description of both structural and electronic properties of solids.

  14. A density functional theory study on size-dependent structures, stabilities, and electronic properties of bimetallic MnAgm (M=Na, Li; n + m ≤ 7) clusters

    Institute of Scientific and Technical Information of China (English)

    Sun Hao-Ran; Kuang Xiao-Yu; Li Yan-Fang; Shao Peng; Zhao Ya-Ru

    2012-01-01

    The equilibrium geometries,relative stabilities,and electronic properties of MnAgm(M=-Na,Li; n +-m ≤ 7) as well as pure Agn,Nan,Lin (n ≤ 7) clusters are systematically investigated by means of the density functional theory.The optimized geometries reveal that for 2 ≤ n ≤ 7,there are significant similarities in geometry among pure Agn,Nan,and Lin clusters,and the transitions from planar to three-dimensional configurations occur at n =7,7,and 6,respectively.In contrast,the first three-dimensional (3D) structures are observed at n + m =5 for both NanAgm and LinAgm clusters.When n + m ≥ 5,a striking feature is that the trigonal bipyramid becomes the main subunit of LinAgm.Furthermore,dramatic odd-even alternative behaviours are obtained in the fragmentation energies,secondorder difference energies,highest occupied and lowest unoccupied molecular orbital energy gaps,and chemical hardness for both pure and doped clusters.The analytic results exhibit that clusters with an even electronic configuration (2,4,6) possess the weakest chemical reactivity and more enhanced stability.

  15. Size dependent structural, electronic, and magnetic properties of Sc(N) (N=2-14) clusters investigated by density functional theory.

    Science.gov (United States)

    Bhunia, Snehasis; Vyas, Nidhi; Sahu, Chandan; Ojha, Animesh K

    2014-11-01

    Structural, electronic, and magnetic properties of ScN (N=2-14) clusters have been investigated using density functional theory (DFT) calculations. Different spin states isomer for each cluster size has been optimized with symmetry relaxation. The structural stability, dissociation energy, binding energy, spin stability, vertical ionization energy, electron affinity, chemical hardness, and size dependent magnetic moment per atom are calculated for the energetically most stable spin isomer for each size. The structural stability for a specific size cluster has been explained in terms of atomic shell closing effect, close packed symmetric structure, and chemical bonding. Spin stability of each cluster size is determined by calculating the value of spin gaps. The maximum value for second-order energy difference is observed for the clusters of size N = 2, 6, 11, and 13, which implies that these clusters are relatively more stable. The magnetic moment per atom corresponding to lowest energy structure has also been calculated. The magnetic moment per atom corresponding to lowest energy structures has been calculated. The calculated values of magnetic moment per atom vary in an oscillatory fashion with cluster size. The calculated results are compared with the available experimental data.

  16. Investigating and comparison of electronic and optical properties of MgO nanosheet in (100) and (111) structural directions based on the density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Akhtar, A., E-mail: arsalan_akhtar@outlook.com; Pilevarshahri, R.; Benam, Mohammad Reza

    2016-12-01

    In this paper, we investigate the electronic and optical properties of MgO nanosheet in (100) and (111) directions. Our calculations carried out under the framework of density functional theory (DFT) exploiting WIEN2K code with Full potential, periodic boundary conditions, augmented plane-wave basis sets and GGA approximation. Electronic results indicate that MgO(111) nanosheet has an indirect band gap of 3.67 eV and MgO(100) nanosheet has a direct band gap of 3.14 eV. MgO(100) nanosheet exhibit more ionic bonding than MgO(111) and MgO(111) has more covalent bonding than MgO(100) nanosheet. Moreover, the optical results indicate that variation of dielectric function in x direction is more than the z direction. DOS and imaginary part of the dielectric function survey confirm semiconductor properties with different bang gap for structures. Comparing the imaginary part of dielectric functions in x and z directions for two structures, blue and red shift have been observed respectively. Our results indicate that these two nanostructures are transparent in a wide range of energy spectra and have low reflectivity.

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

    CERN Document Server

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

    2012-01-01

    For the paradigmatic case of H2-dissociation we compare state-of-the-art many-body perturbation theory (MBPT) in the GW approximation and density-functional theory (DFT) in the exact-exchange plus random-phase approximation for the correlation energy (EX+cRPA). 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 non-interacting 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, the DFT framework outperforms the many-body framework when it comes to bond-breaking. We attribute this to the difference in the correlation energy rather than the treatment of the kinetic energy.

  18. e/a classification of Hume–Rothery Rhombic Triacontahedron-type approximants based on all-electron density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, U; Inukai, M; Sato, H; Zijlstra, E S; Lin, Q

    2014-05-16

    There are three key electronic parameters in elucidating the physics behind the Hume–Rothery electron concentration rule: the square of the Fermi diameter (2kF)2, the square of the critical reciprocal lattice vector and the electron concentration parameter or the number of itinerant electrons per atom e/a. We have reliably determined these three parameters for 10 Rhombic Triacontahedron-type 2/1–2/1–2/1 (N = 680) and 1/1–1/1–1/1 (N = 160–162) approximants by making full use of the full-potential linearized augmented plane wave-Fourier band calculations based on all-electron density-functional theory. We revealed that the 2/1–2/1–2/1 approximants Al13Mg27Zn45 and Na27Au27Ga31 belong to two different sub-groups classified in terms of equal to 126 and 109 and could explain why they take different e/a values of 2.13 and 1.76, respectively. Among eight 1/1–1/1–1/1 approximants Al3Mg4Zn3, Al9Mg8Ag3, Al21Li13Cu6, Ga21Li13Cu6, Na26Au24Ga30, Na26Au37Ge18, Na26Au37Sn18 and Na26Cd40Pb6, the first two, the second two and the last four compounds were classified into three sub-groups with = 50, 46 and 42; and were claimed to obey the e/a = 2.30, 2.10–2.15 and 1.70–1.80 rules, respectively.

  19. e/a classification of Hume-Rothery Rhombic Triacontahedron-type approximants based on all-electron density functional theory calculations

    Science.gov (United States)

    Mizutani, U.; Inukai, M.; Sato, H.; Zijlstra, E. S.; Lin, Q.

    2014-08-01

    There are three key electronic parameters in elucidating the physics behind the Hume-Rothery electron concentration rule: the square of the Fermi diameter (2kF)2, the square of the critical reciprocal lattice vector ? and the electron concentration parameter or the number of itinerant electrons per atom e/a. We have reliably determined these three parameters for 10 Rhombic Triacontahedron-type 2/1-2/1-2/1 (N = 680) and 1/1-1/1-1/1 (N = 160-162) approximants by making full use of the full-potential linearized augmented plane wave-Fourier band calculations based on all-electron density-functional theory. We revealed that the 2/1-2/1-2/1 approximants Al13Mg27Zn45 and Na27Au27Ga31 belong to two different sub-groups classified in terms of ? equal to 126 and 109 and could explain why they take different e/a values of 2.13 and 1.76, respectively. Among eight 1/1-1/1-1/1 approximants Al3Mg4Zn3, Al9Mg8Ag3, Al21Li13Cu6, Ga21Li13Cu6, Na26Au24Ga30, Na26Au37Ge18, Na26Au37Sn18 and Na26Cd40Pb6, the first two, the second two and the last four compounds were classified into three sub-groups with ? = 50, 46 and 42; and were claimed to obey the e/a = 2.30, 2.10-2.15 and 1.70-1.80 rules, respectively.

  20. Introduction to Classical Density Functional Theory by a Computational Experiment

    Science.gov (United States)

    Jeanmairet, Guillaume; Levy, Nicolas; Levesque, Maximilien; Borgis, Daniel

    2014-01-01

    We propose an in silico experiment to introduce the classical density functional theory (cDFT). Density functional theories, whether quantum or classical, rely on abstract concepts that are nonintuitive; however, they are at the heart of powerful tools and active fields of research in both physics and chemistry. They led to the 1998 Nobel Prize in…

  1. Time-dependent density functional theory for quantum transport.

    Science.gov (United States)

    Zheng, Xiao; Chen, GuanHua; Mo, Yan; Koo, SiuKong; Tian, Heng; Yam, ChiYung; Yan, YiJing

    2010-09-21

    Based on our earlier works [X. Zheng et al., Phys. Rev. B 75, 195127 (2007); J. S. Jin et al., J. Chem. Phys. 128, 234703 (2008)], we propose a rigorous and numerically convenient approach to simulate time-dependent quantum transport from first-principles. The proposed approach combines time-dependent density functional theory with quantum dissipation theory, and results in a useful tool for studying transient dynamics of electronic systems. Within the proposed exact theoretical framework, we construct a number of practical schemes for simulating realistic systems such as nanoscopic electronic devices. Computational cost of each scheme is analyzed, with the expected level of accuracy discussed. As a demonstration, a simulation based on the adiabatic wide-band limit approximation scheme is carried out to characterize the transient current response of a carbon nanotube based electronic device under time-dependent external voltages.

  2. Thermodynamic extension of density-functional theory. II. Finite-temperature ensemble spin-density functional theory

    CERN Document Server

    Balawender, Robert

    2009-01-01

    The formalism developed in the first paper of the series [arXiv:0901.1060v3] is applied to two thermodynamic systems: (i) of three global observables (the energy, the total electron number and the spin number), (ii) of one global observable (the internal electron energy) and two local (position-dependent) observables (the total electron density and the spin density). The two-component potential of the many-electron system of interest is constructed of a scalar external potential and a collinear magnetic field (coupled only with the spin operator). Various equilibrium characteristics of two systems are defined and investigated. Conditions for the equivalence between two systems (the same equilibrium density matrix demanded) are derived and thoroughly discussed. The applicability of the Hohenberg-Kohn theorem is extended to the thermodynamic spin-density functional theory. Obtained results provide a rigorous mathematical foundation for future derivation of the zero-temperature limit of this theory and determina...

  3. Electronic properties of MoS{sub 2} on monolayer, bilayer and bulk SiC: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Zan, Wenyan; Geng, Wei [State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Liu, Huanxiang [School of Pharmacy, Lanzhou University, Lanzhou 730000 (China); Yao, Xiaojun, E-mail: xjyao@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)

    2016-05-05

    The structure and electronic properties of MoS{sub 2} and SiC (single-layer SiC, double layer SiC, C-terminated SiC and Si-terminated SiC) composites were investigated by using density functional theory calculations. The calculation results show that the electronic properties of MoS{sub 2} are modified at different levels by combining with different thickness of SiC. The heterostructures (MoS{sub 2}/C-terminated SiC and MoS{sub 2}/Si-terminated SiC) possess larger binding energies than MoS{sub 2}/single-layer SiC and MoS{sub 2}/bilayer SiC, suggesting the higher stability for MoS{sub 2}/C-terminated SiC and MoS{sub 2}/Si-terminated SiC composites. It is found that charge transfer is from SiC to MoS{sub 2} in these heterostructures. MoS{sub 2}/single-layer SiC, MoS{sub 2}/double-layer SiC and MoS{sub 2}/C-terminated SiC are semiconductors, whereas MoS{sub 2}/Si-terminated SiC has no gap. - Highlights: • The structure and electronic properties of MoS{sub 2}/SiC composites were investigated. • The electronic property of MoS{sub 2} can be modulated by SiC with different thickness. • The MoS{sub 2}/Si-terminated SiC has higher stability than MoS{sub 2}/C-terminated SiC.

  4. Two symmetric n-type interfaces SrTiO3/LaAlO3 in perovskite: Electronic properties from density functional theory

    Science.gov (United States)

    Reshak, A. H.; Abu-Jafar, M. S.; Al-Douri, Y.

    2016-06-01

    The first principles study of the (001) two symmetric n-type interfaces between two insulating perovskites, the nonpolar SrTiO3 (STO), and the polar LaAlO3 (LAO) was performed. We have analyzed the formation of metallic interface states between the STO and LAO heterointerfaces by using the all-electron full-potential linearized augmented plane-wave approach based on the density functional theory, within the local density approximation, the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA), and the Engel-Vosko GGA (EVGGA) formalism. It has been found that some bands cross the Fermi energy level (EF), forming a metallic nature of two symmetric n-type 6.5STO/1.5LAO interfaces with density of states at EF, N(EF) of about 3.56 (state/eV/unit cell), and bare electronic specific heat coefficient (γ) of about 0.62 mJ/(mol cell K2). The electronic band stature and the partial density of states in the vicinity of EF are mainly originated from Ti1,2,3,4-3dxy orbitals. These bands are responsible for the metallic behavior and the forming of the Fermi surface of the two symmetric n-type 6.5STO/1.5LAO interfaces. To obtain a clear map of the valence band electronic charge density distribution of the two symmetric n-type 6.5STO/1.5LAO interfaces, we have investigated the bond's nature and the interactions between the atoms. It reveals that the charge is attracted towards O atoms as it is clear that the O atoms are surrounded by uniform blue spheres which indicate the maximum charge accumulation.

  5. Density functional theory studies of doping in Titania

    OpenAIRE

    2010-01-01

    The structural and electronic properties of rutile and anatase, and the influence of both mono- and co-doping, have been studied using Density Functional Theory. Ge-doped anatase and rutile exhibit different band gap-narrowing mechanisms; in particular, host Ti 3d states move to lower energy regions in anatase and Ge 4s impurities states locate below the conduction band of rutile. For S-doping, S 3p states locate above the top of the valence band and mix with O 2p states, leading to band gap ...

  6. 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

  7. Electronic structures of WAlO(y) and WAlO(y)(-) (y = 2-4) determined by anion photoelectron spectroscopy and density functional theory calculations.

    Science.gov (United States)

    Mann, Jennifer E; Waller, Sarah E; Jarrold, Caroline Chick

    2012-07-28

    The anion photoelectron spectra of WAlO(y)(-) (y = 2-4) are presented and assigned based on results of density functional theory calculations. The WAlO(2)(-) and WAlO(3)(-) spectra are both broad, with partially resolved vibrational structure. In contrast, the WAlO(4)(-) spectrum features well-resolved vibrational structure with contributions from three modes. There is reasonable agreement between experiment and theory for all oxides, and calculations are in particular validated by the near perfect agreement between the WAlO(4)(-) photoelectron spectrum and a Franck-Condon simulation based on computationally determined spectroscopic parameters. The structures determined from this study suggest strong preferential W-O bond formation, and ionic bonding between Al(+) and WO(y)(-2) for all anions. Neutral species are similarly ionic, with WAlO(2) and WAlO(3) having electronic structure that suggests Al(+) ionically bound to WO(y)(-) and WAlO(4) being described as Al(+2) ionically bound to WO(4)(-2). The doubly-occupied 3sp hybrid orbital localized on the Al center is energetically situated between the bonding O-local molecular orbitals and the anti- or non-bonding W-local molecular orbitals. The structures determined in this study are very similar to structures recently determined for the analogous MoAlO(y)(-)/MoAlO(y) cluster series, with subtle differences found in the electronic structures [S. E. Waller, J. E. Mann, E. Hossain, M. Troyer, and C. C. Jarrold, J. Chem. Phys. 137, 024302 (2012)].

  8. Structural and electronic properties of SrAl{sub 2}O{sub 4}:Eu{sup 2+} from density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Nazarov, M. [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Pulau Pinang (Malaysia); Institute of Applied Physics, Academiei Street 5, Chisinau MD-2028 (Moldova, Republic of); Brik, M.G., E-mail: brik@fi.tartu.ee [Institute of Physics, University of Tartu, Riia 142, Tartu 51014 (Estonia); Spassky, D. [Institute of Physics, University of Tartu, Riia 142, Tartu 51014 (Estonia); Skobeltsyn Institute of Nuclear Physics, M.V. Lomonosov Moscow State University, 119991 Moscow (Russian Federation); Tsukerblat, B. [Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Nor Nazida, A. [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Pulau Pinang (Malaysia); Faculty of Art and Design, Universiti Teknologi MARA (Perak), Seri Iskandar, 32610 Bandar Baru Seri Iskandar, Perak (Malaysia); Ahmad-Fauzi, M.N. [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Nibong Tebal, Pulau Pinang (Malaysia)

    2013-10-05

    Highlights: •Persistent phosphor SrAl{sub 2}O{sub 4}:Eu{sup 2+} was synthesized and studied. •Ab initio calculations of its electronic properties were performed. •Lowest position of the Eu 4f states in the band gap was determined. •Position of the Eu 4f states agrees with the charge transfer transition. -- Abstract: A stoichiometric micro-sized powder SrAl{sub 2}O{sub 4}:Eu{sup 2+} was synthesized by traditional solid state reaction at 1250 °C. Low-temperature spectroscopic measurements revealed two luminescence bands at 450 nm and 512 nm; their origin was discussed. Theoretical calculations of the structural and optical properties of SrAl{sub 2}O{sub 4}:Eu{sup 2+} in the framework of the density functional theory (DFT) were carried out; the obtained results were compared with the corresponding experimental data. For the first time, the position of the lowest 4f states of Eu in the host’s band gap was calculated for both available Sr positions to be at about 4.5–5 eV above the top of the valence band. Reliability of this result is confirmed by good agreement with the experimental value of the O(2p)–Eu(4f) charge transfer energy, which is equal to about 4.9 eV.

  9. Density Functional Theory Study on Electronic and Magnetic Properties of Mn-doped (MgO)n (n=2-10) Clusters

    Institute of Scientific and Technical Information of China (English)

    Peng Wang; Ming-xia Yang; Sheng-li Zhang; Shi-ping Huang; Hui-ping Tian

    2013-01-01

    We study the geometries,stabilities,electronic and magnetic properties of (MgO),(n=2-10) clusters doped with a single Mn atom using the density functional theory with the generalized gradient approximation.The optimized geometries show that the impurity Mn atom prefers to replace the Mg atom which has low coordination number in all the lowest-energy MnMgn-1On (n=2-10) structures.The stability analysis clearly represents that the average binding energies of the doped clusters are larger than those of the corresponding pure (MgO),clusters.Maximum peaks of the second order energy differences are observed for MnMg_1On clusters at n=6,9,implying that these clusters exhibit higher stability than their neighboring clusters.In addition,all the Mn-doped Mg clusters exhibit high total magnetic moments with the exception of MnMgO2 which has 3.00 μB.Their magnetic behavior is attributed to the impurity Mn atom,the charge transfer modes,and the size of MnMgn-1On clusters.

  10. Structural and electronic properties of the heterointerfaces for Cu2ZnSnS4 photovoltaic cells: a density-functional theory study.

    Science.gov (United States)

    Xiao, W; Wang, J N; Wang, J W; Huang, G J; Cheng, L; Jiang, L J; Wang, L G

    2016-04-28

    The quaternary compound semiconductor Cu2ZnSnS4 (CZTS) is a promising photovoltaic absorber material for thin-film solar cell applications. Density-functional theory calculations have been performed to investigate the structural and electronic properties of the CdS/CZTS heterointerfaces in CZTS-based cells. We find that CdS favors epitaxial growth on the Cu-Zn plane of CZTS along the direction of [100], which can eliminate the effects of the wrong bonds at the interfaces and enhance the energetic barrier for charge carrier recombination across the interfaces with an increased band gap. The band alignment is calculated for the epitaxial CZTS/CdS heterointerface by employing the HSE06 functional and the results show a type-II band alignment with VBO and CBO values of 0.95 eV and -0.05 eV, respectively. Also, the experimental phenomenon of Zn segregation at CdS/CZTS interfaces is corroborated. Zn segregation can enhance the stability of the heterointerfaces, but damage the solar cell performance by decreasing the band gap when the Zn concentration is sufficiently high. We show that besides the defects and undesired phases in CZTS, the heterointerfaces between the absorption layers (CZTS) and the buffer layer (CdS) can also be an important factor that affects the performance of CZTS cells. The present work provides a theoretical base for engineering the heterointerfaces and achieving better performance of CZTS-based solar cells.

  11. A density functional theory study of the electronic structures and magnetic properties of Fe(1-x)Cox alloy nanowires encapsulated in (10,0) carbon nanotubes

    Institute of Scientific and Technical Information of China (English)

    Xie You; Zhang Jian-Min

    2011-01-01

    Under the generalized gradient approximation,the electronic structures and magnetic properties of Fe(1-x)Coxalloy nanowires encapsulated inside zigzag (10,0) carbon nanotubes (CNTs) are investigated systematically using firstprinciple density functional theory calculations.For the fully relaxed Fe(1-x)Cox/CNT structures,all the C atoms relax outwards,and thus the diameters of the CNTs are slightly increased.Formation energy analysis shows that the combining processes of all Fe(1-x)Cox/CNT systems are exothermic,and therefore the Fe(1-x)Cox alloy nanowirescan be encapsulated into semiconducting zigzag (10,0) CNTs and form stable hybrid structures.The charges are transferred from the Fe(1-x)Cox nanowires to the more electronegative CNTs,and the Fe-C/Co-C bonds formed have polar covalent bond characteristics.Both the spin polarization and total magnetic moment of the Fe(1-x)Cox/CNT system are smaller than those of the corresponding freestanding Fe(1-x)Cox nanowire,and the magnetic moment of the Fe(1-x)Cox/CNT system decreases monotonously with increasing Co concentration,but the Fe(1-x)Cox/CNT systems still have a large magnetic moment,implying that they can be utilized in high-density magnetic recording devices.

  12. First principles phase transition, elastic properties and electronic structure calculations for cadmium telluride under induced pressure: density functional theory, LDA, GGA and modified Becke-Johnson potential

    Science.gov (United States)

    Kabita, Kh; Maibam, Jameson; Indrajit Sharma, B.; Brojen Singh, R. K.; Thapa, R. K.

    2016-01-01

    We report first principles phase transition, elastic properties and electronic structure for cadmium telluride (CdTe) under induced pressure in the light of density functional theory using the local density approximation (LDA), generalised gradient approximation (GGA) and modified Becke-Johnson (mBJ) potential. The structural phase transition of CdTe from a zinc blende (ZB) to a rock salt (RS) structure within the LDA calculation is 2.2 GPa while that within GGA is found to be at 4 GPa pressure with a volume collapse of 20.9%. The elastic constants and parameters (Zener anisotropy factor, Shear modulus, Poisson’s ratio, Young’s modulus, Kleinmann parameter and Debye’s temperature) of CdTe at different pressures of both the phases have been calculated. The band diagram of the CdTe ZB structure shows a direct band gap of 1.46 eV as predicted by mBJ calculation which gives better results in close agreement with experimental results as compared to LDA and GGA. An increase in the band gap of the CdTe ZB phase is predicted under induced pressure while the metallic nature is retained in the CdTe RS phase.

  13. Density functional theory with quantum nuclei

    CERN Document Server

    Requist, Ryan

    2016-01-01

    It is proved that the ground state energy of an electron-nuclear system is a variational functional of the conditional electronic density n_R(r), the nuclear wavefunction \\chi(R) and the quantum geometric tensor of the conditional electronic wavefunction $T_{\\mu\

  14. Differentiable but exact formulation of density-functional theory.

    Science.gov (United States)

    Kvaal, Simen; Ekström, Ulf; Teale, Andrew M; Helgaker, Trygve

    2014-05-14

    The universal density functional F of density-functional theory is a complicated and ill-behaved function of the density-in particular, F is not differentiable, making many formal manipulations more complicated. While F has been well characterized in terms of convex analysis as forming a conjugate pair (E, F) with the ground-state energy E via the Hohenberg-Kohn and Lieb variation principles, F is nondifferentiable and subdifferentiable only on a small (but dense) subset of its domain. In this article, we apply a tool from convex analysis, Moreau-Yosida regularization, to construct, for any ε > 0, pairs of conjugate functionals ((ε)E, (ε)F) that converge to (E, F) pointwise everywhere as ε → 0(+), and such that (ε)F is (Fréchet) differentiable. For technical reasons, we limit our attention to molecular electronic systems in a finite but large box. It is noteworthy that no information is lost in the Moreau-Yosida regularization: the physical ground-state energy E(v) is exactly recoverable from the regularized ground-state energy (ε)E(v) in a simple way. All concepts and results pertaining to the original (E, F) pair have direct counterparts in results for ((ε)E, (ε)F). The Moreau-Yosida regularization therefore allows for an exact, differentiable formulation of density-functional theory. In particular, taking advantage of the differentiability of (ε)F, a rigorous formulation of Kohn-Sham theory is presented that does not suffer from the noninteracting representability problem in standard Kohn-Sham theory.

  15. Differentiable but exact formulation of density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kvaal, Simen, E-mail: simen.kvaal@kjemi.uio.no; Ekström, Ulf; Helgaker, Trygve [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo (Norway); Teale, Andrew M. [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo (Norway); School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2014-05-14

    The universal density functional F of density-functional theory is a complicated and ill-behaved function of the density—in particular, F is not differentiable, making many formal manipulations more complicated. While F has been well characterized in terms of convex analysis as forming a conjugate pair (E, F) with the ground-state energy E via the Hohenberg–Kohn and Lieb variation principles, F is nondifferentiable and subdifferentiable only on a small (but dense) subset of its domain. In this article, we apply a tool from convex analysis, Moreau–Yosida regularization, to construct, for any ε > 0, pairs of conjugate functionals ({sup ε}E, {sup ε}F) that converge to (E, F) pointwise everywhere as ε → 0{sup +}, and such that {sup ε}F is (Fréchet) differentiable. For technical reasons, we limit our attention to molecular electronic systems in a finite but large box. It is noteworthy that no information is lost in the Moreau–Yosida regularization: the physical ground-state energy E(v) is exactly recoverable from the regularized ground-state energy {sup ε}E(v) in a simple way. All concepts and results pertaining to the original (E, F) pair have direct counterparts in results for ({sup ε}E, {sup ε}F). The Moreau–Yosida regularization therefore allows for an exact, differentiable formulation of density-functional theory. In particular, taking advantage of the differentiability of {sup ε}F, a rigorous formulation of Kohn–Sham theory is presented that does not suffer from the noninteracting representability problem in standard Kohn–Sham theory.

  16. Simulating Ru L3-edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    Energy Technology Data Exchange (ETDEWEB)

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, N.; Schoenlein, R. W.; Govind, Niranjan; Khalil, Munira

    2013-05-01

    Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+, [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.

  17. Machine-learned approximations to Density Functional Theory Hamiltonians

    Science.gov (United States)

    Hegde, Ganesh; Bowen, R. Chris

    2017-01-01

    Large scale Density Functional Theory (DFT) based electronic structure calculations are highly time consuming and scale poorly with system size. While semi-empirical approximations to DFT result in a reduction in computational time versus ab initio DFT, creating such approximations involves significant manual intervention and is highly inefficient for high-throughput electronic structure screening calculations. In this letter, we propose the use of machine-learning for prediction of DFT Hamiltonians. Using suitable representations of atomic neighborhoods and Kernel Ridge Regression, we show that an accurate and transferable prediction of DFT Hamiltonians for a variety of material environments can be achieved. Electronic structure properties such as ballistic transmission and band structure computed using predicted Hamiltonians compare accurately with their DFT counterparts. The method is independent of the specifics of the DFT basis or material system used and can easily be automated and scaled for predicting Hamiltonians of any material system of interest. PMID:28198471

  18. Machine-learned approximations to Density Functional Theory Hamiltonians

    Science.gov (United States)

    Hegde, Ganesh; Bowen, R. Chris

    2017-02-01

    Large scale Density Functional Theory (DFT) based electronic structure calculations are highly time consuming and scale poorly with system size. While semi-empirical approximations to DFT result in a reduction in computational time versus ab initio DFT, creating such approximations involves significant manual intervention and is highly inefficient for high-throughput electronic structure screening calculations. In this letter, we propose the use of machine-learning for prediction of DFT Hamiltonians. Using suitable representations of atomic neighborhoods and Kernel Ridge Regression, we show that an accurate and transferable prediction of DFT Hamiltonians for a variety of material environments can be achieved. Electronic structure properties such as ballistic transmission and band structure computed using predicted Hamiltonians compare accurately with their DFT counterparts. The method is independent of the specifics of the DFT basis or material system used and can easily be automated and scaled for predicting Hamiltonians of any material system of interest.

  19. Applications of large-scale density functional theory in biology

    Science.gov (United States)

    Cole, Daniel J.; Hine, Nicholas D. M.

    2016-10-01

    Density functional theory (DFT) has become a routine tool for the computation of electronic structure in the physics, materials and chemistry fields. Yet the application of traditional DFT to problems in the biological sciences is hindered, to a large extent, by the unfavourable scaling of the computational effort with system size. Here, we review some of the major software and functionality advances that enable insightful electronic structure calculations to be performed on systems comprising many thousands of atoms. We describe some of the early applications of large-scale DFT to the computation of the electronic properties and structure of biomolecules, as well as to paradigmatic problems in enzymology, metalloproteins, photosynthesis and computer-aided drug design. With this review, we hope to demonstrate that first principles modelling of biological structure-function relationships are approaching a reality.

  20. Multireference spin-adapted variant of density functional theory.

    Science.gov (United States)

    Khait, Yuriy G; Hoffmann, Mark R

    2004-03-15

    A new Kohn-Sham formalism is developed for studying the lowest molecular electronic states of given space and spin symmetry whose densities are represented by weighted sums of several reference configurations. Unlike standard spin-density functional theory, the new formalism uses total spin conserving spin-density operators and spin-invariant density matrices so that the method is fully spin-adapted and solves the so-called spin-symmetry dilemma. The formalism permits the use of an arbitrary set of reference (noninteracting) configurations with any number of open shells. It is shown that the requirement of degeneracy of the total noninteracting energies of the reference configurations (or configuration state functions) is equivalent to the stationary condition of the exact energy relative to the weights of the configurations (or configuration state functions). Consequently, at any molecular geometry, the weights can be determined by minimization of the energy, and, for given reference weights, the Kohn-Sham orbitals can be determined. From this viewpoint, the developed theory can be interpreted as an analog of the multiconfiguration self-consistent field approach within density functional theory.

  1. Unraveling the electronic structures of low-valent naphthalene and anthracene iron complexes: X-ray, spectroscopic, and density functional theory studies.

    Science.gov (United States)

    Schnöckelborg, Eva-Maria; Khusniyarov, Marat M; de Bruin, Bas; Hartl, František; Langer, Thorsten; Eul, Matthias; Schulz, Stephen; Pöttgen, Rainer; Wolf, Robert

    2012-06-18

    Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown-6){Cp*Fe(η(4)-C(10)H(8))}] (K1), [K(18-crown-6){Cp*Fe(η(4)-C(14)H(10))}] (K2), [Cp*Fe(η(4)-C(10)H(8))] (1), and [Cp*Fe(η(4)-C(14)H(10))] (2) were synthesized and characterized by NMR, UV-vis, and (57)Fe Mössbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(η(4)-C(10)H(8))](-) (1(-)) and [Cp*Fe(η(4)-C(14)H(10))](-) (2(-)) and reversibly oxidized to the cations [Cp*Fe(η(6)-C(10)H(8))](+) (1(+)) and [Cp*Fe(η(6)-C(14)H(10))](+) (2(+)). Reduced orbital charges and spin densities of the naphthalene complexes 1(-/0/+) and the anthracene derivatives 2(-/0/+) were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1(-) and 2(-) are best represented by low-spin Fe(II) ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin Fe(I) ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin Fe(II) ion coordinated to a ligand radical L(•-). Our study thus reveals the redox noninnocent character of the naphthalene

  2. Resonance Raman, electron paramagnetic resonance, and density functional theory calculations of a phenolate-bound iron porphyrin complex: electrostatic versus covalent contribution to bonding.

    Science.gov (United States)

    Das, Pradip Kumar; Dey, Abhishek

    2014-07-21

    Resonance Raman (rR), electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations of a phenolate-bound iron porphyrin complex are reported. The complex is found to exist in a five-coordinate high-spin state in a noncoordinating solvent and in a six-coordinate low-spin state in a coordinating solvent. The vibrations originating from the iron phenolate-bound chromophores reproduced those reported for heme tyrosine active sites in nature. The EPR parameters and iron-pyrrole (Fe-Npyr) vibrations of phenolate, thiolate, and imidazole ligated iron porphyrin complexes indicate that the phenolate axial ligand acts as a π anisotropic ligand, which is more covalent than a neutral imidazole ligand but less covalent than a thiolate axial ligand. While the Fe(III/II) potential of the phenolate compound in a noncoordinating solvent is 500 mV more negative than that of the imidazole-bound complex, it is also 110 mV more negative than that of the thiolate-bound complex. DFT calculations reproduce the geometry and vibrational frequencies and show that while both phenolate and thiolate axial ligands bear π and σ interaction with the ferric center, the former is significantly less covalent than the thiolate. The higher covalency of the thiolate ligand is responsible for the lower Fe-Npyr vibration and higher V/λ (from EPR) of the thiolate-bound complexes relative to those of the phenolate-bound complex, whereas the greater electrostatic stabilization of the Fe(III)-OPh bond is responsible for lowering the Fe(III/II) E° of the phenolate-bound complex relative to that of the thiolate-bound complex in a medium having a reasonable dielectric constant.

  3. Understanding the Thermal Stability of Palladium-Platinum Core-Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory.

    Science.gov (United States)

    Vara, Madeline; Roling, Luke T; Wang, Xue; Elnabawy, Ahmed O; Hood, Zachary D; Chi, Miaofang; Mavrikakis, Manos; Xia, Younan

    2017-05-23

    Core-shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core-shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core-shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core-shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. The opposite trend for alloying of the core-shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.

  4. Probing the Structures and Electronic Properties of Dual-Phosphorus-Doped Gold Cluster Anions (AunP-2, n = 1–8): A Density functional Theory Investigation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Kang-Ming; Huang, Teng; Liu, Yi-Rong; Jiang, Shuai; Zhang, Yang; Lv, Yu-Zhou; Gai, Yan-Bo; Huang, Wei

    2015-07-29

    The geometries of gold clusters doped with two phosphorus atoms, (AunP-2, n = 1–8) were investigated using density functional theory (DFT) methods. Various two-dimensional (2D) and three-dimensional (3D) structures of the doped clusters were studied. The results indicate that the structures of dual-phosphorus-doped gold clusters exhibit large differences from those of pure gold clusters with small cluster sizes. In our study, as for Au6P-2, two cis–trans isomers were found. The global minimum of Au8P-2 presents a similar configuration to that of Au-20, a pyramid-shaped unit, and the potential novel optical and catalytic properties of this structure warrant further attention. The higher stability of AunP-2 clusters relative to Au-n+2 (n = 1–8) clusters was verified based on various energy parameters, and the results indicate that the phosphorus atom can improve the stabilities of the gold clusters. We then explored the evolutionary path of (n = 1–8) clusters. We found that AunP-2 clusters exhibit the 2D–3D structural transition at n = 6, which is much clearer and faster than that of pure gold clusters and single-phosphorus-doped clusters. The electronic properties of AunP-2 (n = 1–8) were then investigated. The photoelectron spectra provide additional fundamental information on the structures and molecular orbitals shed light on the evolution of AunP-2 (n = 1–8). Natural bond orbital (NBO) described the charge distribution in stabilizing structures and revealed the strong relativistic effects of the gold atoms.

  5. Steady-State Density Functional Theory for Finite Bias Conductances.

    Science.gov (United States)

    Stefanucci, G; Kurth, S

    2015-12-09

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

  6. Density functional theory study of BnC clusters.

    Science.gov (United States)

    Liu, Chunhui; Han, Peilin; Tang, Mingsheng

    2011-05-15

    B(n)C clusters (n = 3-10) were studied at the density functional theory (DFT) (B3LYP)/6-311G** level of theory. The calculations predicted that the most stable configurations of the B(n) C clusters are the (n + 1)-membered cyclic structures. For boron-carbon clusters, the configurations containing greater numbers of three-membered boron rings are more favorable, except for the B(7)C and B(9)C clusters. Through molecular orbital analysis of these B(n)C clusters, we have concluded that π-electron delocalization plays a crucial role in the stability of n + 1-membered cyclic structures. In this paper, the relative stability of each cluster is discussed based on their single atomic-binding energies. The capability of clusters to obtain or lose an electron was also discussed, based on their vertical electron detachment energies (VDEs), adiabatic electron detachment energies (ADEs), vertical electron affinities (VEAs) and adiabatic electron affinities (AEAs). Copyright © 2011 John Wiley & Sons, Ltd.

  7. Superconductivity in layered binary silicides: A density functional theory study

    Science.gov (United States)

    Flores-Livas, José A.; Debord, Régis; Botti, Silvana; San Miguel, Alfonso; Pailhès, Stéphane; Marques, Miguel A. L.

    2011-11-01

    A class of metal disilicides (of the form XSi2, where X is a divalent metal) crystallizes in the EuGe2 structure, formed by hexagonal corrugated silicon planes intercalated with metal atoms. These compounds are superconducting like other layered superconductors, such as MgB2. Moreover, their properties can be easily tuned either by external pressure or by negative chemical pressure (i.e., by changing the metal), which makes disilicides an ideal testbed to study superconductivity in layered systems. In view of this, we present an extensive density functional theory study of the electronic and phonon band structures as well as the electron-phonon interaction of metal disilicides. Our results explain the variation of the superconducting transition temperature with pressure and the species of the intercalating atom, and allow us to predict superconductivity for compounds not yet synthesized belonging to this family.

  8. Time-dependent density functional theory: Causality and other problems

    Energy Technology Data Exchange (ETDEWEB)

    Ruggenthaler, Michael; Bauer, Dieter [Max-Planck-Inst. fuer Kernphysik, Heidelberg (Germany)

    2007-07-01

    Time-dependent density functional theory (TDDFT) is a reformulation of the time dependent many-body problem in quantum mechanics which is capable of reducing the computational cost to calculate, e.g., strongly driven many-electron systems enormously. Recent developments were able to overcome fundamental problems associated with ionization processes. Still vital issues have to be clarified. Besides the construction of the underlying functionals we investigate the causality problem of TDDFT by general considerations and by studying a exactly solvable system of two correlated electrons in an intense laser-pulse. For the latter system, the two alternative approaches to the construction of the action functional or a constrained functional derivative by van Leeuwen and Gal, respectively, are explored.

  9. Excitation Spectra of Nucleobases with Multiconfigurational Density Functional Theory

    DEFF Research Database (Denmark)

    Hubert, Mickaël; Jensen, Hans Jørgen Aa; Hedegård, Erik D.

    2016-01-01

    Range-separated hybrid methods between wave function theory and density functional theory (DFT) can provide high-accuracy results, while correcting some of the inherent flaws of both the underlying wave function theory and DFT. We here assess the accuracy for excitation energies of the nucleobases...

  10. Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex.

    Science.gov (United States)

    Gupta, Rupal; Lacy, David C; Bominaar, Emile L; Borovik, A S; Hendrich, Michael P

    2012-06-13

    High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit coupling of the ground state with an excited S = 1 electronic configuration at 1.2 eV. (17)O isotope enrichment experiments allowed the determination of the hyperfine constants ((17)O)A(z) = 10 MHz for [Fe(IV)H(3)buea(O)](-) and ((17)O)A(y) = 8 MHz, ((17)O)A(z) = 12 MHz for [Fe(III)H(3)buea(OH)](-). The isotropic hyperfine constant (((17)O)A(iso) = -16.8 MHz) was derived from the experimental value to allow a quantitative determination of the spin polarization (ρ(p) = 0.56) of the oxo p orbitals of the Fe-oxo bond in [Fe(IV)H(3)buea(O)](-). This is the first experimental determination for non-heme complexes and indicates significant covalency in the Fe-oxo bond. High-field Mössbauer spectroscopy gave an (57)Fe A(dip) tensor of (+5.6, +5

  11. Atomic and molecular adsorption on transition-metal carbide (111) surfaces from density-functional theory: a trend study of surface electronic factors.

    Science.gov (United States)

    Vojvodic, A; Ruberto, C; Lundqvist, B I

    2010-09-22

    This study explores atomic and molecular adsorption on a number of early transition-metal carbides (TMCs) in NaCl structure by means of density-functional theory calculations. The investigated substrates are the TM-terminated TMC(111) surfaces, of interest because of the presence of different types of surface resonances (SRs) on them and because of their technological importance in growth processes. Also, TM compounds have shown potential in catalysis applications. Trend studies are conducted with respect to both period and group in the periodic table, choosing the substrates ScC, TiC, VC, ZrC, NbC, δ-MoC, TaC, and WC (in NaCl structure) and the adsorbates H, B, C, N, O, F, NH, NH(2), and NH(3). Trends in adsorption strength are explained in terms of surface electronic factors, by correlating the calculated adsorption-energy values with the calculated surface electronic structures. The results are rationalized by use of a concerted-coupling model (CCM), which has previously been applied successfully to the description of adsorption on TiC(111) and TiN(111) surfaces (Ruberto et al 2007 Solid State Commun. 141 48). First, the clean TMC(111) surfaces are characterized by calculating surface energies, surface relaxations, Bader charges, and surface-localized densities of states (DOSs). Detailed comparisons between surface and bulk DOSs reveal the existence of transition-metal localized SRs (TMSRs) in the pseudogap and of several C-localized SRs (CSRs) in the upper valence band on all considered TMC(111) surfaces. The spatial extent and the dangling bond nature of these SRs are supported by real-space analyses of the calculated Kohn-Sham wavefunctions. Then, atomic and molecular adsorption energies, geometries, and charge transfers are presented. An analysis of the adsorbate-induced changes in surface DOSs reveals a presence of both adsorbate-TMSR and adsorbate-CSRs interactions, of varying strengths depending on the surface and the adsorbate. These variations are

  12. Calculate Electric Field Gradient of TiO2 Within Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>TiO2 electric field gradient has been calculated utilizing WIEN2K program, which is ab initio based on density function theory (DFT). DFT uses the charge density as a variable instead of electronic wave

  13. Differentiable but exact formulation of density-functional theory

    CERN Document Server

    Kvaal, Simen; Teale, Andrew M; Helgaker, Trygve

    2013-01-01

    The universal density functional $F$ of density-functional theory is a complicated and ill-behaved function of the density--in particular, $F$ is not differentiable, making many formal manipulations more complicated. Whilst $F$ has been well characterized in terms of convex analysis as forming a conjugate pair $(F,E)$ with the ground-state energy $E$ via the Hohenberg-Kohn and Lieb variation principles, $F$ is only subdifferentiable on a small (but dense) set of its domain. In this article, we apply a tool from convex analysis, Moreau-Yosida regularization, to construct, for any $\\epsilon>0$, pairs of conjugate functionals $({}^\\epsilon\\!E,{}^\\epsilon\\! F)$ that converge to $(E,F)$ pointwise everywhere as $\\epsilon\\rightarrow 0^+$, and such that ${}^\\epsilon\\!F$ is (Fr\\'echet) differentiable. For technical reasons, we limit our attention to molecular electronic systems in a finite but large box, which does not change the physics. It is noteworthy that no information is lost in the Moreau-Yosida regularization...

  14. Reflection-asymmetric nuclear deformations within the Density Functional Theory

    CERN Document Server

    Olsen, E; Nazarewicz, W; Stoitsov, M; 10.1088/1742-6596/402/1/012034

    2013-01-01

    Within the nuclear density functional theory (DFT) we study the effect of reflection-asymmetric shapes on ground-state binding energies and binding energy differences. To this end, we developed the new DFT solver AxialHFB that uses an approximate second-order gradient to solve the Hartree-Fock-Bogoliubov equations of superconducting DFT with the quasi-local Skyrme energy density functionals. Illustrative calculations are carried out for even-even isotopes of radium and thorium.

  15. Revisiting the Fermi Surface in Density Functional Theory

    Science.gov (United States)

    Das, Mukunda P.; Green, Frederick

    2016-06-01

    The Fermi surface is an abstract object in the reciprocal space of a crystal lattice, enclosing the set of all those electronic band states that are filled according to the Pauli principle. Its topology is dictated by the underlying lattice structure and its volume is the carrier density in the material. The Fermi surface is central to predictions of thermal, electrical, magnetic, optical and superconducting properties in metallic systems. Density functional theory is a first-principles method used to estimate the occupied-band energies and, in particular, the isoenergetic Fermi surface. In this review we survey several key facts about Fermi surfaces in complex systems, where a proper theoretical understanding is still lacking. We address some critical difficulties.

  16. Study of Magnesium Diboride Clusters Using Hybrid Density Functional Theory

    Directory of Open Access Journals (Sweden)

    D. Rodríguez

    2007-12-01

    Full Text Available Using hybrid density functional theory and a relatively large basis set, the lowest energy equilibrium structure, vibrational spectrum, and natural orbital analysis were obtained for magnesium diboride clusters [(MgB2x for x=1,2, and 3]. For comparison, boron clusters [Bx for x=2,4, and 6] were also considered. The MgB2 and (MgB22 showed equilibrium structures with the boron atoms in arrangements similar to what was obtained for pure boron atoms, whereas, for (MgB23 a different arrangement of boron was obtained. From the population analysis, large electron density in the boron atoms forming the clusters was observed.

  17. Nonequilibrium Anderson model made simple with density functional theory

    Science.gov (United States)

    Kurth, S.; Stefanucci, G.

    2016-12-01

    The single-impurity Anderson model is studied within the i-DFT framework, a recently proposed extension of density functional theory (DFT) for the description of electron transport in the steady state. i-DFT is designed to give both the steady current and density at the impurity, and it requires the knowledge of the exchange-correlation (xc) bias and on-site potential (gate). In this work we construct an approximation for both quantities which is accurate in a wide range of temperatures, gates, and biases, thus providing a simple and unifying framework to calculate the differential conductance at negligible computational cost in different regimes. Our results mark a substantial advance for DFT and may inform the construction of functionals applicable to other correlated systems.

  18. Oxygen adsorption on pyrite (100) surface by density functional theory

    Institute of Scientific and Technical Information of China (English)

    孙伟; 胡岳华; 邱冠周; 覃文庆

    2004-01-01

    Pyrite (FeS2) bulk and (100) surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 (100) surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference.The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.

  19. Density functional theory study of the structural, electronic, lattice dynamical, and thermodynamic properties of Li4SiO4 and its capability for CO2 capture

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Yuhua; Parlinski, K.

    2011-01-01

    The structural, electronic, lattice dynamical, optical, thermodynamic, and CO{sub 2} capture properties of monoclinic and triclinic phases of Li{sub 4}SiO{sub 4} are investigated by combining density functional theory with phonon lattice dynamics calculations. We found that these two phases have some similarities in their bulk and thermodynamic properties. The calculated bulk modulus and the cohesive energies of these two phases are close to each other. Although both of them are insulators, the monoclinic phase of Li{sub 4}SiO{sub 4} has a direct band gap of 5.24 eV while the triclinic Li{sub 4}SiO{sub 4} phase has an indirect band gap of 4.98 eV. In both phases of Li{sub 4}SiO{sub 4}, the s orbital of O mainly contributes to the lower-energy second valence band (VB{sub 2}) and the p orbitals contribute to the fist valence band (VB{sub 1}) and the conduction bands (CBs). The s orbital of Si mainly contributes to the lower portions of the VB1 and VB{sub 2}, and Si p orbitals mainly contribute to the higher portions of the VB{sub 1} and VB{sub 2}. The s and p orbitals of Li contribute to both VBs and to CBs, and Li p orbitals have a higher contribution than the Li s orbital. There is possibly a phonon soft mode existing in triclinic {gamma}-Li{sub 4}SiO{sub 4}; in the monoclinic Li{sub 4}SiO{sub 4}, there are three phonon soft modes, which correspond to the one type of Li disordered over a few sites. Their LO-TO splitting indicates that both phases of Li{sub 4}SiO{sub 4} are polar anisotropic materials. The calculated infrared absorption spectra for LO and TO modes are different for these two phases of Li{sub 4}SiO{sub 4}. The calculated relationships of the chemical potential versus temperature and CO{sub 2} pressure for reaction of Li{sub 4}SiO{sub 4} with CO{sub 2} shows that Li{sub 4}SiO{sub 4} could be a good candidate for a high-temperature CO{sub 2} sorbent while used for postcombustion capture technology.

  20. Introduction to Classical Density Functional Theory by Computational Experiment

    CERN Document Server

    Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel

    2014-01-01

    We present here an introductory practical course to classical density functional theory (cDFT). Density functional theories, whether quantum or classical, rely largely on nonintuitive abstract concepts and applied mathematics. They are nevertheless a powerful tool and an active field of research in physics and chemistry that led to the 1998 Nobel prize in chemistry. We here illustrate the DFT in its most mathematically simple and yet physically relevant form: the classical density functional theory of an ideal fluid in an external field, as applied to the prediction of the structure of liquid neon at the molecular scale. This introductory course is built around the production of a cDFT code written by students using the Mathematica language. In this way, they are brought to deal with (i) the cDFT theory itself, (ii) some basic concepts around the statistical mechanics of simple fluids, (iii) the underlying mathematical and numerical problem of functional minimization, and (iv) a functional programming languag...

  1. Electronic properties of graphene nanoribbons: A density functional investigation

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Sandeep, E-mail: skumar198712@gmail.com; Sharma, Hitesh, E-mail: dr.hitesh.phys@gmail.com [Department of Physics, Punjab Technical University Kapurthala, Punjab-144601 (India)

    2015-05-15

    Density functional theory calculations have been performed on graphene nano ribbons (GNRs) to investigate the electronic properties as a function of chirality, size and hydrogenation on the edges. The calculations were performed on GNRs with armchair and zigzag configurations with 28, 34, 36, 40, 50, 56, 62, 66 carbon atoms. The structural stability of AGNR and ZGNR increases with the size of nanoribbon where as hydrogenation of GNR tends to lowers their structural stability. All GNRs considered have shown semiconducting behavior with HOMO-LUMO gap decreasing with the increase in the GNR size. The hydrogenation of GNR decreases its HOMO-LUMO gap significantly. The results are in agreement with the available experimental and theoretical results.

  2. Screened-exchange density functional theory description of the electronic structure and phase stability of the chalcopyrite materials AgInSe2 and AuInSe2

    Science.gov (United States)

    Kim, Namhoon; Martin, Pamela Peña; Rockett, Angus A.; Ertekin, Elif

    2016-04-01

    We present a systematic assessment of the structural properties, the electronic density of states, the charge densities, and the phase stabilities of AgInSe2 and AuInSe2 using screened-exchange hybrid density functional theory, and compare their properties to those of CuInSe2. For AgInSe2, hybrid density functional theory properly captures several experimentally measured properties, including the increase in the band gap and the change in the direction of the lattice distortion parameter u in comparison to CuInSe2. While the electronic properties of AuInSe2 have not yet been experimentally characterized, we predict it to be a small gap (≈0.15 eV) semiconductor. We also present the phase stability of AgInSe2 and AuInSe2 according to screened-exchange density functional theory, and compare the results to predictions from conventional density functional theory, results tabulated from several online materials data repositories, and experiment (when available). In comparison to conventional density functional theory, the hybrid functional predicts phase stabilities of AgInSe2 in better agreement with experiment: discrepancies in the calculated formation enthalpies are reduced by approximately a factor of 3, from ≈0.20 eV/atom to ≈0.07 eV/atom, similar to the improvement observed for CuInSe2. We further predict that AuInSe2 is not a stable phase, and can only be present under nonequilibrium conditions.

  3. Hybrid density functional theory band structure engineering in hematite.

    Science.gov (United States)

    Pozun, Zachary D; Henkelman, Graeme

    2011-06-14

    We present a hybrid density functional theory (DFT) study of doping effects in α-Fe(2)O(3), hematite. Standard DFT underestimates the band gap by roughly 75% and incorrectly identifies hematite as a Mott-Hubbard insulator. Hybrid DFT accurately predicts the proper structural, magnetic, and electronic properties of hematite and, unlike the DFT+U method, does not contain d-electron specific empirical parameters. We find that using a screened functional that smoothly transitions from 12% exact exchange at short ranges to standard DFT at long range accurately reproduces the experimental band gap and other material properties. We then show that the antiferromagnetic symmetry in the pure α-Fe(2)O(3) crystal is broken by all dopants and that the ligand field theory correctly predicts local magnetic moments on the dopants. We characterize the resulting band gaps for hematite doped by transition metals and the p-block post-transition metals. The specific case of Pd doping is investigated in order to correlate calculated doping energies and optical properties with experimentally observed photocatalytic behavior.

  4. Curvature and Frontier Orbital Energies in Density Functional Theory.

    Science.gov (United States)

    Stein, Tamar; Autschbach, Jochen; Govind, Niranjan; Kronik, Leeor; Baer, Roi

    2012-12-20

    Perdew et al. discovered two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between integer electron points. (ii) Across an integer number of electrons, the exchange-correlation potential "jumps" by a constant, known as the derivative discontinuity (DD). Here we show analytically that in both the original and the generalized Kohn-Sham formulation of DFT the two properties are two sides of the same coin. The absence of a DD dictates deviation from piecewise linearity, but the latter, appearing as curvature, can be used to correct for the former, thereby restoring the physical meaning of orbital energies. A simple correction scheme for any semilocal and hybrid functional, even Hartree-Fock theory, is shown to be effective on a set of small molecules, suggesting a practical correction for the infamous DFT gap problem. We show that optimally tuned range-separated hybrid functionals can inherently minimize both DD and curvature, thus requiring no correction, and that this can be used as a sound theoretical basis for novel tuning strategies.

  5. Density-functional perturbation theory goes time-dependent

    OpenAIRE

    Gebauer, Ralph; Rocca, Dario; Baroni, Stefano

    2009-01-01

    The scope of time-dependent density-functional theory (TDDFT) is limited to the lowest portion of the spectrum of rather small systems (a few tens of atoms at most). In the static regime, density-functional perturbation theory (DFPT) allows one to calculate response functions of systems as large as currently dealt with in ground-state simulations. In this paper we present an effective way of combining DFPT with TDDFT. The dynamical polarizability is first expressed as an off-diagonal matrix e...

  6. Density functional theory for polymeric systems in 2D.

    Science.gov (United States)

    Słyk, Edyta; Roth, Roland; Bryk, Paweł

    2016-06-22

    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.

  7. Embedding germanium in graphene: A density functional theory study

    Science.gov (United States)

    Xu, Zhuo; Li, Yangping; Tan, Tingting; Liu, Zhengtang

    2017-03-01

    Based on the density functional theory, we investigate the structural, electronic, and magnetic properties of graphene sheet with substitutional Ge atoms in both single and double vacancies, and graphene sheet with Ge-chain impurity. We find the substitutional Ge is chemically bonded to graphene, and is more stable in the double vacancy site. The electronic properties indicate that metallic and semiconductor states with a range of band gaps from 0 to 0.87 eV could be obtained depending on different substitution sites, concentrations, and vacancy types. Magnetic moment is observed in graphene with single vacancy. Tunable electronic behaviors are also observed in graphene sheet with Ge-chain impurity, and a magnetic moment of 2.9 μB is observed in single Ge-chain incorporated 4 × 4 graphene supercell. From these investigations, we conclude that by doping of Ge in vacancy-contained graphene, it could provide great advantages for its application in future nanoscale devices.

  8. Hardness of FeB4: density functional theory investigation.

    Science.gov (United States)

    Zhang, Miao; Lu, Mingchun; Du, Yonghui; Gao, Lili; Lu, Cheng; Liu, Hanyu

    2014-05-07

    A recent experimental study reported the successful synthesis of an orthorhombic FeB4 with a high hardness of 62(5) GPa [H. Gou et al., Phys. Rev. Lett. 111, 157002 (2013)], which has reignited extensive interests on whether transition-metal borides compounds will become superhard materials. However, it is contradicted with some theoretical studies suggesting transition-metal boron compounds are unlikely to become superhard materials. Here, we examined structural and electronic properties of FeB4 using density functional theory. The electronic calculations show the good metallicity and covalent Fe-B bonding. Meanwhile, we extensively investigated stress-strain relations of FeB4 under various tensile and shear loading directions. The calculated weakest tensile and shear stresses are 40 GPa and 25 GPa, respectively. Further simulations (e.g., electron localization function and bond length along the weakest loading direction) on FeB4 show the weak Fe-B bonding is responsible for this low hardness. Moreover, these results are consistent with the value of Vickers hardness (11.7-32.3 GPa) by employing different empirical hardness models and below the superhardness threshold of 40 GPa. Our current results suggest FeB4 is a hard material and unlikely to become superhard (>40 GPa).

  9. Phase-Space Explorations in Time-Dependent Density Functional Theory

    OpenAIRE

    Rajam, Arun K.; Hessler, Paul; Gaun, Christian; Maitra, Neepa T.

    2009-01-01

    We discuss two problems which are particularly challenging for approximations in time-dependent density functional theory (TDDFT) to capture: momentum-distributions in ionization processes, and memory-dependence in real-time dynamics. We propose an extension of TDDFT to phase-space densities, discuss some formal aspects of such a "phase-space density functional theory" and explain why it could ameliorate the problems in both cases. For each problem, a two-electron model system is exactly nume...

  10. Global and local curvature in density functional theory

    Science.gov (United States)

    Zhao, Qing; Ioannidis, Efthymios I.; Kulik, Heather J.

    2016-08-01

    Piecewise linearity of the energy with respect to fractional electron removal or addition is a requirement of an electronic structure method that necessitates the presence of a derivative discontinuity at integer electron occupation. Semi-local exchange-correlation (xc) approximations within density functional theory (DFT) fail to reproduce this behavior, giving rise to deviations from linearity with a convex global curvature that is evidence of many-electron, self-interaction error and electron delocalization. Popular functional tuning strategies focus on reproducing piecewise linearity, especially to improve predictions of optical properties. In a divergent approach, Hubbard U-augmented DFT (i.e., DFT+U) treats self-interaction errors by reducing the local curvature of the energy with respect to electron removal or addition from one localized subshell to the surrounding system. Although it has been suggested that DFT+U should simultaneously alleviate global and local curvature in the atomic limit, no detailed study on real systems has been carried out to probe the validity of this statement. In this work, we show when DFT+U should minimize deviations from linearity and demonstrate that a "+U" correction will never worsen the deviation from linearity of the underlying xc approximation. However, we explain varying degrees of efficiency of the approach over 27 octahedral transition metal complexes with respect to transition metal (Sc-Cu) and ligand strength (CO, NH3, and H2O) and investigate select pathological cases where the delocalization error is invisible to DFT+U within an atomic projection framework. Finally, we demonstrate that the global and local curvatures represent different quantities that show opposing behavior with increasing ligand field strength, and we identify where these two may still coincide.

  11. Density functional theory in surface science and heterogeneous catalysis

    DEFF Research Database (Denmark)

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

    2006-01-01

    amount of experimental data gathered during the last decades. This article shows how density functional theory can be used to describe the state of the surface during reactions and the rate of catalytic reactions. It will also show how we are beginning to understand the variation in catalytic activity...

  12. Charge and spin fluctuations in the density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Gyoerffy, B.L.; Barbieri, A. (Bristol Univ. (UK). H.H. Wills Physics Lab.); Staunton, J.B. (Warwick Univ., Coventry (UK). Dept. of Physics); Shelton, W.A.; Stocks, G.M. (Oak Ridge National Lab., TN (USA))

    1990-01-01

    We introduce a conceptual framework which allow us to treat charge and spin fluctuations about the Local density Approximation (LDA) to the Density Functional Theory (DFT). We illustrate the approach by explicit study of the Disordered Local Moment (DLM) state in Fe above the Curie Temperature {Tc} and the Mott insulating state in MnO. 27 refs., 6 figs.

  13. Orbital-Free Density Functional Theory for Molecular Structure Calculations

    Institute of Scientific and Technical Information of China (English)

    Huajie Chen; Aihui Zhou

    2008-01-01

    We give here an overview of the orbital-free density functional theory that is used for modeling atoms and molecules. We review typical approximations to the kinetic energy, exchange-correlation corrections to the kinetic and Hartree energies, and constructions of the pseudopotentials. We discuss numerical discretizations for the orbital-free methods and include several numerical results for illustrations.

  14. A Tryst With Density: Walter Kohn and Density Functional Theory

    Indian Academy of Sciences (India)

    Shobhana Narasimhan

    2017-08-01

    Walter Kohn transformed theoretical chemistry and solid statephysics with his development of density functional theory, forwhich he was awarded the Nobel Prize. This article tries toexplain, in simple terms, why this was an important advancein the field, and to describe precisely what it was that he (togetherwith his collaborators Pierre Hohenberg and Lu JeuSham) achieved.

  15. Exact ensemble density-functional theory for excited states

    CERN Document Server

    Yang, Zeng-hui; Pribram-Jones, Aurora; Burke, Kieron; Needs, Richard J; Ullrich, Carsten A

    2014-01-01

    We construct exact Kohn-Sham potentials for the ensemble density-functional theory (EDFT) of excited states from the ground and excited states of helium. The exchange-correlation potential is compared with current approximations, which miss prominent features. The ensemble derivative discontinuity is tested, and the virial theorem is proven and illustrated.

  16. Reproducibility in density functional theory calculations of solids

    DEFF Research Database (Denmark)

    Lejaeghere, Kurt; Bihlmayer, Gustav; Björkman, Torbjörn

    2016-01-01

    The widespread popularity of density functional theory has given rise to an extensive range of dedicated codes for predicting molecular and crystalline properties. However, each code implements the formalism in a different way, raising questions about the reproducibility of such predictions. We r...

  17. Linear-response thermal time-dependent density functional theory

    CERN Document Server

    Pribram-Jones, Aurora; Burke, Kieron

    2015-01-01

    The van Leeuwen proof of linear-response time-dependent density functional theory (TDDFT) is generalized to thermal ensembles. This allows generalization to finite temperatures of the Gross-Kohn relation, the exchange-correlation kernel of TDDFT, and fluctuation dissipation theorem for DFT. This produces a natural method for generating new thermal exchange-correlation (XC) approximations.

  18. Chiroptical Properties of Amino Acids: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Martine Adrian-Scotto

    2010-04-01

    Full Text Available Amino acids are involved in many scientific theories elucidating possible origins of life on Earth. One of the challenges when discussing the evolutionary origin of biopolymers such as proteins and oligonucleotides in living organisms is the phenomenon that these polymers implement monomers of exclusively one handedness, a feature called biomolecular homochirality. Many attempts have been made to understand this process of racemic symmetry breaking. Assuming an extraterrestrial origin of the molecular building blocks of living organisms, their susceptibility to asymmetric photolysis by the absorption of circularly polarized electromagnetic radiation in interstellar space was proposed. In order to predict whether the interaction of circularly polarized light with various racemic amino acids can induce an enantiomeric excess, we investigated the electronic and chiroptical properties of the amino acids valine and isovaline by a molecular modelling approach based on quantum chemistry (Density Functional Theory. The average spectra of both L-valine and L-isovaline have been produced on the basis of Boltzmann population analysis using computed spectra for the various conformations of each amino acid.

  19. Time-dependent density-functional theory for extended systems

    Energy Technology Data Exchange (ETDEWEB)

    Botti, Silvana [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Schindlmayr, Arno [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Del Sole, Rodolfo [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Reining, Lucia [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown)

    2007-03-15

    For the calculation of neutral excitations, time-dependent density functional theory (TDDFT) is an exact reformulation of the many-body time-dependent Schroedinger equation, based on knowledge of the density instead of the many-body wavefunction. The density can be determined in an efficient scheme by solving one-particle non-interacting Schroedinger equations-the Kohn-Sham equations. The complication of the problem is hidden in the-unknown-time-dependent exchange and correlation potential that appears in the Kohn-Sham equations and for which it is essential to find good approximations. Many approximations have been suggested and tested for finite systems, where even the very simple adiabatic local-density approximation (ALDA) has often proved to be successful. In the case of solids, ALDA fails to reproduce optical absorption spectra, which are instead well described by solving the Bethe-Salpeter equation of many-body perturbation theory (MBPT). On the other hand, ALDA can lead to excellent results for loss functions (at vanishing and finite momentum transfer). In view of this and thanks to recent successful developments of improved linear-response kernels derived from MBPT, TDDFT is today considered a promising alternative to MBPT for the calculation of electronic spectra, even for solids. After reviewing the fundamentals of TDDFT within linear response, we discuss different approaches and a variety of applications to extended systems.

  20. Charge transfer in time-dependent density functional theory

    Science.gov (United States)

    Maitra, Neepa T.

    2017-10-01

    Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in their computational modeling, due to its unprecedented balance between accuracy and efficiency. However, although exact in principle, in practise approximations must be made for the exchange-correlation functional in this theory, and the standard functional approximations perform poorly for excitations which have a long-range charge-transfer component. Intense progress has been made in developing more sophisticated functionals for this problem, which we review. We point out an essential difference between the properties of the exchange-correlation kernel needed for an accurate description of charge-transfer between open-shell fragments and between closed-shell fragments. We then turn to charge-transfer dynamics, which, in contrast to the excitation problem, is a highly non-equilibrium, non-perturbative, process involving a transfer of one full electron in space. This turns out to be a much more challenging problem for TDDFT functionals. We describe dynamical step and peak features in the exact functional evolving over time, that are missing in the functionals currently used. The latter underestimate the amount of charge transferred and manifest a spurious shift in the charge transfer resonance position. We discuss some explicit examples.

  1. Density Functional Theory Studies of Magnetically Confined Fermi Gas

    Institute of Scientific and Technical Information of China (English)

    陈宇俊; 马红孺

    2001-01-01

    A theory is developed for magnetically confined Fermi gas at a low temperature based on the density functional theory. The theory is illustrated by the numerical calculation of the density distributions of Fermi atoms 40K with parameters according to DeMarco and Jin's experiment [Science, 285(1999)1703]. Our results are in close agreement with the experiment. To check the theory, we also performed calculations using our theory at a high temperature, which compared very well to the results of the classical limit.

  2. Particle vibrational coupling in covariant density functional theory

    CERN Document Server

    Ring, P; 10.1134/S1063778809080055

    2009-01-01

    A consistent combination of covariant density functional theory (CDFT) and Landau-Migdal Theory of Finite Fermi Systems (TFFS) is presented. Both methods are in principle exact, but Landau-Migdal theory cannot describe ground state properties and density functional theory does not take into account the energy dependence of the self-energy and therefore fails to yield proper single-% particle spectra as well as the coupling to complex configurations in the width of giant resonances. Starting from an energy functional, phonons and their vertices are calculated without any further parameters. They form the basis of particle-vibrational coupling leading to an energy dependence of the self-energy and an induced energy-dependent interaction in the response equation. A subtraction procedure avoids double counting. Applications in doubly magic nuclei and in a chain of superfluid nuclei show excellent agreement with experimental data.

  3. Inclusion of Dispersion Effects in Density Functional Theory

    DEFF Research Database (Denmark)

    Møgelhøj, Andreas

    In this thesis, applications and development will be presented within the field of van der Waals interactions in density functional theory. The thesis is based on the three projects: i) van der Waals interactions effect on the structure of liquid water at ambient conditions, ii) development...... and benchmarking of a new van der Waals density functional, and iii) the application of the newly developed functional to CO desorption from Ru(0001). The effect of van der Waals interactions in water was studied by performing ab initio molecular dynamics simulations using PBE and the two recent van der Waals...... density functionals optPBE-vdW and vdW-DF2 with identical computational setup. The two van der Waals functionals have been found to give excellent descriptions of the constituents of water (e.g., water dimers and hexamers). Including van der Waals interactions gives a softer water structure as seen from...

  4. Efficient Density Functional Approximation for Electronic Properties of Conjugated Systems

    Science.gov (United States)

    Caldas, Marília J.; Pinheiro, José Maximiano, Jr.; Blum, Volker; Rinke, Patrick

    2014-03-01

    There is on-going discussion about reliable prediction of electronic properties of conjugated oligomers and polymers, such as ionization potential IP and energy gap. Several exchange-correlation (XC) functionals are being used by the density functional theory community, with different success for different properties. In this work we follow a recent proposal: a fraction α of exact exchange is added to the semi-local PBE XC aiming consistency, for a given property, with the results obtained by many-body perturbation theory within the G0W0 approximation. We focus the IP, taken as the negative of the highest occupied molecular orbital energy. We choose α from a study of the prototype family trans-acetylene, and apply this same α to a set of oligomers for which there is experimental data available (acenes, phenylenes and others). Our results indicate we can have excellent estimates, within 0,2eV mean ave. dev. from the experimental values, better than through complete EN - 1 -EN calculations from the starting PBE functional. We also obtain good estimates for the electrical gap and orbital energies close to the band edge. Work supported by FAPESP, CNPq, and CAPES, Brazil, and DAAD, Germany.

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

    Science.gov (United States)

    Umezawa, Naoto

    2017-09-01

    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, HTC, is introduced by a similarity transformation of a many-body Hamiltonian, H , with respect to a complex function F: HTC=1/F H F . It is proved that an expectation value of HTC for a normalized single Slater determinant, Dn, corresponds to the total energy: E [n ] = ⟨Ψn|H |Ψn ⟩ /⟨Ψn|Ψn ⟩ = ⟨Dn|HTC|Dn ⟩ under the two assumptions: (1) The electron density n (r ) associated with a trial wave function Ψn = DnF is v -representable and (2) Ψn and Dn give rise to the same electron density n (r ). 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.

  6. Density functional theory investigation of opto-electronic properties of thieno[3,4-b]thiophene and benzodithiophene polymer and derivatives and their applications in solar cell.

    Science.gov (United States)

    Khoshkholgh, Mehri Javan; Marsusi, Farah; Abolhassani, Mohammad Reza

    2015-02-05

    PTBs polymers with thieno[3,4-b]thiophene [TT] and benzodithiophene [BDT] units have particular properties, which demonstrate it as one of the best group of donor materials in organic solar cells. In the present work, density functional theory (DFT) is applied to investigate the optimized structure, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), band gap and dihedral angle of PTB7 at B3LYP/6-31G(d). Two different approaches are applied to carry out these investigations: Oligomer extrapolation technique and periodic boundary condition (PBC) method. The results obtained from PBC-DFT method are in fair agreement with experiments. Based on these reliable outcomes; the investigations continued to perform some derivatives of PTB7. In this study, sulfur is substituted by nitrogen, oxygen, silicon, phosphor or selenium atoms in pristine PTB7. Due to the shift of HOMO and LUMO levels, smaller band gaps are predicted to appear in some derivatives in comparison with PTB7. Maximum theoretical efficiencies, η, of the mentioned derivatives as well as local difference of dipole moments between the ground and excited states (Δμge) are computed. The results indicate that substitution of sulfur by nitrogen or oxygen in BDT unit, and silicon or phosphor in TT unit of pristine PTB7 leads to a higher η as well as Δμge.

  7. Density functional theory predictions of isotropic hyperfine coupling constants.

    Science.gov (United States)

    Hermosilla, L; Calle, P; García de la Vega, J M; Sieiro, C

    2005-02-17

    The reliability of density functional theory (DFT) in the determination of the isotropic hyperfine coupling constants (hfccs) of the ground electronic states of organic and inorganic radicals is examined. Predictions using several DFT methods and 6-31G, TZVP, EPR-III and cc-pVQZ basis sets are made and compared to experimental values. The set of 75 radicals here studied was selected using a wide range of criteria. The systems studied are neutral, cationic, anionic; doublet, triplet, quartet; localized, and conjugated radicals, containing 1H, 9Be, 11B, 13C, 14N, 17O, 19F, 23Na, 25Mg, 27Al, 29Si, 31P, 33S, and 35Cl nuclei. The considered radicals provide 241 theoretical hfcc values, which are compared with 174 available experimental ones. The geometries of the studied systems are obtained by theoretical optimization using the same functional and basis set with which the hfccs were calculated. Regression analysis is used as a basic and appropriate methodology for this kind of comparative study. From this analysis, we conclude that DFT predictions of the hfccs are reliable for B3LYP/TZVP and B3LYP/EPR-III combinations. Both functional/basis set scheme are the more useful theoretical tools for predicting hfccs if compared to other much more expensive methods.

  8. Density Functional Theory Study of Spirodienone Stereoisomers in Lignin

    Energy Technology Data Exchange (ETDEWEB)

    Elder, Thomas [USDA-Forest; Berstis, Laura [National; Biosciences; Beckham, Gregg T. [National; Crowley, Michael F. [National; Biosciences

    2017-07-10

    The spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ~3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a ..beta..-1 bond, has been proposed to be a precursor for acyclic ..beta..-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C-O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.

  9. Simple preconditioning for time-dependent density functional perturbation theory

    Science.gov (United States)

    Lehtovaara, Lauri; Marques, Miguel A. L.

    2011-07-01

    By far, the most common use of time-dependent density functional theory is in the linear-reponse regime, where it provides information about electronic excitations. Ideally, the linear-response equations should be solved by a method that avoids the use of the unoccupied Kohn-Sham states — such as the Sternheimer method — as this reduces the complexity and increases the precision of the calculation. However, the Sternheimer equation becomes ill-conditioned near and indefinite above the first resonant frequency, seriously hindering the use of efficient iterative solution methods. To overcome this serious limitation, and to improve the general convergence properties of the iterative techniques, we propose a simple preconditioning strategy. In our method, the Sternheimer equation is solved directly as a linear equation using an iterative Krylov subspace method, i.e., no self-consistent cycle is required. Furthermore, the preconditioner uses the information of just a few unoccupied states and requires simple and minimal modifications to existing implementations. In this way, convergence can be reached faster and in a considerably wider frequency range than the traditional approach.

  10. Daubechies wavelets for linear scaling density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Mohr, Stephan [Institut für Physik, Universität Basel, Klingelbergstr. 82, 4056 Basel (Switzerland); Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Ratcliff, Laura E.; Genovese, Luigi; Caliste, Damien; Deutsch, Thierry [Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Boulanger, Paul [Univ. Grenoble Alpes, INAC-SP2M, F-38000 Grenoble, France and CEA, INAC-SP2M, F-38000 Grenoble (France); Institut Néel, CNRS and Université Joseph Fourier, B.P. 166, 38042 Grenoble Cedex 09 (France); Goedecker, Stefan [Institut für Physik, Universität Basel, Klingelbergstr. 82, 4056 Basel (Switzerland)

    2014-05-28

    We demonstrate that Daubechies wavelets can be used to construct a minimal set of optimized localized adaptively contracted basis functions in which the Kohn-Sham orbitals can be represented with an arbitrarily high, controllable precision. Ground state energies and the forces acting on the ions can be calculated in this basis with the same accuracy as if they were calculated directly in a Daubechies wavelets basis, provided that the amplitude of these adaptively contracted basis functions is sufficiently small on the surface of the localization region, which is guaranteed by the optimization procedure described in this work. This approach reduces the computational costs of density functional theory calculations, and can be combined with sparse matrix algebra to obtain linear scaling with respect to the number of electrons in the system. Calculations on systems of 10 000 atoms or more thus become feasible in a systematic basis set with moderate computational resources. Further computational savings can be achieved by exploiting the similarity of the adaptively contracted basis functions for closely related environments, e.g., in geometry optimizations or combined calculations of neutral and charged systems.

  11. Evidence for anisotropic dielectric properties of monoclinic hafnia using valence electron energy-loss spectroscopy in high-resolution transmission electron microscopy and ab initio time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Guedj, C. [University Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); Hung, L.; Sottile, F. [LSI, CNRS, CEA, École Polytechnique, F-91128 Palaiseau (France); European Theoretical Spectroscopy Facility (ETSF) (France); Zobelli, A. [LPS, CNRS and University Paris Sud, F-91405 Orsay (France); Blaise, P. [University Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); European Theoretical Spectroscopy Facility (ETSF) (France); Olevano, V. [University Grenoble Alpes, F-38000 Grenoble (France); European Theoretical Spectroscopy Facility (ETSF) (France); CNRS, Institut Néel, F-38042 Grenoble (France)

    2014-12-01

    The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO{sub 2}) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO{sub 2}, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO{sub 2} may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectric permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.

  12. Evidence for anisotropic dielectric properties of monoclinic hafnia using valence electron energy-loss spectroscopy in high-resolution transmission electron microscopy and ab initio time-dependent density-functional theory

    Science.gov (United States)

    Guedj, C.; Hung, L.; Zobelli, A.; Blaise, P.; Sottile, F.; Olevano, V.

    2014-12-01

    The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO2) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO2, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO2 may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectric permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.

  13. Density functional theory study of neutral and oxidized thiophene oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Yafei; Wei, Chengwei [School of Physics Science and Technology and Jiangsu Key Laboratory for NSLSCS, Nanjing Normal University, Nanjing 210023 (China); Blaisten-Barojas, Estela, E-mail: blaisten@gmu.edu [Computational Materials Science Center and School of Physics, Astronomy and Computational Sciences, George Mason University, Fairfax, Virginia 22030 (United States)

    2013-11-14

    The effect of oxidation on the energetics and structure of thiophene (Th) oligomers is studied with density functional theory at the B3PW91/6-311++G(d,p) level. Neutral n-Th oligomers (2 < n < 13) are gently curved planar chains. Ionization potential and electron affinity results show that n-Th oligomers are easier to be oxidized as their chain length increases. Oxidation states +2, +4, +6, and +8 are energetically stable in 12-Th. Upon oxidation the conjugated backbone of 12-Th switches from extended benzenoid phase to quinoid phase localized on groups of monomers regularly spaced along the chain. Oxidized states +2, +4, +6, and +8 of 12-Th display two +1e localized at the ends of their chains only because of the finite size of the chains. In 12-Th this end-effect extends over the two terminal monomers forming a positive-negative charge duet. This peculiar charge localization makes n-Th oligomers different from other conducting polymers with similar structure, such as polypyrrole. The spectrum of single-electron molecular states of oxidized 12-Th displays two localized single-electron states in the HOMO-LUMO energy gap per +2 oxidation state. Oligothiophene 12-Th doped with F atoms at 1:2 concentration presents a charge transfer of 3.4 e from oligomer to dopants that increases to 4.8 e in the presence of solvent. The charge distribution in these F-doped oligomers is similar to the +4 oxidation state of 12-Th. It is predicted that dopants produce an enhanced charge transfer localized in the proximity of their locations enhancing the formation of bipolarons in the central part of the oligomer chain.

  14. Nitrogenase structure and function relationships by density functional theory.

    Science.gov (United States)

    Harris, Travis V; Szilagyi, Robert K

    2011-01-01

    Modern density functional theory has tremendous potential with matching popularity in metalloenzymology to reveal the unseen atomic and molecular details of structural data, spectroscopic measurements, and biochemical experiments by providing insights into unobservable structures and states, while also offering theoretical justifications for observed trends and differences. An often untapped potential of this theoretical approach is to bring together diverse experimental structural and reactivity information and allow for these to be critically evaluated at the same level. This is particularly applicable for the tantalizingly complex problem of the structure and molecular mechanism of biological nitrogen fixation. In this chapter we provide a review with extensive practical details of the compilation and evaluation of experimental data for an unbiased and systematic density functional theory analysis that can lead to remarkable new insights about the structure-function relationships of the iron-sulfur clusters of nitrogenase.

  15. Relativistic density functional theory for finite nuclei and neutron stars

    CERN Document Server

    Piekarewicz, J

    2015-01-01

    The main goal of the present contribution is a pedagogical introduction to the fascinating world of neutron stars by relying on relativistic density functional theory. Density functional theory provides a powerful--and perhaps unique--framework for the calculation of both the properties of finite nuclei and neutron stars. Given the enormous densities that may be reached in the core of neutron stars, it is essential that such theoretical framework incorporates from the outset the basic principles of Lorentz covariance and special relativity. After a brief historical perspective, we present the necessary details required to compute the equation of state of dense, neutron-rich matter. As the equation of state is all that is needed to compute the structure of neutron stars, we discuss how nuclear physics--particularly certain kind of laboratory experiments--can provide significant constrains on the behavior of neutron-rich matter.

  16. Spin projection with double hybrid density functional theory.

    Science.gov (United States)

    Thompson, Lee M; Hratchian, Hrant P

    2014-07-21

    A spin projected double-hybrid density functional theory is presented that accounts for different scaling of opposite and same spin terms in the second order correction. This method is applied to three dissociation reactions which in the unprojected formalism exhibit significant spin contamination with higher spin states. This gives rise to a distorted potential surface and can lead to poor geometries and energies. The projected method presented is shown to improve the description of the potential over unprojected double hybrid density functional theory. Comparison is made with the reference states of the two double hybrid functionals considered here (B2PLYP and mPW2PLYP) in which the projected potential surface is degraded by an imbalance in the description of dynamic and static correlation.

  17. 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.

  18. Density functional theory across chemistry, physics and biology.

    Science.gov (United States)

    van Mourik, Tanja; Bühl, Michael; Gaigeot, Marie-Pierre

    2014-03-13

    The past decades have seen density functional theory (DFT) evolve from a rising star in computational quantum chemistry to one of its major players. This Theme Issue, which comes half a century after the publication of the Hohenberg-Kohn theorems that laid the foundations of modern DFT, reviews progress and challenges in present-day DFT research. Rather than trying to be comprehensive, this Theme Issue attempts to give a flavour of selected aspects of DFT.

  19. Reproducibility in density functional theory calculations of solids

    OpenAIRE

    2016-01-01

    This is the author accepted manuscript.The final version is available from the American Association for the Advancement of Science via http://dx.doi.org/10.1126/science.aad3000 The widespread popularity of density-functional theory has given rise to a vast range of dedicated codes to predict molecular and crystalline properties. However, each code implements the formalism in a different way, raising questions on the reproducibility of such predictions. We report the results of a community-...

  20. The Role of the Basis Set: Assessing Density Functional Theory

    CERN Document Server

    Boese, A D; Handy, N C; Martin, Jan M. L.; Handy, Nicholas C.

    2003-01-01

    When developing and assessing density functional theory methods, a finite basis set is usually employed. In most cases, however, the issue of basis set dependency is neglected. Here, we assess several basis sets and functionals. In addition, the dependency of the semiempirical fits to a given basis set for a generalised gradient approximation and a hybrid functional is investigated. The resulting functionals are then tested for other basis sets, evaluating their errors and transferability.

  1. Nuclear charge radii: Density functional theory meets Bayesian neural networks

    CERN Document Server

    Utama, Raditya; Piekarewicz, Jorge

    2016-01-01

    The distribution of electric charge in atomic nuclei is fundamental to our understanding of the complex nuclear dynamics and a quintessential observable to validate nuclear structure models. We explore a novel approach that combines sophisticated models of nuclear structure with Bayesian neural networks (BNN) to generate predictions for the charge radii of thousands of nuclei throughout the nuclear chart. A class of relativistic energy density functionals is used to provide robust predictions for nuclear charge radii. In turn, these predictions are refined through Bayesian learning for a neural network that is trained using residuals between theoretical predictions and the experimental data. Although predictions obtained with density functional theory provide a fairly good description of experiment, our results show significant improvement (better than 40%) after BNN refinement. Moreover, these improved results for nuclear charge radii are supplemented with theoretical error bars. We have successfully demonst...

  2. 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.

  3. Clustering and pasta phases in nuclear density functional theory

    CERN Document Server

    Schuetrumpf, Bastian; Nazarewicz, Witold

    2016-01-01

    Nuclear density functional theory (DFT) is the tool of choice in describing properties of complex nuclei and intricate phases of bulk nucleonic matter. It is a microscopic approach based on an energy density functional representing the nuclear interaction. An attractive feature of nuclear DFT is that it can be applied to both finite nuclei and pasta phases appearing in the inner crust of neutron stars. While nuclear pasta clusters in a neutron star can be easily characterized through their density distributions, the level of clustering of nucleons in a nucleus can often be difficult to assess. To this end, we use the concept of nucleonic localization. We demonstrate that the localization measure provides us with fingerprints of clusters in light and heavy nuclei, including fissioning systems. Furthermore we investigate the rod-like pasta phase using twist-averaged boundary conditions, which enable calculations in finite volumes accessible by state of the art DFT solvers.

  4. Efficient Diffuse Basis Sets for Density Functional Theory.

    Science.gov (United States)

    Papajak, Ewa; Truhlar, Donald G

    2010-03-09

    Eliminating all but the s and p diffuse functions on the non-hydrogenic atoms and all diffuse functions on the hydrogen atoms from the aug-cc-pV(x+d)Z basis sets of Dunning and co-workers, where x = D, T, Q, ..., yields the previously proposed "minimally augmented" basis sets, called maug-cc-pV(x+d)Z. Here, we present extensive and systematic tests of these basis sets for density functional calculations of chemical reaction barrier heights, hydrogen bond energies, electron affinities, ionization potentials, and atomization energies. The tests show that the maug-cc-pV(x+d)Z basis sets are as accurate as the aug-cc-pV(x+d)Z ones for density functional calculations, but the computational cost savings are a factor of about two to seven.

  5. Time-dependent density functional theory (TD-DFT) coupled with reference interaction site model self-consistent field explicitly including spatial electron density distribution (RISM-SCF-SEDD)

    Science.gov (United States)

    Yokogawa, D.

    2016-09-01

    Theoretical approach to design bright bio-imaging molecules is one of the most progressing ones. However, because of the system size and computational accuracy, the number of theoretical studies is limited to our knowledge. To overcome the difficulties, we developed a new method based on reference interaction site model self-consistent field explicitly including spatial electron density distribution and time-dependent density functional theory. We applied it to the calculation of indole and 5-cyanoindole at ground and excited states in gas and solution phases. The changes in the optimized geometries were clearly explained with resonance structures and the Stokes shift was correctly reproduced.

  6. 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.

  7. Sternheimer shieldings and EFG polarizabilities: a density-functional theory study

    Science.gov (United States)

    Rizzo, Antonio; Ruud, Kenneth; Helgaker, Trygve; Sałek, Paweł; Ågren, Hans; Vahtras, Olav

    2003-04-01

    The electric field gradient (EFG) at the nucleus, the generalized Sternheimer shielding constants, and the EFG hyperpolarizabilities of a set of reference molecules are computed using analytic density-functional (up to quadratic) response theory. At the three-parameter Becke-Lee-Yang-Parr (B3LYP) level, density functional theory (DFT) underestimates correlation effects compared with other approaches such as coupled-cluster and multiconfigurational self-consistent field. For the prediction of EFG properties of hydrogen nuclei and electron-rich atoms such as halides, DFT/B3LYP provides results even less reliable than Hartree-Fock theory.

  8. Range-separated double-hybrid density-functional theory applied to periodic systems

    OpenAIRE

    Sansone, Giuseppe; Civalleri, Bartolomeo; Usvyat, Denis; Toulouse, Julien; Sharkas, Kamal; Maschio, Lorenzo

    2015-01-01

    International audience; Quantum chemistry methods exploiting density-functional approximations for short-range electron-electron interactions and second-order M{{\\o}}ller-Plesset (MP2) perturbation theory for long-range electron-electron interactions have been implemented for periodic systems using Gaussian-type basis functions and the local correlation framework. The performance of these range-separated double hybrids has been benchmarked on a significant set of systems including rare-gas, m...

  9. Application of Density Functional Theory to Systems Containing Metal Atoms

    Science.gov (United States)

    Bauschlicher, Charles W., Jr.

    2006-01-01

    The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.

  10. 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...... for molecules and solids. Fluctuations within the ensemble can then be used to estimate errors relative to experiment on calculated quantities such as binding energies, bond lengths, and vibrational frequencies. It is demonstrated that the error bars on energy differences may vary by orders of magnitude...

  11. 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...

  12. Atomistic force field for alumina fit to density functional theory.

    Science.gov (United States)

    Sarsam, Joanne; Finnis, Michael W; Tangney, Paul

    2013-11-28

    We present a force field for bulk alumina (Al2O3), which has been parametrized by fitting the energies, forces, and stresses of a large database of reference configurations to those calculated with density functional theory (DFT). We use a functional form that is simpler and computationally more efficient than some existing models of alumina parametrized by a similar technique. Nevertheless, we demonstrate an accuracy of our potential that is comparable to those existing models and to DFT. We present calculations of crystal structures and energies, elastic constants, phonon spectra, thermal expansion, and point defect formation energies.

  13. 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...

  14. Dynamical density functional theory with hydrodynamic interactions in confined geometries

    Science.gov (United States)

    Goddard, B. D.; Nold, A.; Kalliadasis, S.

    2016-12-01

    We study the dynamics of colloidal fluids in both unconfined geometries and when confined by a hard wall. Under minimal assumptions, we derive a dynamical density functional theory (DDFT) which includes hydrodynamic interactions (HI; bath-mediated forces). By using an efficient numerical scheme based on pseudospectral methods for integro-differential equations, we demonstrate its excellent agreement with the full underlying Langevin equations for systems of hard disks in partial confinement. We further use the derived DDFT formalism to elucidate the crucial effects of HI in confined systems.

  15. Augmented Lagrangian Method for Constrained Nuclear Density Functional Theory

    CERN Document Server

    Staszczak, A; Baran, A; Nazarewicz, W

    2010-01-01

    The augmented Lagrangiam method (ALM), widely used in quantum chemistry constrained optimization problems, is applied in the context of the nuclear Density Functional Theory (DFT) in the self-consistent constrained Skyrme Hartree-Fock-Bogoliubov (CHFB) variant. The ALM allows precise calculations of multidimensional energy surfaces in the space of collective coordinates that are needed to, e.g., determine fission pathways and saddle points; it improves accuracy of computed derivatives with respect to collective variables that are used to determine collective inertia; and is well adapted to supercomputer applications.

  16. Multiphase aluminum equations of state via density functional theory

    Science.gov (United States)

    Sjostrom, Travis; Crockett, Scott; Rudin, Sven

    2016-10-01

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

  17. Quantification of Uncertainties in Nuclear Density Functional theory

    CERN Document Server

    Schunck, N; Higdon, D; Sarich, J; Wild, S

    2014-01-01

    Reliable predictions of nuclear properties are needed as much to answer fundamental science questions as in applications such as reactor physics or data evaluation. Nuclear density functional theory is currently the only microscopic, global approach to nuclear structure that is applicable throughout the nuclear chart. In the past few years, a lot of effort has been devoted to setting up a general methodology to assess theoretical uncertainties in nuclear DFT calculations. In this paper, we summarize some of the recent progress in this direction. Most of the new material discussed here will be be published in separate articles.

  18. 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...... in combination with maximally localized Wannier functions and the norm-conserving pseudopotential code SIESTA which applies an atomic orbital basis set. All calculations have been converged with respect to the supercell size and the number of k(parallel to) points in the surface plane. For all systems we find...

  19. Dynamic density functional theory with hydrodynamic interactions and fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Donev, Aleksandar, E-mail: donev@courant.nyu.edu; Vanden-Eijnden, Eric, E-mail: eve2@courant.nyu.edu [Courant Institute of Mathematical Sciences, New York University, New York, New York 10012 (United States)

    2014-06-21

    We derive a closed equation for the empirical concentration of colloidal particles in the presence of both hydrodynamic and direct interactions. The ensemble average of our functional Langevin equation reproduces known deterministic Dynamic Density Functional Theory (DDFT) [M. Rex and H. Löwen, “Dynamical density functional theory with hydrodynamic interactions and colloids in unstable traps,” Phys. Rev. Lett. 101(14), 148302 (2008)], and, at the same time, it also describes the microscopic fluctuations around the mean behavior. We suggest separating the ideal (non-interacting) contribution from additional corrections due to pairwise interactions. We find that, for an incompressible fluid and in the absence of direct interactions, the mean concentration follows Fick's law just as for uncorrelated walkers. At the same time, the nature of the stochastic terms in fluctuating DDFT is shown to be distinctly different for hydrodynamically-correlated and uncorrelated walkers. This leads to striking differences in the behavior of the fluctuations around Fick's law, even in the absence of pairwise interactions. We connect our own prior work [A. Donev, T. G. Fai, and E. Vanden-Eijnden, “A reversible mesoscopic model of diffusion in liquids: from giant fluctuations to Fick's law,” J. Stat. Mech.: Theory Exp. (2014) P04004] on fluctuating hydrodynamics of diffusion in liquids to the DDFT literature, and demonstrate that the fluid cannot easily be eliminated from consideration if one wants to describe the collective diffusion in colloidal suspensions.

  20. Stochastic Time-Dependent Current-Density Functional Theory

    Science.gov (United States)

    D'Agosta, Roberto

    2008-03-01

    Static and dynamical density functional methods have been applied with a certain degree of success to a variety of closed quantum mechanical systems, i.e., systems that can be described via a Hamiltonian dynamics. However, the relevance of open quantum systems - those coupled to external environments, e.g., baths or reservoirs - cannot be overestimated. To investigate open quantum systems with DFT methods we have introduced a new theory, we have named Stochastic Time-Dependent Current Density Functional theory (S-TDCDFT) [1]: starting from a suitable description of the system dynamics via a stochastic Schrödinger equation [2], we have proven that given an initial quantum state and the coupling between the system and the environment, there is a one-to-one correspondence between the ensemble-averaged current density and the external vector potential applied to the system.In this talk, I will introduce the stochastic formalism needed for the description of open quantum systems, discuss in details the theorem of Stochastic TD-CDFT, and provide few examples of its applicability like the dissipative dynamics of excited systems, quantum-measurement theory and other applications relevant to charge and energy transport in nanoscale systems.[1] M. Di Ventra and R. D'Agosta, Physical Review Letters 98, 226403 (2007)[2] N.G. van Kampen, Stochastic processes in Physics and Chemistry, (North Holland, 2001), 2nd ed.

  1. Relations among several nuclear and electronic density functional reactivity indexes

    Science.gov (United States)

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

    2003-11-01

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

  2. 4-Arylflavan-3-ols as Proanthocyanidin Models: Absolute Configuration via Density Functional Calculation of Electronic Circular Dichroism

    Science.gov (United States)

    Density functional theory/B3LYP has been employed to optimize the conformations of selected 4-arylflavan-3-ols and their phenolic methyl ether 3-O-acetates. The electronic circular dichroism spectra of the major conformers have been calculated using time-dependent density functional theory to valida...

  3. 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.

  4. Density-functional perturbation theory goes time-dependent

    Directory of Open Access Journals (Sweden)

    Gebauer, Ralph

    2008-05-01

    Full Text Available The scope of time-dependent density-functional theory (TDDFT is limited to the lowest portion of the spectrum of rather small systems (a few tens of atoms at most. In the static regime, density-functional perturbation theory (DFPT allows one to calculate response functions of systems as large as currently dealt with in ground-state simulations. In this paper we present an effective way of combining DFPT with TDDFT. The dynamical polarizability is first expressed as an off-diagonal matrix element of the resolvent of the Kohn-Sham Liouvillian super-operator. A DFPT representation of response functions allows one to avoid the calculation of unoccupied Kohn-Sham orbitals. The resolvent of the Liouvillian is finally conveniently evaluated using a newly developed non-symmetric Lanczos technique, which allows for the calculation of the entire spectrum with a single Lanczos recursion chain. Each step of the chain essentially requires twice as many operations as a single step of the iterative diagonalization of the unperturbed Kohn-Sham Hamiltonian or, for that matter, as a single time step of a Car-Parrinello molecular dynamics run. The method will be illustrated with a few case molecular applications.

  5. Covariant density functional theory: Reexamining the structure of superheavy nuclei

    CERN Document Server

    Agbemava, S E; Nakatsukasa, T; Ring, P

    2015-01-01

    A systematic investigation of even-even superheavy elements in the region of proton numbers $100 \\leq Z \\leq 130$ and in the region of neutron numbers from the proton-drip line up to neutron number $N=196$ is presented. For this study we use five most up-to-date covariant energy density functionals of different types, with a non-linear meson coupling, with density dependent meson couplings, and with density-dependent zero-range interactions. Pairing correlations are treated within relativistic Hartree-Bogoliubov (RHB) theory based on an effective separable particle-particle interaction of finite range and deformation effects are taken into account. This allows us to assess the spread of theoretical predictions within the present covariant models for the binding energies, deformation parameters, shell structures and $\\alpha$-decay half-lives. Contrary to the previous studies in covariant density functional theory, it was found that the impact of $N=172$ spherical shell gap on the structure of superheavy elemen...

  6. Chemical reactivity in the framework of pair density functional theories.

    Science.gov (United States)

    Otero, Nicolás; Mandado, Marcos

    2012-05-15

    Chemical reactivity descriptors are derived within the framework of the pair density functional theory. These indices provide valuable information about bonding rearrangements and activating mechanisms upon electrophilic or nucleophilic reactions. Indices derived and tested in this work represent nonlocal counterparts of the local reactivity indices derived in the context of conceptual density functional theory (CDFT) and frequently used in reactivity studies; the Fukui function, the local softness and the dual descriptor. In this work, we show how these nonlocal indices provide a quantum chemical basis to explain the success of qualitative resonance models in chemical reactivity predictions. Also, local information is implicitly contained as CDFT indices are obtained by simple integration. As illustrative examples, we have considered in this work the Markovnikov's rule, the reactivity of enolate anion, the nucleophilic conjugate addition to α,β-unsaturated compounds and the electrophilic aromatic substitution of benzene derivatives. The densities used in this work were obtained with Hartree-Fock, Kohn-Sham DFT, and singles and doubles configuration interaction (CISD) approaches. Copyright © 2012 Wiley Periodicals, Inc.

  7. Comparative study of patulin, ascladiol, and neopatulin by Density Functional Theory

    Science.gov (United States)

    Patulin, a secondary metabolite produced by several fungal species, is a potential contaminant of fruit and vegetable products. To better understand the structure and electronic properties of this mycotoxin and its biosynthetic precursors, a density functional theory (DFT) study was performed on co...

  8. Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom

    Science.gov (United States)

    Baseden, Kyle A.; Tye, Jesse W.

    2014-01-01

    Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…

  9. Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom

    Science.gov (United States)

    Baseden, Kyle A.; Tye, Jesse W.

    2014-01-01

    Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…

  10. NBO analysis and vibrational frequencies of tautomers of citrinin by density functional theory

    Science.gov (United States)

    Citrinin is a toxic polyketide contaminant of a number of agricultural commodities, notably Monascus-fermented red rice. Detailed structures and electronic properties of three tautomeric forms of citrinin were investigated using density functional theory calculations at various extended basis sets ...

  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. Uncertainty Quantification and Propagation in Nuclear Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Schunck, N; McDonnell, J D; Higdon, D; Sarich, J; Wild, S M

    2015-03-17

    Nuclear density functional theory (DFT) is one of the main theoretical tools used to study the properties of heavy and superheavy elements, or to describe the structure of nuclei far from stability. While on-going eff orts seek to better root nuclear DFT in the theory of nuclear forces, energy functionals remain semi-phenomenological constructions that depend on a set of parameters adjusted to experimental data in fi nite nuclei. In this paper, we review recent eff orts to quantify the related uncertainties, and propagate them to model predictions. In particular, we cover the topics of parameter estimation for inverse problems, statistical analysis of model uncertainties and Bayesian inference methods. Illustrative examples are taken from the literature.

  13. A molecular density functional theory to study solvation in water

    CERN Document Server

    Jeanmairet, Guillaume

    2014-01-01

    A classical density functional theory is applied to study solvation of solutes in water. An approx- imate form of the excess functional is proposed for water. This functional requires the knowledge of pure solvent direct correlation functions. Those functions can be computed by using molecular simulations such as molecular dynamic or Monte Carlo. It is also possible to use functions that have been determined experimentally. The functional minimization gives access to the solvation free energy and to the equilibrium solvent density. Some correction to the functional are also proposed to get the proper tetrahedral order of solvent molecules around a charged solute and to reproduce the correct long range hydrophobic behavior of big apolar solutes. To proceed the numerical minimization of the functional, the theory has been discretized on two tridimensional grids, one for the space coordinates, the other for the angular coordinates, in a functional minimization code written in modern Fortran, mdft. This program i...

  14. Density functional theory for inhomogeneous associating chain fluids.

    Science.gov (United States)

    Bryk, P; Sokołowski, S; Pizio, O

    2006-07-14

    We propose a nonlocal density functional theory for associating chain molecules. The chains are modeled as tangent spheres, which interact via Lennard-Jones (12,6) attractive interactions. A selected segment contains additional, short-ranged, highly directional interaction sites. The theory incorporates an accurate treatment of the chain molecules via the intramolecular potential formalism and should accurately describe systems with strongly varying external fields, e.g., attractive walls. Within our approach we investigate the structure of the liquid-vapor interface and capillary condensation of a simple model of associating chains with only one associating site placed on the first segment. In general, the properties of inhomogeneous associating chains depend on the association energy. Similar to the bulk systems we find the behavior of associating chains of a given length to be in between that for the nonassociating chains of the same length and that for the nonassociating chains twice as large.

  15. Density functional theory study of the oligomerization of carboxylic acids.

    Science.gov (United States)

    Di Tommaso, Devis; Watson, Ken L

    2014-11-20

    We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA → (CA)4,(D+D) and (CA)3 + CA → (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the α and β solid forms of tetrolic acid. (vi) Stable tetramers of

  16. Zinc surface complexes on birnessite: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

    2009-01-05

    Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.

  17. 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-functional

  18. Periodic Density Functional Theory Solver using Multiresolution Analysis with MADNESS

    Science.gov (United States)

    Harrison, Robert; Thornton, William

    2011-03-01

    We describe the first implementation of the all-electron Kohn-Sham density functional periodic solver (DFT) using multi-wavelets and fast integral equations using MADNESS (multiresolution adaptive numerical environment for scientific simulation; http://code.google.com/p/m-a-d-n-e-s-s). The multiresolution nature of a multi-wavelet basis allows for fast computation with guaranteed precision. By reformulating the Kohn-Sham eigenvalue equation into the Lippmann-Schwinger equation, we can avoid using the derivative operator which allows better control of overall precision for the all-electron problem. Other highlights include the development of periodic integral operators with low-rank separation, an adaptable model potential for nuclear potential, and an implementation for Hartree Fock exchange. This work was supported by NSF project OCI-0904972 and made use of resources at the Center for Computational Sciences at Oak Ridge National Laboratory under contract DE-AC05-00OR22725.

  19. Density Functional Theory using Multiresolution Analysis with MADNESS

    Science.gov (United States)

    Thornton, Scott; Harrison, Robert

    2012-02-01

    We describe the first implementation of the all-electron Kohn-Sham density functional periodic solver (DFT) using multi-wavelets and fast integral equations using MADNESS (multiresolution adaptive numerical environment for scientific simulation; http://code.google.com/p/m-a-d-n-e-s-s). The multiresolution nature of a multi-wavelet basis allows for fast computation with guaranteed precision. By reformulating the Kohn-Sham eigenvalue equation into the Lippmann-Schwinger equation, we can avoid using the derivative operator which allows better control of overall precision for the all-electron problem. Other highlights include the development of periodic integral operators with low-rank separation, an adaptable model potential for the nuclear potential, and an implementation for Hartree-Fock exchange.

  20. Nuclear charge radii: density functional theory meets Bayesian neural networks

    Science.gov (United States)

    Utama, R.; Chen, Wei-Chia; Piekarewicz, J.

    2016-11-01

    The distribution of electric charge in atomic nuclei is fundamental to our understanding of the complex nuclear dynamics and a quintessential observable to validate nuclear structure models. The aim of this study is to explore a novel approach that combines sophisticated models of nuclear structure with Bayesian neural networks (BNN) to generate predictions for the charge radii of thousands of nuclei throughout the nuclear chart. A class of relativistic energy density functionals is used to provide robust predictions for nuclear charge radii. In turn, these predictions are refined through Bayesian learning for a neural network that is trained using residuals between theoretical predictions and the experimental data. Although predictions obtained with density functional theory provide a fairly good description of experiment, our results show significant improvement (better than 40%) after BNN refinement. Moreover, these improved results for nuclear charge radii are supplemented with theoretical error bars. We have successfully demonstrated the ability of the BNN approach to significantly increase the accuracy of nuclear models in the predictions of nuclear charge radii. However, as many before us, we failed to uncover the underlying physics behind the intriguing behavior of charge radii along the calcium isotopic chain.

  1. Study of local response effects in interatomic collisions with two active electrons in the framework of time-dependent density functional theory; Untersuchung lokaler Responseffekte in interatomaren Stoessen mit zwei aktiven Elektronen im Rahmen zeitabhaengiger Dichtefunktionaltheorie

    Energy Technology Data Exchange (ETDEWEB)

    Keim, M.

    2005-07-01

    In the present thesis response effects in interatomic collisions with two active electrons are studied in the range of non-relativistic collision energies. The starting point is the mapping of the time-dependent interacting many-electron sytem on an effective one-particle picture on the base of the time-dependent density functional theory (TDDFT). By means of the basis generator method the one-particle equations aring in the framework of the TDDFT concept are solved in a finite-dimensional model space. In the study of ionization cross section in the collisional systeem anti p+He it is shown that by response effects an essential diminuishing of the cross sections in comparison to the no-response case is reached. Analoguously the ionization cross sections for the collisional systems p-He, He{sup 2+}-He, Li{sup 3+}-He and p-Li{sup +} behave.

  2. Electronic structure and optical properties of CdS{sub x}Se{sub 1−x} solid solution nanostructures from X-ray absorption near edge structure, X-ray excited optical luminescence, and density functional theory investigations

    Energy Technology Data Exchange (ETDEWEB)

    Murphy, M. W. [DESY (Deutsches Elektronen-Synchrotron), FS-PEX, Notkestrasse 85, 22607 Hamburg (Germany); Yiu, Y. M., E-mail: yyiu@uwo.ca; Sham, T. K. [Department of Chemistry, University of Western Ontario, London, ON N6A5B7 (Canada); Ward, M. J. [Cornell High Energy Synchrotron Source (CHESS), Cornell University, Ithaca, NY 14853 (United States); Liu, L. [Institute of Functional Nano and Soft Materials (FUNSOM) and Soochow University-Western University Center for Synchrotron Radiation Research, Soochow University, Suzhou, Jiangsu, 215123 (China); Hu, Y. [Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N2V3 (Canada); Zapien, J. A. [Center Of Super-Diamond and Advanced Films (COSDAF) and Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR (China); Liu, Yingkai [Institute of Physics and Electronic Information, Yunnan Normal University, Kunming, Yunnan, 650500 (China)

    2014-11-21

    The electronic structure and optical properties of a series of iso-electronic and iso-structural CdS{sub x}Se{sub 1−x} solid solution nanostructures have been investigated using X-ray absorption near edge structure, extended X-ray absorption fine structure, and X-ray excited optical luminescence at various absorption edges of Cd, S, and Se. It is found that the system exhibits compositions, with variable local structure in-between that of CdS and CdSe accompanied by tunable optical band gap between that of CdS and CdSe. Theoretical calculation using density functional theory has been carried out to elucidate the observations. It is also found that luminescence induced by X-ray excitation shows new optical channels not observed previously with laser excitation. The implications of these observations are discussed.

  3. Density Function Theory Studies on Reaction of HCS with OH

    Institute of Scientific and Technical Information of China (English)

    PEI Ke-Mei; LI Yi-Min; LI Hai-Yang

    2003-01-01

    The exothermic reaction of HCS with OH on the single-state potential energy surface was explored by means of Density Function Theory(DFT). The equilibrium structural parameters, the harmonic vibrational frequencies, the total energies and the zero point energies(ZPE) of all the species in the reaction were computed. Six intermediates and seven transition states were located, three exothermic channels were found. The frequency analysis and the Intrinsic Reaction Coordinate(IRC) calculation confirm that the transitions are truthful. The results indicate that there are three exothermic channels and their corresponding products are: P1(H2O+CS), P2(H2S+CO), P3(OCS+H2), and P1 has a larger branch ratio.

  4. Density functional theory studies of HCOOH decomposition on Pd(111)

    Science.gov (United States)

    Scaranto, Jessica; Mavrikakis, Manos

    2016-08-01

    The investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO2 + H2 and dehydration to CO + H2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in the presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.

  5. Dynamic density functional theory of solid tumor growth: Preliminary models

    Directory of Open Access Journals (Sweden)

    Arnaud Chauviere

    2012-03-01

    Full Text Available Cancer is a disease that can be seen as a complex system whose dynamics and growth result from nonlinear processes coupled across wide ranges of spatio-temporal scales. The current mathematical modeling literature addresses issues at various scales but the development of theoretical methodologies capable of bridging gaps across scales needs further study. We present a new theoretical framework based on Dynamic Density Functional Theory (DDFT extended, for the first time, to the dynamics of living tissues by accounting for cell density correlations, different cell types, phenotypes and cell birth/death processes, in order to provide a biophysically consistent description of processes across the scales. We present an application of this approach to tumor growth.

  6. Nucleation for Lennard-Jones Fluid by Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    FU Dong

    2005-01-01

    @@ A non-mean field density functional theory is employed to investigate the vapour-liquid nucleation. The excess Helmholtz free energy functional is formulated in terms of a local density approximation for short ranged repulsion and a density-gradient expansion for long-ranged attractions. An analytical expression for the direct correlation function of a Lennard-Jones fluid is utilized to take into account the effect of long-ranged attractions on intermolecular correlations. With the predicted bulk properties and surface tension as input, the nucleation properties including density profile, work of formation and number of particles at the reduced temperatures T* = 0.694 and 0.741 are inuestigated. The obtained number of particles in the critical nucleus agrees well with the simulation data.

  7. Electrostatic potential of several small molecules from density functional theory

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A number of density functional theory (DFT) methods were used to calculate the electrostatic potential for the series of molecules N2, F2, NH3, H2O, CHF3, CHCl3, C6H6, TiF4, CO(NH2)2 and C4H5N3O compared with QCISD (quadratic configuration interaction method including single and double substitutions) results. Comparisons were made between the DFT computed results and the QCISD ab initio ones and MP2 ab initio ones, compared with the root-mean-square deviation and electrostatic potential difference contours figures. It was found that the hybrid DFT method B3LYP, yields electrostatic potential in good agreement with the QCISD results. It is suggest this is a useful approach, especially for large molecules that are difficult to study by ab initio methods.

  8. Nuclear energy density functional inspired by an effective field theory

    CERN Document Server

    Papakonstantinou, Panagiota; Lim, Yeunhwan; Hyun, Chang Ho

    2016-01-01

    Inspired by an effective field theory (EFT) for Fermi systems, we write the nuclear energy density functional (EDF) as an expansion in powers of the Fermi momentum $k_F$, or the cubic root of the density $\\rho^{1/3}$. With the help of pseudodata from microscopic calculations we fit the coefficients of the functional within a wide range of densities relevant for nuclei and neutron stars. The functional already at low order can reproduce known or adopted values of nuclear matter near saturation, a range of existing microscopic results on asymmetric matter, and a neutron-star mass-radius relation consistent with observations. Our approach leads to a transparent expansion of Skyrme-type EDFs and opens up many possibilities for future explorations in nuclei and homogeneous matter.

  9. Geometry-based density functional theory an overview

    CERN Document Server

    Schmidt, M

    2003-01-01

    An overview of recent developments and applications of a specific density functional approach that originates from Rosenfeld's fundamental measure theory for hard spheres is given. Model systems that were treated include penetrable spheres that interact with a step function pair potential, the Widom-Rowlinson model, the Asakura-Oosawa colloid-polymer mixture, ternary mixtures of spheres, needles, and globular polymers, hard-body amphiphilic mixtures, fluids in porous media, and random sequential adsorption that describes non-equilibrium processes such as colloidal deposition and random car parking. In these systems various physical phenomena were studied, such as correlations in liquids, freezing and demixing phase behaviour, the properties of fluid interfaces with and without orientational order, and wetting and layering phenomena at walls.

  10. Solvation of complex surfaces via molecular density functional theory

    CERN Document Server

    Levesque, Maximilien; Rotenberg, Benjamin; Jeanmairet, Guillaume; Vuilleumier, Rodolphe; Borgis, Daniel

    2012-01-01

    We show that classical molecular density functional theory (MDFT), here in the homogeneous reference fluid approximation in which the functional is inferred from the properties of the bulk solvent, is a powerful new tool to study, at a fully molecular level, the solvation of complex surfaces and interfaces by polar solvents. This implicit solvent method allows for the determination of structural, orientational and energetic solvation properties that are on a par with all-atom molecular simulations performed for the same system, while reducing the computer time by two orders of magnitude. This is illustrated by the study of an atomistically-resolved clay surface composed of over a thousand atoms wetted by a molecular dipolar solvent. The high numerical efficiency of the method is exploited to carry a systematic analysis of the electrostatic and non-electrostatic components of the surface-solvent interaction within the popular CLAYFF force field. Solvent energetics and structure are found to depend weakly upon ...

  11. Scalable Nuclear Density Functional Theory with Sky3D

    CERN Document Server

    Afibuzzaman, Md; Aktulga, Hasan Metin

    2016-01-01

    In nuclear astro-physics, the quantum simulation of large inhomogenous dense systems as present in the crusts of neutron stars presents big challenges. The feasible number of particles in a simulation box with periodic boundary conditions is strongly limited due to the immense computational cost of the quantum methods. In this paper, we describe the techniques used to parallelize Sky3D, a nuclear density functional theory code that operates on an equidistant grid, and optimize its performance on distributed memory architectures. We also describe cache blocking techniques to accelerate the compute-intensive matrix calculation part in Sky3D. Presented techniques allow Sky3D to achieve good scaling and high performance on a large number of cores, as demonstrated through detailed performance analysis on Edison, a Cray XC30 supercomputer.

  12. A numerical efficient way to minimize classical density functional theory.

    Science.gov (United States)

    Edelmann, Markus; Roth, Roland

    2016-02-21

    The minimization of the functional of the grand potential within the framework of classical density functional theory in three spatial dimensions can be numerically very demanding. The Picard iteration, that is often employed, is very simple and robust but can be rather slow. While a number of different algorithms for optimization problems have been suggested, there is still great need for additional strategies. Here, we present an approach based on the limited memory Broyden algorithm that is efficient and relatively simple to implement. We demonstrate the performance of this algorithm with the minimization of an inhomogeneous bulk structure of a fluid with competing interactions. For the problems we studied, we find that the presented algorithm improves performance by roughly a factor of three.

  13. Calculations of Optical Rotation from Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    António Canal Neto; Francisco Elias Jorge

    2007-01-01

    Density function theory calculations of frequency-dependent optical rotations [α]ω for three rigid chiral molecules are reported. Calculations have been carried out at the sodium D line frequency, using the ADZP basis set and a wide variety of functionals. Gauge-invariant atomic orbitals are used to guarantee origin-independent values of [α]D. In addition, study of geometry dependence of [α]D. Is reported. Using the geometries optimized at the B3LYP/ADZP level, the mean absolute deviation of B3LYP/ADZP and experimental [α]D values yields 60.1°/(dm g/cm3). According to our knowledge, this value has not been achieved until now with any other model.

  14. Ions in solution: density corrected density functional theory (DC-DFT).

    Science.gov (United States)

    Kim, Min-Cheol; Sim, Eunji; Burke, Kieron

    2014-05-14

    Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes of density functional theory calculations are significantly improved by using densities more accurate than the self-consistent densities. We discuss how to identify such cases, and how DC-DFT applies more generally. To illustrate, we calculate potential energy surfaces of HO·Cl(-) and HO·H2O complexes using various common approximate functionals, with and without this density correction. Commonly used approximations yield wrongly shaped surfaces and/or incorrect minima when calculated self consistently, while yielding almost identical shapes and minima when density corrected. This improvement is retained even in the presence of implicit solvent.

  15. Ions in solution: Density Corrected Density Functional Theory (DC-DFT)

    CERN Document Server

    Kim, Min-Cheol; Burke, Kieron

    2014-01-01

    Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes of density functional theory calculations are significantly improved by using densities more accurate than the self-consistent densities. We discuss how to identify such cases, and how DC-DFT applies more generally. To illustrate, we calculate potential energy surfaces of HO$\\cdot$Cl$^-$ and HO$\\cdot$H$_2$O complexes using various common approximate functionals, with and without this density correction. Commonly used approximations yield wrongly shaped surfaces and/or incorrect minima when calculated self consistently, while yielding almost identical shapes and minima when density corrected. This improvement is retained even in the presence of implicit solvent.

  16. Gedanken Densities and Exact Constraints in Density Functional Theory

    CERN Document Server

    Perdew, John P; Sun, Jianwei; Burke, Kieron

    2014-01-01

    Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is no...

  17. Electron-capture decay rate of 7Be@C60 by first-principles calculations based on density functional theory

    NARCIS (Netherlands)

    Morisato, T.; Ohno, K.; Ohtsuki, T.; Hirose, K.; Sluiter, M.; Kawazoe, Y.

    2008-01-01

    Carrying out a first-principles calculation assuming linear relationship between the electron density at Be nucleus and the electron-capture (EC) decay rate, we explained why 7Be@C60 shows higher EC decay rate than 7Be crystal, which was originally found experimentally by Ohtsuki et al. [Phys. Rev.

  18. Subspace accelerated inexact Newton method for large scale wave functions calculations in Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Fattebert, J

    2008-07-29

    We describe an iterative algorithm to solve electronic structure problems in Density Functional Theory. The approach is presented as a Subspace Accelerated Inexact Newton (SAIN) solver for the non-linear Kohn-Sham equations. It is related to a class of iterative algorithms known as RMM-DIIS in the electronic structure community. The method is illustrated with examples of real applications using a finite difference discretization and multigrid preconditioning.

  19. Density functional theory investigations of radical scavenging activity of 3′-Methyl-quercetin

    Directory of Open Access Journals (Sweden)

    Abdullah G. Al-Sehemi

    2016-09-01

    Full Text Available The possible eight rotamers of 3′-Methyl-quercetin have been optimized by using density functional theory (DFT at B3LYP/6-31G∗ level of theory. The molecular structure and molecular properties of the most stable rotamers have been investigated at the same level of theory. We have computed the descriptors; electronegativity (χ, hardness (η, electrophilicity (ω, softness (S and electrophilicity index (ωi by DFT approach. We have shed light on the structure–property relationship. The absorption spectrum has been computed by time dependent density functional theory (TD-DFT at TD-B3LYP/6-31G∗ level of theory. Radical scavenging activity has been explained on the basis of bond dissociation enthalpy (BDE and the adiabatic ionization potential (IP. Two mechanisms have been explained for the radical scavenging processes, i.e., hydrogen atom transfer and one-electron transfer.

  20. Exact maps in density functional theory for lattice models

    Science.gov (United States)

    Dimitrov, Tanja; Appel, Heiko; Fuks, Johanna I.; Rubio, Angel

    2016-08-01

    In the present work, we employ exact diagonalization for model systems on a real-space lattice to explicitly construct the exact density-to-potential and graphically illustrate the complete exact density-to-wavefunction map that underly the Hohenberg-Kohn theorem in density functional theory. Having the explicit wavefunction-to-density map at hand, we are able to construct arbitrary observables as functionals of the ground-state density. We analyze the density-to-potential map as the distance between the fragments of a system increases and the correlation in the system grows. We observe a feature that gradually develops in the density-to-potential map as well as in the density-to-wavefunction map. This feature is inherited by arbitrary expectation values as functional of the ground-state density. We explicitly show the excited-state energies, the excited-state densities, and the correlation entropy as functionals of the ground-state density. All of them show this exact feature that sharpens as the coupling of the fragments decreases and the correlation grows. We denominate this feature as intra-system steepening and discuss how it relates to the well-known inter-system derivative discontinuity. The inter-system derivative discontinuity is an exact concept for coupled subsystems with degenerate ground state. However, the coupling between subsystems as in charge transfer processes can lift the degeneracy. An important conclusion is that for such systems with a near-degenerate ground state, the corresponding cut along the particle number N of the exact density functionals is differentiable with a well-defined gradient near integer particle number.

  1. A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)

    DEFF Research Database (Denmark)

    O'Boyle, N.M.; Albrecht, Tim; Murgida, D.H.

    2007-01-01

    from the metal center to the P0P ligand. The surface is modeled by a cluster of 28 gold atoms and gives a good description of the effect of immobilization on the electronic properties of the complexes. The results show that the coupling between the immobilized complex and the gold surface involves...... electronic polarization at the adsorbate/substrate interface rather than the formation of a covalent bond. However, the cluster is too small to fully represent bulk gold with the result that, contrary to what is experimentally observed, the DFT calculation predicts that the gold surface is more easily...

  2. The importance of current contributions to shielding constants in density-functional theory.

    Science.gov (United States)

    Reimann, Sarah; Ekström, Ulf; Stopkowicz, Stella; Teale, Andrew M; Borgoo, Alex; Helgaker, Trygve

    2015-07-28

    The sources of error in the calculation of nuclear-magnetic-resonance shielding constants determined by density-functional theory are examined. Highly accurate Kohn-Sham wave functions are obtained from coupled-cluster electron density functions and used to define accurate-but current independent-density-functional shielding constants. These new reference values, in tandem with high-accuracy coupled-cluster shielding constants, provide a benchmark for the assessment of errors in common density-functional approximations. In particular the role of errors arising in the diamagnetic and paramagnetic terms is investigated, with particular emphasis on the role of current-dependence in the latter. For carbon and nitrogen the current correction is found to be, in some cases, larger than 10 ppm. This indicates that the absence of this correction in general purpose exchange-correlation functionals is one of the main sources of error in shielding calculations using density functional theory. It is shown that the current correction improves the shielding performance of many popular approximate DFT functionals.

  3. Steady-State Density Functional Theory for Non-equilibrium Quantum Systems

    Science.gov (United States)

    Shuanglong, Liu

    Recently, electron transport properties of molecular junctions under finite bias voltages have attracted a lot of attention because of the potential application of molecular electronic devices. When a molecular junction is under zero bias voltage at zero temperature, it is in equilibrium ground state and all its properties can be solved by ground-state density functional theory (GS-DFT) where ground-state electron density determines everything. Under finite bias voltage, the molecular junction is in non-equilibrium steady state. According to Hershfield's non-equilibrium statistics, a system in non-equilibrium steady state corresponds to an effective equilibrium system. This correspondence provides the basis for the steady-state density functional theory (SS-DFT) which will be developed in this thesis. (Abstract shortened by UMI.).

  4. A Method to Formulate the Unit Cell for Density Functional Theory (DFT) Calculations of the Electronic Band Structure of Heterostructures of Two-dimensional Nanosheets

    Science.gov (United States)

    2015-04-01

    distribution is unlimited. i CONTENTS Page Introduction 1 Two-dimensional Material Geometry and Analogs with Close-packed Systems 1 Matching...distribution is unlimited. 1 INTRODUCTION Two-dimensional (2D) material heterostructures offer novel and compelling electronic and optical...methods have undoubtedly been created for matching lattice constants of dissimilar nanomaterials , very few are actually covered explicitly in literature

  5. Mean Spherical Approximation-Based Partitioned Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shi-Qi

    2003-01-01

    Previous literature claims that the density functional theory for non-uniform non-hard sphere interaction potential fluid can be improved on by treating the tail part by the third order functional perturbation expansion approximation (FPEA) with the symmetrical and intuitive consideration-based simple function C0(3)(r1, r2, r3) =ζ∫ dr4a(r4 - r1)a(r4 - r2)a(r4 - r3) as the uniform third order direct correlation function (DCF) for the tail part,here kernel function a(r) = (6/πσ3)Heaviside(σ/2 - r). The present contribution concludes that for the mean spherical approximation-based second order DCF, the terms higher than second order in the FPEA of the tail part of the non-uniform first order DCF are exactly zero. The reason for the partial success of the previous a kernel function-based third order FPEA for the tail part is due to the adjustable parameter ζ and the short range of the a kernel function.Improvement over the previous theories is proposed and tested.

  6. Mean Spherical Approximation-Based Partitioned Density Functional Theory

    Institute of Scientific and Technical Information of China (English)

    ZHOUShi-Qi

    2003-01-01

    Previous literature claims that the density functional theory for non-uniform non-hard sphere interaction potential fluid can be improved on by treating the tail part by the third order functional perturbation expansion approximation (FPEA) with the symmetrical and intuitive consideration-based simple function C0(3)(r1, r2, r3) =(∫dr4a(r4-r1)a(r4-r2)a(r4-r3) as the uniform third order direct correlation function (DCF) for the tail part,here kernel function a(r) = (6/πσ3)Heaviside(σ/2 - r). The present contribution concludes that for the mean spherical approximation-based second order DCF, the terms higher than second order in the FPEA of the tail part of the non-uniform first order DCF are exactly zero. The reason for the partial success of the previous a kernel function-based third order FPEA for the tail part is due to the adjustable parameter ξ and the short range of the a kernel function.Improvement over the previous theories is proposed and tested.

  7. Dynamics of localized particles from density functional theory

    Science.gov (United States)

    Reinhardt, J.; Brader, J. M.

    2012-01-01

    A fundamental assumption of the dynamical density functional theory (DDFT) of colloidal systems is that a grand-canonical free-energy functional may be employed to generate the thermodynamic driving forces. Using one-dimensional hard rods as a model system, we analyze the validity of this key assumption and show that unphysical self-interactions of the tagged particle density fields, arising from coupling to a particle reservoir, are responsible for the excessively fast relaxation predicted by the theory. Moreover, our findings suggest that even employing a canonical functional would not lead to an improvement for many-particle systems, if only the total density is considered. We present several possible schemes to suppress these effects by incorporating tagged densities. When applied to confined systems, we demonstrate, using a simple example, that DDFT necessarily leads to delocalized tagged particle density distributions, which do not respect the fundamental geometrical constraints apparent in Brownian dynamics simulation data. The implication of these results for possible applications of DDFT to treat the glass transition are discussed.

  8. Electron Transfer Reaction between M-C6H6 and M+-C6H6 Complexes in the Gas Phase: Density Functional Theory Study

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    DFT/BLYP method is used to theoretically investigate the electron transfer (ET) reactions between M (Li, Na, Mg)-C6H6 and M+-C6H6 complexes in the gas phase. The geometry optimization of the precursor complexes and the transition state in the process of ET reaction was performed at 6-31G basis set level. The activation energy, the coupling matrix element and the rate constant of the ET reaction are calculated at semi-quantitative level.

  9. Comparative density functional theory and post-Hartree-Fock (CCSD, CASSCF) studies on the electronic structure of halogen nitrites ClONO and BrONO using quantum chemical topology.

    Science.gov (United States)

    Berski, Slawomir; Gordon, Agnieszka J

    2011-09-07

    In this paper, the electronic structures of cis- and trans-ClONO and BrONO are studied at the CCSD∕aug-cc-pVTZ, CASSCF(14,12)/aug-cc-pVTZ, and B3LYP/aug-cc-pVTZ computational levels. For the Cl-O bond, topological analysis of the electron density field, ρ(r), shows the prevalence of the shared-electron type bond (∇(2)ρ((3,-1)) 0). Topological analysis of the electron localization function, η(r), and electron localizability indicator (ELI-D), (D) (σ)(r), shows that the electronic structure of the central N-O bond is very sensitive to both electron correlation improvements (coupled-cluster single double (CCSD), CASSCF, density functional theory (DFT)) and bond length alteration. Depending on the method used, the N-O bond can be characterized as a "normal" N-O bond with a disynaptic V(N,O) basin (DFT); a protocovalent N-O bond with two monosynaptic, V(N) and V(O), basins (CCSD, CASSCF); or a new type, first discovered for FONO, characterized by a single monosynaptic, V(N) basin (CCSD, DFT). The total basin population oscillates between 0.46-0.96 e (CCSD) and 0.86-1.02 e (CASSCF). The X-O bond is described by the single disynaptic basin, V(X,O), with a basin population between 0.76 and 0.81 e (CCSD) or 0.77 and 0.85 e (CASSCF). Analysis of the localized electron detector distribution for the cis-Cl-O1-N=O2 shows a manifold in the Cl···O2 region, associated with decreased electron density. © 2011 American Institute of Physics

  10. Phase stability, electronic and elastic properties of Fe{sub 6−x}W{sub x}C (x = 0−6) from density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Z.Q., E-mail: zqlv@ysu.edu.cn [State Key Laboratory of Metastable Material Science and Technology, Yanshan University, Qinhuangdao 066004 (China); College of Mechanical Engineering, Yanshan University, Qinhuangdao 066004 (China); Zhou, Z.A. [State Key Laboratory of Metastable Material Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Sun, S.H. [College of Science, Yanshan University, Qinhuangdao 066004 (China); Fu, W.T., E-mail: wtfu@ysu.edu.cn [State Key Laboratory of Metastable Material Science and Technology, Yanshan University, Qinhuangdao 066004 (China)

    2015-08-15

    The calculated formation enthalpies of Fe{sub 3}W{sub 3}C (W in the 48f site) and Fe{sub 2}W{sub 4}C are negative, and they are of higher stability than other (Fe,W){sub 6}C phases. The 16d and 32e sites are comfortable for Fe atoms, while the W atom is preferential in the 48f site during the formation process of (Fe,W){sub 6}C carbides. An exchange of electrons takes place between the Fe/W and the C atom, and also appears between the Fe and W atom. In M–M bonds, besides metallic characters, a valence character between W–W bonds exists. Besides the nonmetal C atom with negative charges (obtaining electrons), the partial metal atoms of Fe and W in different M{sub 6}C-type carbides show an electronegative phenomenon. The carbides W{sub 6}C, Fe{sub 5}WC, Fe{sub 2}W{sub 4}C and Fe{sub 3}W{sub 3}C-II likely have high temperature superconductive characters. The hardness of Fe{sub 3}W{sub 3}C (16.5 GPa) is the highest in these phases, and that of Fe{sub 2}W{sub 4}C (13.7 GPa) is the second highest. The Debye temperature (θ{sub D}) of Fe{sub 3}W{sub 3}C–I (Fe in the 48f site) is lowest (254 K) in these carbides, and that of Fe{sub 3}W{sub 3}C-II suddenly changes to 568 K when W is in the 48f site. The change of the atom in the 48f site intensively influences the properties of M{sub 6}C (M = Fe/W). - Graphical abstract: Display Omitted - Highlights: • The 16d and 32e sites are comfortable for Fe atoms, whereas W atom is preferential in 48f site. • An exchange of electrons takes place in the Fe/W–C, and also appears between the Fe and W atom. • Besides C atom with negative charges, Fe and W partially exists the electronegative phenomenon. • θ{sub D} of Fe{sub 3}W{sub 3}C (Fe in 48f) is 254 K, whereas that of Fe{sub 3}W{sub 3}C (W in 48f) changes to 568 K.

  11. Density functional theory study on LaNi4.5Al0.5 hydride phase: electronic properties and sites occupation

    Institute of Scientific and Technical Information of China (English)

    Chen Dong; Yu Ben-Hai; Wang Chun-Lei; Gao Tao

    2007-01-01

    In this paper the crystal structure, electronic structure and hydrogen site occupation of LaNi4.5Al0.5Hy hydride phase (y=5.0, 6.0) have been investigated by using full-potential linearized augmented plane wave method. The hydrogen atoms were found to prefer the 6m, 12o and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion, the total density of states at EF increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, H plays a dominant role in the stability of LaNi4.sAl0.5Hy hydride phase. The smaller the shift of EF towards the higher energy region, the more stable the compounds will be. The obtained results are compared with experimental data and discussed in the light of previous works.

  12. Investigation of electron density changes at the onset of a chemical reaction using the state-specific dual descriptor from conceptual density functional theory.

    Science.gov (United States)

    De Proft, Frank; Forquet, Valérian; Ourri, Benjamin; Chermette, Henry; Geerlings, Paul; Morell, Christophe

    2015-04-14

    The electron density changes from reactants towards the transition state of a chemical reaction is expressed as a linear combination of the state-specific dual descriptors (SSDD) of the corresponding reactant complexes. Consequently, the SSDD can be expected to bear important resemblance to the so-called natural orbitals for chemical valence (NOCV), introduced as the orbitals that diagonalize the deformation density matrix of interacting molecules. This agreement is shown for three case studies: the complexation of a Lewis acid with a Lewis base, a SN2 nucleophilic substitution reaction and a Diels-Alder cycloaddition reaction. As such, the SSDD computed for reactant complexes are shown to provide important information about charge transfer interactions during a chemical reaction.

  13. Electronic structure and magneto-optical Kerr effect spectra of ferromagnetic shape-memory Ni-Mn-Ga alloys: Experiment and density functional theory calculations

    Science.gov (United States)

    Uba, S.; Bonda, A.; Uba, L.; Bekenov, L. V.; Antonov, V. N.; Ernst, A.

    2016-08-01

    In this joint experimental and ab initio study, we focused on the influence of the chemical composition and martensite phase transition on the electronic, magnetic, optical, and magneto-optical properties of the ferromagnetic shape-memory Ni-Mn-Ga alloys. The polar magneto-optical Kerr effect (MOKE) spectra for the polycrystalline sample of the Ni-Mn-Ga alloy of Ni60Mn13Ga27 composition were measured by means of the polarization modulation method over the photon energy range 0.8 ≤h ν ≤5.8 eV in magnetic field up to 1.5 T. The optical properties (refractive index n and extinction coefficient k ) were measured directly by spectroscopic ellipsometry using the rotating analyzer method. To complement experiments, extensive first-principles calculations were made with two different first-principles approaches combining the advantages of a multiple scattering Green function method and a spin-polarized fully relativistic linear-muffin-tin-orbital method. The electronic, magnetic, and MO properties of Ni-Mn-Ga Heusler alloys were investigated for the cubic austenitic and modulated 7M-like incommensurate martensitic phases in the stoichiometric and off-stoichiometric compositions. The optical and MOKE properties of Ni-Mn-Ga systems are very sensitive to the deviation from the stoichiometry. It was shown that the ab initio calculations reproduce well experimental spectra and allow us to explain the microscopic origin of the Ni2MnGa optical and magneto-optical response in terms of interband transitions. The band-by-band decomposition of the Ni2MnGa MOKE spectra is presented and the interband transitions responsible for the prominent structures in the spectra are identified.

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

    Science.gov (United States)

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

    2013-09-14

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

  15. Density Functional Theory for Phase-Ordering Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianzhong [Univ. of California, Riverside, CA (United States)

    2016-03-30

    Colloids display astonishing structural and dynamic properties that can be dramatically altered by modest changes in the solution condition or an external field. This complex behavior stems from a subtle balance of colloidal forces and intriguing mesoscopic and macroscopic phase transitions that are sensitive to the processing conditions and the dispersing environment. Whereas the knowledge on the microscopic structure and phase behavior of colloidal systems at equilibrium is now well-advanced, quantitative predictions of the dynamic properties and the kinetics of phase-ordering transitions in colloids are not always realized. Many important mesoscopic and off-equilibrium colloidal states remain poorly understood. The proposed research aims to develop a new, unifying approach to describe colloidal dynamics and the kinetics of phase-ordering transitions based on accomplishments from previous work for the equilibrium properties of both uniform and inhomogeneous systems and on novel concepts from the state-of-the-art dynamic density functional theory. In addition to theoretical developments, computational research is designed to address a number of fundamental questions on phase-ordering transitions in colloids, in particular those pertinent to a competition of the dynamic pathways leading to various mesoscopic structures, off-equilibrium states, and crystalline phases. By providing a generic theoretical framework to describe equilibrium, metastable as well as non-ergodic phase transitions concurrent with the colloidal self-assembly processes, accomplishments from this work will have major impacts on both fundamental research and technological applications.

  16. Density functional theory investigation of antiproton-helium collisions

    CERN Document Server

    Henkel, N; Lüdde, H J; Kirchner, T; 10.1103/PhysRevA.80.032704

    2011-01-01

    We revisit recent developments in the theoretical foundations of time-dependent density functional theory (TDDFT). TDDFT is then applied to the calculation of total cross sections for ionization processes in the antiproton-Helium collision system. The Kohn-Sham potential is approximated as the sum of the Hartree-exchange potential and a correlation potential that was proposed in the context of laser-induced ionization. Furthermore, some approaches to the problem of calculating the ionization probabilities from the density are discussed. Small projectile energies below 5keV are considered as well as those in the range from 5 to 1000 keV. Results are compared with former calculations and with experimental data. We find that the correlation potential yields no obvious improvement of the results over the exchange-only approximation where the correlation potential is neglected. Furthermore, we find the problem of calculating the desired observables crucial, introducing errors of at least the same order of magnitud...

  17. Density functional theory study of phase IV of solid hydrogen

    Science.gov (United States)

    Pickard, Chris J.; Martinez-Canales, Miguel; Needs, Richard J.

    2012-06-01

    We have studied solid hydrogen up to pressures of 300 GPa and temperatures of 350 K using density functional theory methods and have found “mixed structures” that are more stable than those predicted earlier. Mixed structures consist of alternate layers of strongly bonded molecules and weakly bonded graphene-like sheets. Quasiharmonic vibrational calculations show that mixed structures are the most stable at room temperature over the pressure range 250-295 GPa. These structures are stabilized with respect to strongly bonded molecular phases at room temperature by the presence of lower frequency vibrational modes arising from the graphene-like sheets. Our results for the mixed structures are consistent with the experimental Raman data [M. I. Eremets and I. A. Troyan, Nat. Mater.1476-112210.1038/nmat3175 10, 927 (2011) and R. T. Howie , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.108.125501 108, 125501 (2012)]. We find that mixed phases are reasonable structural models for phase IV of hydrogen.

  18. Applications of density functional theory in materials science and engineering

    Science.gov (United States)

    Alvarado, Manuel, Jr.

    Density Functional Theory (DFT) is a powerful tool that can be used to model various systems in materials science. Our research applies DFT to two problems of interest. First, an organic/inorganic complex dye system known as a Mayan pigment is modeled to determine chemical binding sites, verifying each model with physical data such as UV/Vis spectra. Preliminary studies on palygorskite-based mayan pigments (mayacrom blue, mayacrom purple) show excellent agreement with experimental studies when using a dimer dye geometry binding with tetrahedrally-coordinated aluminum impurity sites in palygorksite. This approach is applied to a sepiolite-based organic/inorganic dye system using thioindigo attached to a tetrahedral aluminum impurity site with an additional aluminum impurity site in close proximity to the binding site. As a second application of DFT, various grain orientations in beta-Sn are modeled under imposed strains in order to calculate elastic properties of this system. These calculations are intended to clarify discrepancies in published, experimental crystal compliance values.

  19. Exact Maps in Density Functional Theory for Lattice Models

    CERN Document Server

    Dimitrov, Tanja; Fuks, Johanna I; Rubio, Angel

    2015-01-01

    In the present work, we employ exact diagonalization for model systems on a real-space lattice to explicitly construct the exact density-to-potential and for the first time the exact density-to-wavefunction map that underly the Hohenberg-Kohn theorem in density functional theory. Having the explicit wavefunction-to- density map at hand, we are able to construct arbitrary observables as functionals of the ground-state density. We analyze the density-to-potential map as the distance between the fragments of a system increases and the correlation in the system grows. We observe a feature that gradually develops in the density-to-potential map as well as in the density-to-wavefunction map. This feature is inherited by arbitrary expectation values as functional of the ground-state density. We explicitly show the excited-state energies, the excited-state densities, and the correlation entropy as functionals of the ground-state density. All of them show this exact feature that sharpens as the coupling of the fragmen...

  20. Solvation of complex surfaces via molecular density functional theory.

    Science.gov (United States)

    Levesque, Maximilien; Marry, Virginie; Rotenberg, Benjamin; Jeanmairet, Guillaume; Vuilleumier, Rodolphe; Borgis, Daniel

    2012-12-14

    We show that classical molecular density functional theory, here in the homogeneous reference fluid approximation in which the functional is inferred from the properties of the bulk solvent, is a powerful new tool to study, at a fully molecular level, the solvation of complex surfaces and interfaces by polar solvents. This implicit solvent method allows for the determination of structural, orientational, and energetic solvation properties that are on a par with all-atom molecular simulations performed for the same system, while reducing the computer time by two orders of magnitude. This is illustrated by the study of an atomistically-resolved clay surface composed of over a thousand atoms wetted by a molecular dipolar solvent. The high numerical efficiency of the method is exploited to carry a systematic analysis of the electrostatic and non-electrostatic components of the surface-solvent interaction within the popular Clay Force Field (CLAYFF). Solvent energetics and structure are found to depend weakly upon the atomic charges distribution of the clay surface, even for a rather polar solvent. We conclude on the consequences of such findings for force-field development.

  1. Metal catalyzed ethylene epoxidation: A comparative density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Ruipeng Ren; Yongkang Lü; Xianyong Pang; Guichang Wang

    2011-01-01

    Ethylene epoxidation on Ag(111), Pt(111), Rh(111) and Mo(100) has been studied by density functional theory (DFT) calculations. The results show that the adsorption energies of possible adsorbed species involved in the ethylene epoxidation increase in the order: Ag<Pt<Rh<Mo, and the activation energies of the formation of epoxide (EtO) and acetaldehyde (Ac) follow the same order. Moreover, it is found that the smallest difference in the activation energies between EtO formation and Ac formation is shown on Ag. These results indicate that the metallic Ag shows the highest between activity and selectivity for ethylene epoxidation among the studied metal surfaces. Perhaps, the stability of OMME intermediate is the crucial factor in controlling the activity and selectivity. And the stronger the binding of OMME, the lower the activity and selectivity are. In addition, the relationships between the reaction enthalpy and activation energy on these four metal surfaces are investigated,and it is found that such a correlation is only applied for OMME(a) → EtO(a) and OMME(a) → Ac(a), while invalid for the case of C2H4(a) +O(a) → OMME(a).

  2. Insights into phase transitions and entanglement from density functional theory

    Science.gov (United States)

    Wei, Bo-Bo

    2016-11-01

    Density functional theory (DFT) has met great success in solid state physics, quantum chemistry and in computational material sciences. In this work we show that DFT could shed light on phase transitions and entanglement at finite temperatures. Specifically, we show that the equilibrium state of an interacting quantum many-body system which is in thermal equilibrium with a heat bath at a fixed temperature is a universal functional of the first derivatives of the free energy with respect to temperature and other control parameters respectively. This insight from DFT enables us to express the average value of any physical observable and any entanglement measure as a universal functional of the first derivatives of the free energy with respect to temperature and other control parameters. Since phase transitions are marked by the nonanalytic behavior of free energy with respect to control parameters, the physical quantities and entanglement measures may present nonanalytic behavior at critical point inherited from their dependence on the first derivative of free energy. We use two solvable models to demonstrate these ideas. These results give new insights for phase transitions and provide new profound connections between entanglement and phase transitions in interacting quantum many-body physics.

  3. Density functional theory study of the structural, electronic and optical properties of C-doped anatase TiO{sub 2} (101) surface

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Dandan; Zhou, Wei; Liu, Yanyu; Zhou, Baozeng; Wu, Ping, E-mail: pingwu@tju.edu.cn

    2015-08-28

    The effects of electronic and local structures on the optical properties of C-doped anatase TiO{sub 2} (101) surface were investigated. When C is at Ti or interstitial site, a planar CO{sub 3} unit is observed and leads to the decrease of band gap. While for C substituted at O site, although it introduces impurity states, the intrinsic band gap does not change. Furthermore, the dipole moment is calculated to explore the effect of local crystal structure on the photocatalytic ability. The results show that the dipole moment can promote the separation of charge carriers and enhance the photocatalytic activity. - Highlights: • Optical properties of C-doped anatase TiO{sub 2} (101) surface were investigated. • The incorporation of C atom can lead to the red shift of absorption edge. • The case of C at O site performs the best ability of visible light absorption. • The dipole moment caused by distortion has effects on the optical properties.

  4. Path Integral Molecular Dynamics for Hydrogen with Orbital-Free Density Functional Theory

    Science.gov (United States)

    Runge, Keith; Karasiev, Valentin; Deymier, Pierre

    2014-03-01

    The computational bottleneck for performing path-integral molecular dynamics (PIMD) for nuclei on a first principles electronic potential energy surface has been the speed with which forces from the electrons can be generated. Recent advances in orbital-free density functional theory (OF-DFT) not only allow for faster generation of first principles forces but also include the effects of temperature on the electron density. We will present results of calculations on hydrogen in warm dense matter conditions where the protons are described by PIMD and the electrons by OF-DFT. Work supported by U.S. Dept. of Energy, grant DE-SC0002139.

  5. Density functional theory investigation of the electronic structure and thermoelectric properties of layered MoS{sub 2}, MoSe{sub 2} and their mixed-layer compound

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Changhoon; Hong, Jisook [Department of Chemistry, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Lee, Wang Ro [Faculty of Liberal Education, Chonbuk National University, Jeonju, Jeonbuk 561-756 (Korea, Republic of); Kim, Dae Yeon [Agency for Defense Development (ADD), Chinhae, Kyungnam 645-600 (Korea, Republic of); Shim, Ji Hoon, E-mail: jhshim@postech.ac.kr [Department of Chemistry, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of); Divisions of Advanced Nuclear Engineering, Pohang University of Science and Technology, Pohang 790-784 (Korea, Republic of)

    2014-03-15

    First principles density functional theory calculations were carried out for the 2H-MoQ{sub 2} (Q=S and Se) and their hypothetical mixed-layer compound. Due to the different electronegativities of S and Se atoms on MoQ{sub 2}, the band gap size could be adjusted in mixed-layer compound MoS{sub 2}/MoSe{sub 2}. Also, the indirect band gap in pure MoQ{sub 2} compounds is changed to the pseudo direct band gap in mixed-layer MoS{sub 2}/MoSe{sub 2} which is similar to the monolayer compound. The layer mixing enhances the thermoelectric properties because of the increased density of states around the Fermi level and the decreased band gap size. Therefore, we suggest that this layer mixing approach should be regarded as a useful way to modulate their electronic structures and to improve their thermoelectric properties. -- Graphical abstract: On the basis of density functional calculations we predict that the mixed-layer compounds 2H-MoS{sub 2}/2H-MoSe{sub 2}, in which two different layers 2H-MoS{sub 2} and 2H-MoSe{sub 2}, have enhanced thermoelectric properties because of the increased density of states around the Fermi level and the decreased band gap size. Highlights: • We explored a way of improving TE properties of 2H-MoQ{sub 2} on DFT methods. • The mixed-layer compounds MoS{sub 2}/MoSe{sub 2} have enhanced thermoelectric properties. • This is caused by modulated electronic structure of mixed layer compound. • Layer mixing approach should be regarded as a useful way to improve TE properties.

  6. The decay of excited He from Stochastic Density-Functional Theory: a quantum measurement theory interpretation

    OpenAIRE

    2007-01-01

    Recently, time-dependent current-density functional theory has been extended to include the dynamical interaction of quantum systems with external environments [Phys. Rev. Lett. {\\bf 98}, 226403 (2007)]. Here we show that such a theory allows us to study a fundamentally important class of phenomena previously inaccessible by standard density-functional methods: the decay of excited systems. As an example we study the decay of an ensemble of excited He atoms, and discuss these results in the c...

  7. Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

    Energy Technology Data Exchange (ETDEWEB)

    Ringholm, Magnus; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, 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); PDC Center for High Performance Computing, Royal Institute of Technology, S-10044 Stockholm (Sweden); Oggioni, Luca [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø – The Arctic University of Norway, 9037 Tromsø (Norway); Department of Physics G. Occhialini, University of Milano Bicocca, Piazza della scienza 3, 20126 Milan (Italy); Ekström, Ulf [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo (Norway)

    2014-10-07

    We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

  8. Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

    Science.gov (United States)

    Ringholm, Magnus; Bast, Radovan; Oggioni, Luca; Ekström, Ulf; Ruud, Kenneth

    2014-10-01

    We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

  9. Ultra-nonlocality in density functional theory for photo-emission spectroscopy.

    Science.gov (United States)

    Uimonen, A-M; Stefanucci, G; van Leeuwen, R

    2014-05-14

    We derive an exact expression for the photocurrent of photo-emission spectroscopy using time-dependent current density functional theory (TDCDFT). This expression is given as an integral over the Kohn-Sham spectral function renormalized by effective potentials that depend on the exchange-correlation kernel of current density functional theory. We analyze in detail the physical content of this expression by making a connection between the density-functional expression and the diagrammatic expansion of the photocurrent within many-body perturbation theory. We further demonstrate that the density functional expression does not provide us with information on the kinetic energy distribution of the photo-electrons. Such information can, in principle, be obtained from TDCDFT by exactly modeling the experiment in which the photocurrent is split into energy contributions by means of an external electromagnetic field outside the sample, as is done in standard detectors. We find, however, that this procedure produces very nonlocal correlations between the exchange-correlation fields in the sample and the detector.

  10. Informing saccharide structural NMR studies with density functional theory calculations.

    Science.gov (United States)

    Klepach, Thomas; Zhao, Hongqiu; Hu, Xiaosong; Zhang, Wenhui; Stenutz, Roland; Hadad, Matthew J; Carmichael, Ian; Serianni, Anthony S

    2015-01-01

    Density functional theory (DFT) is a powerful computational tool to enable structural interpretations of NMR spin-spin coupling constants ( J-couplings) in saccharides, including the abundant (1)H-(1)H ( JHH), (13)C-(1)H ( JCH), and (13)C-(13)C ( JCC) values that exist for coupling pathways comprised of 1-4 bonds. The multiple hydroxyl groups in saccharides, with their attendant lone-pair orbitals, exert significant effects on J-couplings that can be difficult to decipher and quantify without input from theory. Oxygen substituent effects are configurational and conformational in origin (e.g., axial/equatorial orientation of an OH group in an aldopyranosyl ring; C-O bond conformation involving an exocyclic OH group). DFT studies shed light on these effects, and if conducted properly, yield quantitative relationships between a specific J-coupling and one or more conformational elements in the target molecule. These relationships assist studies of saccharide structure and conformation in solution, which are often challenged by the presence of conformational averaging. Redundant J-couplings, defined as an ensemble of J-couplings sensitive to the same conformational element, are particularly helpful when the element is flexible in solution (i.e., samples multiple conformational states on the NMR time scale), provided that algorithms are available to convert redundant J-values into meaningful conformational models. If the latter conversion is achievable, the data can serve as a means of testing, validating, and refining theoretical methods like molecular dynamics (MD) simulations, which are currently relied upon heavily to assign conformational models of saccharides in solution despite a paucity of experimental data needed to independently validate the method.

  11. 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.

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

    Science.gov (United States)

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

    2016-06-09

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

  13. Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

    Science.gov (United States)

    Kong, Fanjie; Hu, Yanfei

    2014-03-01

    The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

  14. Nobel Prize in Chemistry 1998 "for his development of the density-functional theory" : Walter Kohn

    CERN Multimedia

    1999-01-01

    Prof. Walter Kohn presents "Electronic structure of matter : wave functions and density functionals".Since the 1920's Schroedinger wave functions have been the principal theoretical concept for understanding and computing the electronic structure of matter. More recently, Density Functional Theory (DFT), couched in terms of the electronic density distribution, n(r), has provided a new perspective and new computational possibilities, especially for systems consisting of very many (up to ~1000) atoms. In this talk some fundamental limitations of wave function methods for very-many-atom-systems will be discussed. The DFT approach will be explained together with some physical/chemical applications and a discussion of its strenghts and weaknesses. W Kohn has received the prize with J A Pople for his development of computational methods in quantum chemistr.

  15. Density functional theory based generalized effective fragment potential method

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Kiet A., E-mail: kiet.nguyen@wpafb.af.mil, E-mail: ruth.pachter@wpafb.af.mil [Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433 (United States); UES, Inc., Dayton, Ohio 45432 (United States); Pachter, Ruth, E-mail: kiet.nguyen@wpafb.af.mil, E-mail: ruth.pachter@wpafb.af.mil [Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433 (United States); Day, Paul N. [Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433 (United States); General Dynamics Information Technology, Inc., Dayton, Ohio 45431 (United States)

    2014-06-28

    We present a generalized Kohn-Sham (KS) density functional theory (DFT) based effective fragment potential (EFP2-DFT) method for the treatment of solvent effects. Similar to the original Hartree-Fock (HF) based potential with fitted parameters for water (EFP1) and the generalized HF based potential (EFP2-HF), EFP2-DFT includes electrostatic, exchange-repulsion, polarization, and dispersion potentials, which are generated for a chosen DFT functional for a given isolated molecule. The method does not have fitted parameters, except for implicit parameters within a chosen functional and the dispersion correction to the potential. The electrostatic potential is modeled with a multipolar expansion at each atomic center and bond midpoint using Stone's distributed multipolar analysis. The exchange-repulsion potential between two fragments is composed of the overlap and kinetic energy integrals and the nondiagonal KS matrices in the localized molecular orbital basis. The polarization potential is derived from the static molecular polarizability. The dispersion potential includes the intermolecular D3 dispersion correction of Grimme et al. [J. Chem. Phys. 132, 154104 (2010)]. The potential generated from the CAMB3LYP functional has mean unsigned errors (MUEs) with respect to results from coupled cluster singles, doubles, and perturbative triples with a complete basis set limit (CCSD(T)/CBS) extrapolation, of 1.7, 2.2, 2.0, and 0.5 kcal/mol, for the S22, water-benzene clusters, water clusters, and n-alkane dimers benchmark sets, respectively. The corresponding EFP2-HF errors for the respective benchmarks are 2.41, 3.1, 1.8, and 2.5 kcal/mol. Thus, the new EFP2-DFT-D3 method with the CAMB3LYP functional provides comparable or improved results at lower computational cost and, therefore, extends the range of applicability of EFP2 to larger system sizes.

  16. Transport through correlated systems with density functional theory

    Science.gov (United States)

    Kurth, S.; Stefanucci, G.

    2017-10-01

    We present recent advances in density functional theory (DFT) for applications in the field of quantum transport, with particular emphasis on transport through strongly correlated systems. We review the foundations of the popular Landauer–Büttiker(LB)  +  DFT approach. This formalism, when using approximations to the exchange-correlation (xc) potential with steps at integer occupation, correctly captures the Kondo plateau in the zero bias conductance at zero temperature but completely fails to capture the transition to the Coulomb blockade (CB) regime as the temperature increases. To overcome the limitations of LB  +  DFT, the quantum transport problem is treated from a time-dependent (TD) perspective using TDDFT, an exact framework to deal with nonequilibrium situations. The steady-state limit of TDDFT shows that in addition to an xc potential in the junction, there also exists an xc correction to the applied bias. Open shell molecules in the CB regime provide the most striking examples of the importance of the xc bias correction. Using the Anderson model as guidance we estimate these corrections in the limit of zero bias. For the general case we put forward a steady-state DFT which is based on one-to-one correspondence between the pair of basic variables, steady density on and steady current across the junction and the pair local potential on and bias across the junction. Like TDDFT, this framework also leads to both an xc potential in the junction and an xc correction to the bias. Unlike TDDFT, these potentials are independent of history. We highlight the universal features of both xc potential and xc bias corrections for junctions in the CB regime and provide an accurate parametrization for the Anderson model at arbitrary temperatures and interaction strengths, thus providing a unified DFT description for both Kondo and CB regimes and the transition between them.

  17. Density functional theory for field emission from carbon nano-structures.

    Science.gov (United States)

    Li, Zhibing

    2015-12-01

    Electron field emission is understood as a quantum mechanical many-body problem in which an electronic quasi-particle of the emitter is converted into an electron in vacuum. Fundamental concepts of field emission, such as the field enhancement factor, work-function, edge barrier and emission current density, will be investigated, using carbon nanotubes and graphene as examples. A multi-scale algorithm basing on density functional theory is introduced. We will argue that such a first principle approach is necessary and appropriate for field emission of nano-structures, not only for a more accurate quantitative description, but, more importantly, for deeper insight into field emission.

  18. Role of electronic correlation in high-low temperature phase transition of hexagonal nickel sulfide: a comparative density functional theory study with and without correction for on-site Coulomb interaction.

    Science.gov (United States)

    Zhang, Wei-Bing; Li, Jie; Tang, Bi-Yu

    2013-06-28

    The structural, electronic, magnetic, and elastic properties of hexagonal nickel sulfide (NiS) have been investigated comparatively by Density Functional theory (DFT) and DFT plus correction for on-site Coulomb interaction (DFT+U), in which two different exchange correlation functionals local density approximations (LDA) and general gradient approximations (GGA) in the form of Perdew-Burke-Ernzerhof (PBE) are used. Our results indicate LDA and PBE methods predict hexagonal NiS to be a paramagnetic metal whereas LDA(PBE)+U calculations with reasonable on-site Coulomb interaction energy give the antiferromagnetic insulating state of low temperature hexagonal NiS successfully. Meanwhile, compared with LDA(PBE) results, LDA(PBE)+U methods give larger lattice parameters, crystal volume, and shear constant c44, consistent with the experimental picture during high-low temperature phase transition of hexagonal NiS, in which an increase of the shear constant c44 and lattice parameters were found in the low-temperature antiferromagnetic phase. The present DFT and DFT+U calculations provide a reasonable description for the properties of high temperature and low temperature hexagonal NiS respectively, which indicates that electronic correlation is responsible for this high-low temperature phase transition.

  19. Effects of K doping on electronic structure of Ba{sub 1−x}K{sub x}Fe{sub 2}As{sub 2} superconductor by ab-initio density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Sandoghchi, M. [Advanced Materials Laboratory (AML), Department of Physics, Sharif University of Technology, P.O. Box 11365-9161, Tehran (Iran, Islamic Republic of); Khosroabadi, H., E-mail: khosroabadi@sharif.edu [Advanced Materials Laboratory (AML), Department of Physics, Sharif University of Technology, P.O. Box 11365-9161, Tehran (Iran, Islamic Republic of); Magnet Research Laboratory (MRL), Department of Physics, Sharif University of Technology, P.O. Box 11365-916, Tehran (Iran, Islamic Republic of); Akhavan, M. [Magnet Research Laboratory (MRL), Department of Physics, Sharif University of Technology, P.O. Box 11365-916, Tehran (Iran, Islamic Republic of)

    2014-12-15

    Highlights: • The lattice parameters changes by K doping is explained by ionic charge and the metal–metal bonding scenario. • Creation of a larger peak near the Fermi level and increase the DOS at the Fermi level by K doping. • The effects of K on DOS has been related to the magnetic transition, change of the lattice parameters and FeAs{sub 4} tetrahedron. • Investigation of the number of Fermi level crossed bands by K doping and the band changes near the Fermi level. - Abstract: The crystal and electronic structures of normal phase of Ba{sub 1−x}K{sub x}Fe{sub 2}As{sub 2} for x = 0.0, 0.5 and 1.0 have been studied by using pseudopotential Quantum Espresso code based on ab-initio density functional theory. Effects of K doping on the crystal structure and lattice parameters have been calculated and compared with the experimental and computational reported data for similar compounds. The metal–metal bonding scenario was used to explain the changes of lattice parameters by K doping. The electronic structure of this system including of density of states and band structure have been calculated and investigated by K doping. One of the interesting results is that a larger peak is appeared near the Fermi level by increasing of the K doping. These changes could produce a potential for creation of the superconducting state in this system.

  20. Ab initio study of the effect of pressure on the structural and electronic properties of cubic LaAlO{sub 3} by density function theory using GGA, LDA and PBEsol exchange correlation potentials

    Energy Technology Data Exchange (ETDEWEB)

    Benam, M.R., E-mail: m_benam@pnu.ac.ir [Department of Physics, Payame Noor University, P.O. BOX 19395-3697 (Iran, Islamic Republic of); Abdoshahi, N.; Majidiyan Sarmazdeh, M. [Department of Physics, Payame Noor University, P.O. BOX 19395-3697 (Iran, Islamic Republic of)

    2014-08-01

    In this paper the effect of pressure on the structural and electronic properties of cubic-LaAlO{sub 3} including the equilibrium lattice constant, bulk modulus, derivative of bulk modulus and band structure have been calculated by density functional theory (DFT) using GGA, LDA, and PBEsol exchange correlation potentials. It is found that the change of the lattice constant with pressure has an exponential behavior: with increasing pressure, the lattice constant decreases first sharply at low pressures, and then more slowly at high pressures. Furthermore, the lattice constant calculated by the PBEsol method and the bulk modulus calculated by LDA and PBEsol methods are closer to the available experimental values than those obtained using other exchange correlation potentials. Regarding the electronic properties, it is shown that an increase in pressure increases the band gap, the change being 0.26 eV at 34.00 GPa. The total density of state (t-DOS) calculations demonstrate that increasing pressure has a significant effect on the core and conduction band, but little effect on the valence band. The band structure calculations indicate that, in this material, the band gap changes from indirect to direct at a pressure of about 25 GPa. Also, increasing pressure produces a clear curvature in the band structure near the bottom of the conduction band, a behavior consistent with the strong pressure dependence of the transport properties.

  1. Ab initio study of the effect of pressure on the structural and electronic properties of cubic LaAlO3 by density function theory using GGA, LDA and PBEsol exchange correlation potentials

    Science.gov (United States)

    Benam, M. R.; Abdoshahi, N.; Majidiyan Sarmazdeh, M.

    2014-08-01

    In this paper the effect of pressure on the structural and electronic properties of cubic-LaAlO3 including the equilibrium lattice constant, bulk modulus, derivative of bulk modulus and band structure have been calculated by density functional theory (DFT) using GGA, LDA, and PBEsol exchange correlation potentials. It is found that the change of the lattice constant with pressure has an exponential behavior: with increasing pressure, the lattice constant decreases first sharply at low pressures, and then more slowly at high pressures. Furthermore, the lattice constant calculated by the PBEsol method and the bulk modulus calculated by LDA and PBEsol methods are closer to the available experimental values than those obtained using other exchange correlation potentials. Regarding the electronic properties, it is shown that an increase in pressure increases the band gap, the change being 0.26 eV at 34.00 GPa. The total density of state (t-DOS) calculations demonstrate that increasing pressure has a significant effect on the core and conduction band, but little effect on the valence band. The band structure calculations indicate that, in this material, the band gap changes from indirect to direct at a pressure of about 25 GPa. Also, increasing pressure produces a clear curvature in the band structure near the bottom of the conduction band, a behavior consistent with the strong pressure dependence of the transport properties.

  2. Structure and vibrations of glutathione studied by vibrational spectroscopy and density functional theory.

    Science.gov (United States)

    Singh, Gurpreet; Dogra, Sukh Dev; Kaur, Sarvpreet; Tripathi, S K; Prakash, Satya; Rai, Bimal; Saini, G S S

    2015-01-01

    The vibrational properties of glutathione have been investigated by infrared absorption and Raman spectroscopic techniques, and density functional theory calculations at the B3LYP/6-31+G(d,p) level. Assignments of all the experimentally observed vibrational bands have been done with the help of simulated vibrational spectra and potential energy distribution calculations of glutathione water cluster, which includes the effect of hydrogen bonding. Optimized molecular parameters of energy minimized structure have been compared with the available experimental values. Calculated molecular parameters of glutathione-water cluster match well with the experimental values. Some of the calculated molecular parameters and vibrational frequencies of vapor phase glutathione-water cluster suggest participation of some atoms of glutathione in hydrogen bonding. Experimentally observed UV-Visible absorption spectrum of glutathione has also been reported. Observed band at 203 nm has been assigned to electronic transitions calculated with time dependent density functional theory. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Density functional theory and beyond-opportunities for quantum methods in materials modeling semiconductor technology.

    Science.gov (United States)

    Shankar, Sadasivan; Simka, Harsono; Haverty, Michael

    2008-02-13

    In the semiconductor industry, the use of new materials has been increasing with the advent of nanotechnology. As critical dimensions decrease, and the number of materials increases, the interactions between heterogeneous materials themselves and processing increase in complexity. Traditionally, applications of ab initio techniques are confined to electronic structure and band gap calculations of bulk materials, which are then used in coarse-grained models such as mesoscopic and continuum models. Density functional theory is the most widely used ab initio technique that was successfully extended to several applications. This paper illustrates applications of density functional theory to semiconductor processes and proposes further opportunities for use of such techniques in process development.

  4. Stochastic Optimally-Tuned Ranged-Separated Hybrid Density Functional Theory

    CERN Document Server

    Neuhauser, Daniel; Cytter, Yael; Baer, Roi

    2015-01-01

    We develop a stochastic formulation of the optimally-tuned range-separated hybrid density functional theory which enables significant reduction of the computational effort and scaling of the non-local exchange operator at the price of introducing a controllable statistical error. Our method is based on stochastic representations of the Coulomb convolution integral and of the generalized Kohn-Sham density matrix. The computational cost of the approach is similar to that of usual Kohn-Sham density functional theory, yet it provides much more accurate description of the quasiparticle energies for the frontier orbitals. This is illustrated for a series of silicon nanocrystals up to sizes exceeding 3000 electrons. Comparison with the stochastic GW many-body perturbation technique indicates excellent agreement for the fundamental band gap energies, good agreement for the band-edge quasiparticle excitations, and very low statistical errors in the total energy for large systems. The present approach has a major advan...

  5. Density Functional Theory for General Hard-Core Lattice Gases

    Science.gov (United States)

    Lafuente, Luis; Cuesta, José A.

    2004-09-01

    We put forward a general procedure to obtain an approximate free-energy density functional for any hard-core lattice gas, regardless of the shape of the particles, the underlying lattice, or the dimension of the system. The procedure is conceptually very simple and recovers effortlessly previous results for some particular systems. Also, the obtained density functionals belong to the class of fundamental measure functionals and, therefore, are always consistent through dimensional reduction. We discuss possible extensions of this method to account for attractive lattice models.

  6. Density functional study for structure and electronic properties of FeS2 (100)

    Institute of Scientific and Technical Information of China (English)

    邱冠周; 肖奇; 胡岳华; 覃文庆

    2003-01-01

    The electronic properties of FeS2 (100) surface were studied by using a density-functional theory(DFT) method. The very stable (100) surface does not give any significant geometric relaxation and can be regarded as a simple termination of the bulk structure along a plane of cleaved Fe-S bonds. The electronic structure of FeS2 (100) surface is characterized by surface states in its forbidden zone. The highest occupied and the lowest unoccupied states localize at surface Fe sites. Fe sites are energetically favored over S2 sites for redox interaction with electron donor or acceptor species on (100) surface.

  7. Improving band gap prediction in density functional theory from molecules to solids.

    Science.gov (United States)

    Zheng, Xiao; Cohen, Aron J; Mori-Sánchez, Paula; Hu, Xiangqian; Yang, Weitao

    2011-07-08

    A novel nonempirical scaling correction method is developed to tackle the challenge of band gap prediction in density functional theory. For finite systems the scaling correction largely restores the straight-line behavior of electronic energy at fractional electron numbers. The scaling correction can be generally applied to a variety of mainstream density functional approximations, leading to significant improvement in the band gap prediction. In particular, the scaled version of a modified local density approximation predicts band gaps with an accuracy consistent for systems of all sizes, ranging from atoms and molecules to solids. The scaled modified local density approximation thus provides a useful tool to quantitatively characterize the size-dependent effect on the energy gaps of nanostructures.

  8. Density functional theory of the crystal field in dioxides

    Science.gov (United States)

    Diviš, M.; Kuriplach, J.; Richter, M.; Steinbeck, L.

    1996-04-01

    Presented are the results of ab-initio density functional calculations for PrO2 and UO2 using the general potential LAPW and optimized LCAO method in the local density approximation. The crystal field splitting of ionic Pr4+ and U4+ ground states was calculated and compared with predictions of a superposition model.

  9. Simulating Ru L 3 -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

    Energy Technology Data Exchange (ETDEWEB)

    Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

    2013-05-30

    Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.

  10. The decay of excited He from stochastic density-functional theory: a quantum measurement theory interpretation

    Energy Technology Data Exchange (ETDEWEB)

    Bushong, Neil; Di Ventra, Massimiliano [Department of Physics, University of California, San Diego, La Jolla, CA 92093-0319 (United States)], E-mail: diventra@physics.ucsd.edu

    2008-10-01

    Recently, time-dependent current-density-functional theory has been extended to include the dynamical interaction of quantum systems with external environments (Di Ventra and D'Agosta 2007 Phys. Rev. Lett. 98 226403). Here we show that such a theory allows us to study a fundamentally important class of phenomena previously inaccessible by standard density-functional methods: the decay of excited systems. As an example we study the decay of an ensemble of excited He atoms, and discuss these results in the context of quantum measurement theory.

  11. A density functional theory-based chemical potential equalisation approach to molecular polarizability

    Indian Academy of Sciences (India)

    Amita Wadehra; Swapan K Ghosh

    2005-09-01

    The electron density changes in molecular systems in the presence of external electric fields are modeled for simplicity in terms of the induced charges and dipole moments at the individual atomic sites. 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 illustrative numerical calculations are shown to predict the molecular polarizabilities in good agreement with available results. The usefulness of the approach to the calculation of intermolecular interaction needed for computer simulation is highlighted.

  12. Tuning Range-Separated Density Functional Theory for Photocatalytic Water Splitting Systems

    CERN Document Server

    Bokareva, Olga S; Bokarev, Sergey I; Kühn, Oliver

    2015-01-01

    We discuss the applicability of long-range separated density functional theory (DFT) to the prediction of electronic transitions of a particular photocatalytic system based on an Ir(III) photosensitizer (IrPS). Special attention is paid to the charge-transfer properties which are of key importance for the photoexcitation dynamics, but and cannot be correctly described by means of conventional DFT. The optimization of the range-separation parameter is discussed for IrPS including its complexes with electron donors and acceptors used in photocatalysis. Particular attention is paid to the problems arising for a description of medium effects by a polarizable continuum model.

  13. Density functional theory study on structures and electronic spectra of edge hydrogenated graphene sheets%边缘氢化石墨烯片层结构和光谱性质的密度泛函理论研究

    Institute of Scientific and Technical Information of China (English)

    冯艳萍; 田磊; 董玉慧

    2014-01-01

    以并3-6苯环为氢化石墨烯片层模型,采用量子化学密度泛函理论方法(DFT)在B3LYP/6-31G (d, p)水平上进行了几何结构全优化,讨论了分子结构、能量、前线分子轨道等性质的变化规律。在得到化合物基态稳定构型的基础上,运用含时密度泛函理论(TD-DFT)计算了电子吸收光谱的性质。计算结果显示边缘氢化石墨烯片层均为平面结构,线型扶手椅型结构能量最低,结构最稳定。随着石墨烯片层环数的增加HOMO轨道能量增加,LUMO轨道能量降低,能隙能量降低,最大吸收波长明显红移。%Theoretical studies on the edge hydrogenated graphene sheet models formed by combining 3-6 benzene rings were carried out by using the Density Functional Theory (DFT) at B3LYP/6-31G (d, p) level to obtain the optimized equilibrium structures. The molecular geometric structures, energies, frontier molecular orbitals were investigated in detail. On this basis, the electronic transition energy of the excited state was calculated by using Time-Dependent Density Functional Theory (TD-DFT). The calculation results indicated that the edge hydrogenated graphene sheets were planar, and the linear armchair structure was the most stable one. HOMO energy increased and LUMO energy decreased with the number of benzene rings increasing which leaded to the energy gap decreasing and the maximum absorption spectra red shifted significantly.

  14. Fragment-based treatment of delocalization and static correlation errors in density-functional theory.

    Science.gov (United States)

    Nafziger, Jonathan; Wasserman, Adam

    2015-12-21

    One of the most important open challenges in modern Kohn-Sham (KS) density-functional theory (DFT) is the correct treatment of systems involving fractional electron charges and spins. Approximate exchange-correlation functionals struggle with such systems, leading to pervasive delocalization and static correlation errors. We demonstrate how these errors, which plague density-functional calculations of bond-stretching processes, can be avoided by employing the alternative framework of partition density-functional theory (PDFT) even using the local density approximation for the fragments. Our method is illustrated with explicit calculations on simple systems exhibiting delocalization and static-correlation errors, stretched H2 (+), H2, He2 (+), Li2 (+), and Li2. In all these cases, our method leads to greatly improved dissociation-energy curves. The effective KS potential corresponding to our self-consistent solutions displays key features around the bond midpoint; these are known to be present in the exact KS potential, but are absent from most approximate KS potentials and are essential for the correct description of electron dynamics.

  15. The effects of different possible modes of uniaxial strain on the tunability of electronic and band structures in {MoS}_2 monolayer nanosheet via first-principles density functional theory

    Science.gov (United States)

    Dimple; Jena, Nityasagar; Behere, Shounak Dhananjay; De Sarkar, Abir

    2017-07-01

    Ab-initio density functional theory-based calculations have been performed on monolayer (ML) {MoS}_2 nanosheet to study the variation of its electronic properties with the application of uniaxial tensile and compressive strain along its two non-equivalent lattice directions, namely, the zig-zag and the arm-chair directions. Among all the strain types considered in this study, uniaxial tensile strain applied along the zig-zag direction is found to be the most efficacious, inducing a greater tunability in the band gap over a large energy range (from 1.689 to 0.772 eV corresponding to 0-9% of applied strain), followed by uniaxial tensile strain along arm-chair direction. In contrast, the ML- {MoS}_2 nanosheet is found to be less sensitive to the compressive strain applied uniaxially along both the arm-chair as well as zig-zag directions. Moreover, the charges on Mo and S atoms are not found to undergo considerable changes under the application of uniaxial strain, as the atomic motion along the other direction is free from any constraint.

  16. The effects of different possible modes of uniaxial strain on the tunability of electronic and band structures in $\\rm{MoS_2}$ monolayer nanosheet via first-principles density functional theory

    Indian Academy of Sciences (India)

    DIMPLE; NITYASAGAR JENA; SHOUNAK DHANANJAY BEHERE; ABIR DE SARKAR

    2017-07-01

    $\\it{Ab-initio}$ density functional theory-based calculations have been performed on monolayer (ML) $\\rm{MoS_2}$ nanosheet to study the variation of its electronic properties with the application of uniaxial tensile and compressive strain along its two non-equivalent lattice directions, namely, the zig-zag and the arm-chair directions. Among all the strain types considered in this study, uniaxial tensile strain applied along the zig-zag direction is found to be the most efficacious, inducing a greater tunability in the band gap over a large energy range (from 1.689 to 0.772 eV corresponding to 0–9% of applied strain), followed by uniaxial tensile strain along arm-chair direction. In contrast, the $\\rm{ML–MoS_2}$ nanosheet is found to be less sensitive to the compressive strain applied uniaxially along both the arm-chair as well as zig-zag directions.Moreover, the charges on Mo and S atoms are not found to undergo considerable changes under the application of uniaxial strain, as the atomic motion along the other direction is free from any constraint.

  17. Structural peculiarities of configurational isomers of 1-styrylpyrroles according to 1Н, 13С and 15N NMR spectroscopy and density functional theory calculations: electronic and steric hindrance for planar structure.

    Science.gov (United States)

    Afonin, Andrei V; Ushakov, Igor A; Pavlov, Dmitry V; Schmidt, Elena Yu; Dvorko, Marina Yu

    2013-06-01

    Comparative analysis of the (1)Н and (13)С NMR data for a series of the E and Z-1-styrylpyrroles, E and Z-1-(1-propenyl)pyrroles, 1-vinylpyrroles and styrene suggests that the conjugation between the unsaturated fragments in the former compounds is reduced. This is the result of the mutual influence of the donor p-π and π-π conjugation having opposite directions. According to the NMR data combined with the density functional theory calculations, the Z isomer of 1-styrylpyrrole has essentially a nonplanar structure because of the steric hindrance. However, the E isomer of 1-styrylpyrrole is also an out-of-plane structure despite the absence of a sterical barrier for the planar one. Deviation of the E isomer from the planar structure seems to be caused by an electronic hindrance produced by a mutual influence of the p-π and π-π conjugation. The structure of the E isomer of the 2-substituted 1-styrylpyrroles is similar to that of the 2-substituted 1-vinylpyrroles. The steric effects in the Z isomer of the 2-substituted 1-styrylpyrroles result in the large increase of the dihedral angle between planes of the pyrrole ring and double bond. Copyright © 2013 John Wiley & Sons, Ltd.

  18. Multiconfiguration Pair-Density Functional Theory Spectral Calculations Are Stable to Adding Diffuse Basis Functions.

    Science.gov (United States)

    Hoyer, Chad E; Gagliardi, Laura; Truhlar, Donald G

    2015-11-05

    Time-dependent Kohn-Sham density functional theory (TD-KS-DFT) is useful for calculating electronic excitation spectra of large systems, but the low-energy spectra are often complicated by artificially lowered higher-energy states. This affects even the lowest energy excited states. Here, by calculating the lowest energy spin-conserving excited state for atoms from H to K and for formaldehyde, we show that this problem does not occur in multiconfiguration pair-density functional theory (MC-PDFT). We use the tPBE on-top density functional, which is a translation of the PBE exchange-correlation functional. We compare to a robust multireference method, namely, complete active space second-order perturbation theory (CASPT2), and to TD-KS-DFT with two popular exchange-correlation functionals, PBE and PBE0. We find for atoms that the mean unsigned error (MUE) of MC-PDFT with the tPBE functional improves from 0.42 to 0.40 eV with a double set of diffuse functions, whereas the MUEs for PBE and PBE0 drastically increase from 0.74 to 2.49 eV and from 0.45 to 1.47 eV, respectively.

  19. C-C bond unsaturation degree in monosubstituted ferrocenes for molecular electronics investigated by a combined near-edge x-ray absorption fine structure, x-ray photoemission spectroscopy, and density functional theory approach

    Energy Technology Data Exchange (ETDEWEB)

    Boccia, A.; Lanzilotto, V.; Marrani, A. G.; Zanoni, R. [Dipartimento di Chimica, Universita degli Studi di Roma ' ' La Sapienza' ' , piazzale Aldo Moro 5, I-00185 Rome (Italy); Stranges, S. [Dipartimento di Chimica, Universita degli Studi di Roma ' ' La Sapienza' ' , piazzale Aldo Moro 5, I-00185 Rome (Italy); IOM-CNR, Laboratorio TASC, I-34149 Basovizza, Trieste (Italy); Alagia, M. [IOM-CNR, Laboratorio TASC, I-34149 Basovizza, Trieste (Italy); Fronzoni, G.; Decleva, P. [Dipartimento di Scienze Chimiche, Universita di Trieste, Via L. Giorgieri 1, I-34127 Trieste, Italy and IOM-CNR Democritos, Trieste (Italy)

    2012-04-07

    We present the results of an experimental and theoretical investigation of monosubstituted ethyl-, vinyl-, and ethynyl-ferrocene (EtFC, VFC, and EFC) free molecules, obtained by means of synchrotron-radiation based C 1s photoabsorption (NEXAFS) and photoemission (C 1s XPS) spectroscopies, and density functional theory (DFT) calculations. Such a combined study is aimed at elucidating the role played by the C-C bond unsaturation degree of the substituent on the electronic structure of the ferrocene derivatives. Such substituents are required for molecular chemical anchoring onto relevant surfaces when ferrocenes are used for molecular electronics hybrid devices. The high resolution C 1s NEXAFS spectra exhibit distinctive features that depend on the degree of unsaturation of the hydrocarbon substituent. The theoretical approach to consider the NEXAFS spectrum made of three parts allowed to disentangle the specific contribution of the substituent group to the experimental spectrum as a function of its unsaturation degree. C 1s IEs were derived from the experimental data analysis based on the DFT calculated IE values for the different carbon atoms of the substituent and cyclopentadienyl (Cp) rings. Distinctive trends of chemical shifts were observed for the substituent carbon atoms and the substituted atom of the Cp ring along the series of ferrocenes. The calculated IE pattern was rationalized in terms of initial and final state effects influencing the IE value, with special regard to the different mechanism of electron conjugation between the Cp ring and the substituent, namely the {sigma}/{pi} hyperconjugation in EtFC and the {pi}-conjugation in VFC and EFC.

  20. Density functional theory study on the molecular structure of loganin

    OpenAIRE

    Pandey, Anoop Kumar; Siddiqui, Shamoon Ahmad; Dwivedi, Apoorva; Raj, Kanwal; Misra, Neeraj

    2011-01-01

    The computational Quantum Chemistry (QC) has been used for different types of problems, for example: structural biology, surface phenomena and liquid phase. In this paper we have employed the density functional method for the study of molecular structure of loganin. The equilibrium geometry, harmonic vibrational frequencies and infrared intensities were calculated by B3LYP/6-311G (d, p) method and basis set combinations. It was found that the optimized parameters obtained by the DFT/B3LYP met...

  1. Efficient classical density-functional theories of rigid-molecular fluids and a simplified free energy functional for liquid water

    CERN Document Server

    Sundararaman, Ravishankar

    2014-01-01

    Classical density-functional theory provides an efficient alternative to molecular dynamics simulations for understanding the equilibrium properties of inhomogeneous fluids. However, application of density-functional theory to multi-site molecular fluids has so far been limited by complications due to the implicit molecular geometry constraints on the site densities, whose resolution typically requires expensive Monte Carlo methods. Here, we present a general scheme of circumventing this so-called inversion problem: compressed representations of the orientation density. This approach allows us to combine the superior iterative convergence properties of multipole representations of the fluid configuration with the improved accuracy of site-density functionals. Next, from a computational perspective, we show how to extend the DFT++ algebraic formulation of electronic density-functional theory to the classical fluid case and present a basis-independent discretization of our formulation for molecular classical de...

  2. Molecular dynamics, density functional theory of the metal--electrolyte interface

    Energy Technology Data Exchange (ETDEWEB)

    Price, D.L. [Department of Physics, University of Memphis, Memphis Tennessee 38152 (United States); Halley, J.W. [School of Physics and Astronomy, University of Minnesota, Minneapolis, Minnesota 55455 (United States)

    1995-04-22

    Quantitative, predictive theories for metal--electrolyte interfaces require an atomic-scale representation of the interface, which must include an accurate statistical description of a polar fluid in contact with a solid surface; and also a description of the electronic density and structure of a metal surface in contact with a fluid. Such a complex system presents a difficult computational problem, and has been dealt with in the past essentially by parts; either by molecular dynamics calculations of the fluid structure, or density functional calculations of the metal--surface electronic structure. A complete and self-consistent determination of the surface structure would, however, involve a simultaneous calculation of both the atomic and electronic structure of the interface. This suggests a combination of these two calculational techniques, and it is just this sort of molecular dynamics and density functional combination which comprises the Car--Parrinello, and related, methods. We have developed a Car--Parrinello type combination of molecular dynamics and density functional methods, suitable for application to the metal--electrolyte interface. We briefly describe this calculation and discuss our initial results for a fairly simple metal--water interface.

  3. Optoelectronic Properties of Carbon Nanorings: Excitonic Effects from Time-Dependent Density Functional Theory

    CERN Document Server

    Wong, Bryan M

    2009-01-01

    The electronic structure and size-scaling of optoelectronic properties in cycloparaphenylene carbon nanorings are investigated using time-dependent density functional theory (TDDFT). The TDDFT calculations on these molecular nanostructures indicate that the lowest excitation energy surprisingly becomes larger as the carbon nanoring size is increased, in contradiction with typical quantum confinement effects. In order to understand their unusual electronic properties, I performed an extensive investigation of excitonic effects by analyzing electron-hole transition density matrices and exciton binding energies as a function of size in these nanoring systems. The transition density matrices allow a global view of electronic coherence during an electronic excitation, and the exciton binding energies give a quantitative measure of electron-hole interaction energies in the nanorings. Based on overall trends in exciton binding energies and their spatial delocalization, I find that excitonic effects play a vital role...

  4. Electronic and optical properties of the narrowest armchair graphene nanoribbons studied by density functional methods

    CERN Document Server

    Yeh, Chia-Nan; Chai, Jeng-Da

    2016-01-01

    In the present study, a series of planar poly(p-phenylene) (PPP) oligomers with n phenyl rings (n = 1 - 20), designated as n-PP, are taken as finite-size models of the narrowest armchair graphene nanoribbons with hydrogen passivation. The singlet-triplet energy gap, vertical ionization potential, vertical electron affinity, fundamental gap, optical gap, and exciton binding energy of n-PP are calculated using Kohn-Sham density functional theory and time-dependent density functional theory with various exchange-correlation density functionals. The ground state of n-PP is shown to be singlet for all the chain lengths studied. In contrast to the lowest singlet state (i.e., the ground state), the lowest triplet state and the ground states of the cation and anion of n-PP are found to exhibit some multi-reference character. Overall, the electronic and optical properties of n-PP obtained from the omegaB97 and omegaB97X functionals are in excellent agreement with the available experimental data.

  5. Verdict: Time-Dependent Density Functional Theory "Not Guilty" of Large Errors for Cyanines.

    Science.gov (United States)

    Jacquemin, Denis; Zhao, Yan; Valero, Rosendo; Adamo, Carlo; Ciofini, Ilaria; Truhlar, Donald G

    2012-04-10

    We assess the accuracy of eight Minnesota density functionals (M05 through M08-SO) and two others (PBE and PBE0) for the prediction of electronic excitation energies of a family of four cyanine dyes. We find that time-dependent density functional theory (TDDFT) with the five most recent of these functionals (from M06-HF through M08-SO) is able to predict excitation energies for cyanine dyes within 0.10-0.36 eV accuracy with respect to the most accurate available Quantum Monte Carlo calculations, providing a comparable accuracy to the latest generation of CASPT2 calculations, which have errors of 0.16-0.34 eV. Therefore previous conclusions that TDDFT cannot treat cyanine dyes reasonably accurately must be revised.

  6. Atomic volumes and polarizabilities in density-functional theory.

    Science.gov (United States)

    Kannemann, Felix O; Becke, Axel D

    2012-01-21

    Becke and Johnson introduced an ad hoc definition of atomic volume [J. Chem. Phys. 124, 014204 (2006)] in order to obtain atom-in-molecule polarizabilities from free-atom polarizabilities in their nonempirical exchange-hole dipole moment model of dispersion interactions. Here we explore the dependence of Becke-Johnson atomic volumes on basis sets and density-functional approximations and provide reference data for all atoms H-Lr. A persuasive theoretical foundation for the Becke-Johnson definition is also provided.

  7. Thermodynamic prediction of glass formation tendency, cluster-in-jellium model for metallic glasses, ab initio tight-binding calculations, and new density functional theory development for systems with strong electron correlation

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yongxin [Iowa State Univ., Ames, IA (United States)

    2009-01-01

    also plays an important role, as it may directly track the movement of every atom. Simulation time is a major limit for molecular dynamics, not only because of “slow” computer speed, but also because of the accumulation error in the numerical treatment of the motion equations. There is also a great concern about the reliability of the emperical potentials if using classical molecular dynamics. Ab initio methods based on density functional theory(DFT) do not have this problem, however, it suffers from small simulation cells and is more demanding computationally. When crystal phase is involved, size effect of the simulation cell is more pronounced since long-range elastic energy would be established. Simulation methods which are more efficient in computation but yet have similar reliability as the ab initio methods, like tight-binding method, are highly desirable. While the complexity of metallic glasses comes from the atomistic level, there is also a large field which deals with the complexity from electronic level. The only “ab initio” method applicable to solid state systems is density functional theory with local density approximation( LDA) or generalized gradient approximation(GGA) for the exchange-correlation energy. It is very successful for simple sp element, where it reaches an high accuracy for determining the surface reconstruction. However, there is a large class of materials with strong electron correlation, where DFT based on LDA or GGA fails in a fundamental way. An “ab initio” method which can generally apply to correlated materials, as LDA for simple sp element, is still to be developed. The thesis is prepared to address some of the above problems.

  8. Insight into Structural Phase Transitions from Density Functional Theory

    Science.gov (United States)

    Ruzsinszky, Adrienn

    2014-03-01

    Structural phase transitions caused by high pressure or temperature are very relevant in materials science. The high pressure transitions are essential to understand the interior of planets. Pressure or temperature induced phase transitions can be relevant to understand other phase transitions in strongly correlated systems or molecular crystals.Phase transitions are important also from the aspect of method development. Lower level density functionals, LSDA and GGAs all fail to predict the lattice parameters of different polymorphs and the phase transition parameters at the same time. At this time only nonlocal density functionals like HSE and RPA have been proved to resolve the geometry-energy dilemma to some extent in structural phase transitions. In this talk I will report new results from the MGGA_MS family of meta-GGAs and give an insight why this type of meta-GGAs can give a systematic improvement of the geometry and phase transition parameters together. I will also present results from the RPA and show a possible way to improve beyond RPA.

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

    Science.gov (United States)

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

    2014-07-14

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

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

    Science.gov (United States)

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

    2014-07-01

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

  11. Ferromagnetism in GaN: Gd: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Stevenson, Cynthia; Stevenson, Cynthia

    2008-02-04

    First principle calculations of the electronic structure and magnetic interaction of GaN:Gd have been performed within the Generalized Gradient Approximation (GGA) of the density functional theory (DFT) with the on-site Coulomb energy U taken into account (also referred to as GGA+U). The ferromagnetic p-d coupling is found to be over two orders of magnitude larger than the s-d exchange coupling. The experimental colossal magnetic moments and room temperature ferromagnetism in GaN:Gd reported recently are explained by the interaction of Gd 4f spins via p-d coupling involving holes introduced by intrinsic defects such as Ga vacancies.

  12. 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.

  13. 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.

  14. Ab-initio density functional theory study of a WO3 NH3-sensing mechanism

    Institute of Scientific and Technical Information of China (English)

    Hu Ming; Zhang Jie; Wang Wei-Dan; Qin Yu-Xiang

    2011-01-01

    WO3 bulk and various surfaces are studied by an ab-initio density functional theory technique.The band structures and electronic density states of WO3 bulk are investigated.The surface energies of different WO3 surfaces are compared and then the(002)surface with minimum energy is computed for its NH3 sensing mechanism which explains the results in the experiments.Three adsorption sites are considered.According to the comparisons of the energy and the charge change between before and after adsorption in the optimal adsorption site O1c,the NH3 sensing mechanism is obtained.

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

    Directory of Open Access Journals (Sweden)

    Luis R. Domingo

    2016-06-01

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

  16. Density functional theory optimized basis sets for gradient corrected functionals: 3d transition metal systems.

    Science.gov (United States)

    Calaminici, Patrizia; Janetzko, Florian; Köster, Andreas M; Mejia-Olvera, Roberto; Zuniga-Gutierrez, Bernardo

    2007-01-28

    Density functional theory optimized basis sets for gradient corrected functionals for 3d transition metal atoms are presented. Double zeta valence polarization and triple zeta valence polarization basis sets are optimized with the PW86 functional. The performance of the newly optimized basis sets is tested in atomic and molecular calculations. Excitation energies of 3d transition metal atoms, as well as electronic configurations, structural parameters, dissociation energies, and harmonic vibrational frequencies of a large number of molecules containing 3d transition metal elements, are presented. The obtained results are compared with available experimental data as well as with other theoretical data from the literature.

  17. Robust acceleration of self consistent field calculations for density functional theory.

    Science.gov (United States)

    Baarman, K; Eirola, T; Havu, V

    2011-04-07

    We show that the type 2 Broyden secant method is a robust general purpose mixer for self consistent field problems in density functional theory. The Broyden method gives reliable convergence for a large class of problems and parameter choices. We directly mix the approximation of the electronic density to provide a basis independent mixing scheme. In particular, we show that a single set of parameters can be chosen that give good results for a large range of problems. We also introduce a spin transformation to simplify treatment of spin polarized problems. The spin transformation allows us to treat these systems with the same formalism as regular fixed point iterations.

  18. Nuclear reactivity indices in the context of spin polarized density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Cardenas, Carlos [Departamento de Quimica, Facultad de Ecologia y Recursos Naturales, Universidad Andres Bello, Republica 275, Santiago (Chile)], E-mail: car.cardenas@uandresbello.edu; Lamsabhi, Al Mokhtar [Departamento de Quimica C-9, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco, E-28049 Madrid (Spain); Fuentealba, Patricio [Departamento de Fisica, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago (Chile)

    2006-03-20

    In this work, the nuclear reactivity indices of density functional theory have been generalized to the spin polarized case and their relationship to electron spin polarized indices has been established. In particular, the spin polarized version of the nuclear Fukui function has been proposed and a finite difference approximation has been used to evaluate it. Applications to a series of triatomic molecules demonstrate the ability of the new functions to predict the geometrical changes due to a change in the spin multiplicity. The main equations in the different ensembles have also been presented.

  19. Study of spontaneous fission lifetimes using nuclear density functional theory

    Directory of Open Access Journals (Sweden)

    Sadhukhan Jhilam

    2013-12-01

    Full Text Available The spontaneous fission lifetimes have been studied microscopically by minimizing the collective action integral in a two-dimensional collective space of quadrupole moments (Q20, Q22 representing elongation and triaxiality. The microscopic collective potential and inertia tensor are obtained by solving the self-consistent Hartree-Fock-Bogoliubov (HFB equations with the Skyrme energy density functional and mixed pairing interaction. The mass tensor is computed within the perturbative Adiabatic Time-Dependent HFB (ATDHFB approach in the cranking approximation. The dynamic fission trajectories have been obtained by minimizing the collective action using two different numerical techniques. The values of spontaneous fission lifetimes obtained in this way are compared with the static results.

  20. Pairing Nambu-Goldstone modes within nuclear density functional theory

    CERN Document Server

    Hinohara, Nobuo

    2016-01-01

    We show that the Nambu-Goldstone formalism of the broken gauge symmetry in the presence of the $T=1$ pairing condensate offers a quantitative description of the binding energy differences of open-shell superfluid nuclei. We conclude that the pairing rotational moments of inertia are excellent pairing indicators, which are free from ambiguities attributed to odd-mass systems. We offer a new, unified interpretation of the binding-energy differences traditionally viewed in the shell model picture as signatures of the valence nucleon properties. We present the first systematic analysis of the off-diagonal pairing rotational moments of inertia, and demonstrate the mixing of the neutron and proton pairing rotational modes in the ground states of even-even nuclei. Finally, we discuss the importance of mass measurements of neutron-rich nuclei for constraining the pairing energy density functional.

  1. Density Functional Theory of Polymer Structure and Conformations

    Directory of Open Access Journals (Sweden)

    Zhaoyang Wei

    2016-04-01

    Full Text Available We present a density functional approach to quantitatively evaluate the microscopic conformations of polymer chains with consideration of the effects of chain stiffness, polymer concentration, and short chain molecules. For polystyrene (PS, poly(ethylene oxide (PEO, and poly(methyl methacrylate (PMMA melts with low-polymerization degree, as chain length increases, they display different stretching ratios and show non-universal scaling exponents due to their different chain stiffnesses. In good solvent, increase of PS concentration induces the decline of gyration radius. For PS blends containing short (m1 = 1 − 100 and long (m = 100 chains, the expansion of long chains becomes unobvious once m 1 is larger than 40, which is also different to the scaling properties of ideal chain blends.

  2. Double-hybrid density-functional theory made rigorous

    CERN Document Server

    Sharkas, Kamal; Savin, Andreas

    2010-01-01

    We provide a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order Moller-Plesset correlation with a semilocal exchange-correlation density functional. These double-hybrid approximations contain only one empirical parameter and use a density-scaled correlation energy functional. Neglecting density scaling leads to an one-parameter version of the standard double-hybrid approximations. We assess the performance of these double-hybrid schemes on representative test sets of atomization energies and reaction barrier heights, and we compare to other hybrid approximations, including range-separated hybrids. Our best one-parameter double-hybrid approximation, called 1DH-BLYP, roughly reproduces the two parameters of the standard B2-PLYP or B2GP-PLYP double-hybrid approximations, which shows that these methods are not only empirically close to an optimum for general chemical applications but are also theoretically supported.

  3. The effect of oxide shell thickness on the structural, electronic, and optical properties of Si-SiO2 core-shell nano-crystals: A (time dependent)density functional theory study

    Science.gov (United States)

    Nazemi, Sanaz; Pourfath, Mahdi; Soleimani, Ebrahim Asl; Kosina, Hans

    2016-04-01

    Due to their tunable properties, silicon nano-crystals (NC) are currently being investigated. Quantum confinement can generally be employed for size-dependent band-gap tuning at dimensions smaller than the Bohr radius (˜5 nm for silicon). At the nano-meter scale, however, increased surface-to-volume ratio makes the surface effects dominant. Specifically, in Si-SiO2 core-shell semiconductor NCs the interfacial transition layer causes peculiar electronic and optical properties, because of the co-existence of intermediate oxidation states of silicon (Sin+, n = 0-4). Due to the presence of the many factors involved, a comprehensive understanding of the optical properties of these NCs has not yet been achieved. In this work, Si-SiO2 NCs with a diameter of 1.1 nm and covered by amorphous oxide shells with thicknesses between 2.5 and 4.75 Å are comprehensively studied, employing density functional theory calculations. It is shown that with increased oxide shell thickness, the low-energy part of the optical transition spectrum of the NC is red shifted and attenuated. Moreover, the absorption coefficient is increased in the high-energy part of the spectrum which corresponds to SiO2 transitions. Structural examinations indicate a larger compressive stress on the central silicon cluster with a thicker oxide shell. Examination of the local density of states reveals the migration of frontier molecular orbitals from the oxide shell into the silicon core with the increase of silica shell thickness. The optical and electrical properties are explained through the analysis of the density of states and the spatial distribution of silicon sub-oxide species.

  4. Local and linear chemical reactivity response functions at finite temperature in density functional theory.

    Science.gov (United States)

    Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2015-12-28

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

  5. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Franco-Pérez, Marco, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340 (Mexico); Ayers, Paul W., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Gázquez, José L., E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México, D.F. 09340 (Mexico); Vela, Alberto, E-mail: francopj@mcmaster.ca, E-mail: ayers@mcmaster.ca, E-mail: jlgm@xanum.uam.mx, E-mail: avela@cinvestav.mx [Departamento de Química, Centro de Investigación y de Estudios Avanzados (Cinvestav), Av. Instituto Politécnico Nacional 2508, México, D.F. 07360 (Mexico)

    2015-12-28

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

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

    Science.gov (United States)

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

    2011-04-14

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

  7. 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.

  8. 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.

  9. A posteriori error estimator for adaptive local basis functions to solve Kohn-Sham density functional theory

    CERN Document Server

    Kaye, Jason; Yang, Chao

    2014-01-01

    Kohn-Sham density functional theory is one of the most widely used electronic structure theories. The recently developed adaptive local basis functions form an accurate and systematically improvable basis set for solving Kohn-Sham density functional theory using discontinuous Galerkin methods, requiring a small number of basis functions per atom. In this paper we develop residual-based a posteriori error estimates for the adaptive local basis approach, which can be used to guide non-uniform basis refinement for highly inhomogeneous systems such as surfaces and large molecules. The adaptive local basis functions are non-polynomial basis functions, and standard a posteriori error estimates for $hp$-refinement using polynomial basis functions do not directly apply. We generalize the error estimates for $hp$-refinement to non-polynomial basis functions. We demonstrate the practical use of the a posteriori error estimator in performing three-dimensional Kohn-Sham density functional theory calculations for quasi-2D...

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

    Science.gov (United States)

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

    2017-01-17

    The electronic energy of a system provides the Born-Oppenheimer potential energy for internuclear motion and thus determines molecular structure and spectra, bond energies, conformational energies, reaction barrier heights, and vibrational frequencies. The development of more efficient and more accurate ways to calculate the electronic energy of systems with inherently multiconfigurational electronic structure is essential for many applications, including transition metal and actinide chemistry, systems with partially broken bonds, many transition states, and most electronically excited states. Inherently multiconfigurational systems are called strongly correlated systems or multireference systems, where the latter name refers to the need for using more than one ("multiple") configuration state function to provide a good zero-order reference wave function. This Account describes multiconfiguration pair-density functional theory (MC-PDFT), which was developed as a way to combine the advantages of wave function theory (WFT) and density functional theory (DFT) to provide a better treatment of strongly correlated systems. First we review background material: the widely used Kohn-Sham DFT (which uses only a single Slater determinant as reference wave function), multiconfiguration WFT methods that treat inherently multiconfigurational systems based on an active space, and previous attempts to combine multiconfiguration WFT with DFT. Then we review the formulation of MC-PDFT. It is a generalization of Kohn-Sham DFT in that the electron kinetic energy and classical electrostatic energy are calculated from a reference wave function, while the rest of the energy is obtained from a density functional. However, there are two main differences with respent to Kohn-Sham DFT: (i) The reference wave function is multiconfigurational rather than being a single Slater determinant. (ii) The density functional is a function of the total density and the on-top pair density rather than

  11. Antisites in III-V semiconductors: Density functional theory calculations

    KAUST Repository

    Chroneos, A.

    2014-07-14

    Density functional based simulation, corrected for finite size effects, is used to investigate systematically the formation of antisite defects in III-V semiconductors (III=Al, Ga, and In and V=P, As, and Sb). Different charge states are modelled as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites (III V q) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites (V I I I q) show a consistent decrease in formation energies with increase in group III and group V covalent radii. In general, III V q defects dominate under III-rich conditions and V I I I q under V-rich conditions. Comparison with equivalent vacancy formation energy simulations shows that while antisite concentrations are always dominant under stoichiometric conditions, modest variation in growth or doping conditions can lead to a significantly higher concentration of vacancies. © 2014 AIP Publishing LLC.

  12. Antisites in III-V semiconductors: Density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Chroneos, A., E-mail: alex.chroneos@open.ac.uk [Engineering and Innovation, The Open University, Milton Keynes MK7 6AA (United Kingdom); Tahini, H. A. [Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom); PSE Division, KAUST, Thuwal 23955-6900 (Saudi Arabia); Schwingenschlögl, U., E-mail: udo.schwingenschlogl@kaust.edu.sa [PSE Division, KAUST, Thuwal 23955-6900 (Saudi Arabia); Grimes, R. W., E-mail: r.grimes@imperial.ac.uk [Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom)

    2014-07-14

    Density functional based simulation, corrected for finite size effects, is used to investigate systematically the formation of antisite defects in III-V semiconductors (III = Al, Ga, and In and V = P, As, and Sb). Different charge states are modelled as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites (III{sub V}{sup q}) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites (V{sub III}{sup q}) show a consistent decrease in formation energies with increase in group III and group V covalent radii. In general, III{sub V}{sup q} defects dominate under III-rich conditions and V{sub III}{sup q} under V-rich conditions. Comparison with equivalent vacancy formation energy simulations shows that while antisite concentrations are always dominant under stoichiometric conditions, modest variation in growth or doping conditions can lead to a significantly higher concentration of vacancies.

  13. Theory of optical excitation and relaxation phenomena at semiconductor surfaces: linking density functional and density matrix theory

    Energy Technology Data Exchange (ETDEWEB)

    Buecking, N. [Technische Universitaet Berlin, Institut fuer Theoretische Physik, Nichtlineare Optik und Quantenelektronik, Berlin (Germany); Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany); Scheffler, M. [Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany); Kratzer, P. [Universitaet Duisburg-Essen, Fachbereich Physik - Theoretische Physik, Duisburg (Germany); Knorr, A. [Technische Universitaet Berlin, Institut fuer Theoretische Physik, Nichtlineare Optik und Quantenelektronik, Berlin (Germany)

    2007-08-15

    A theory for the description of optical excitation and the subsequent phonon-induced relaxation dynamics of nonequilibrium electrons at semiconductor surfaces is presented. In the first part, the fundamental dynamical equations for electronic occupations and polarisations are derived using density matrix formalism (DMT) for a surface-bulk system including the interaction of electrons with the optical field and electron-phonon interactions. The matrix elements entering these equations are either determined empirically or by density functional theory (DFT) calculations. In the subsequent parts of the paper, the dynamics at two specific semiconductor surfaces are discussed in detail. The electron relaxation dynamics underlying a time-resolved two photon photoemission experiment at an InP surface is investigated in the limit of a parabolic four band model. Moreover, the electron relaxation dynamics at a Si(100) surface is analysed. Here, the coupling parameters and the band structure are obtained from an DFT calculations. (orig.)

  14. Electronic Absorption Spectra of Neutral Perylene (C20H12), Terrylene (C30H16), and Quaterrylene (C40H20) and their Positive and Negative Ions: Ne Matrix-Isolation Spectroscopy and Time Dependent Density Functional Theory Calculations

    Science.gov (United States)

    Halasinski, Thomas M.; Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Head-Gordon, Martin; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.

  15. Non-perturbative calculation of molecular magnetic properties within current-density functional theory.

    Science.gov (United States)

    Tellgren, E I; Teale, A M; Furness, J W; Lange, K K; Ekström, U; Helgaker, T

    2014-01-21

    We present a novel implementation of Kohn-Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic fields are treated non-perturbatively, which enable the study of both magnetic response properties and the effects of strong fields, using either standard density functionals or current-density functionals-the implementation is the first fully self-consistent implementation of the latter for molecules. Pilot applications are presented for the finite-field calculation of molecular magnetizabilities, hypermagnetizabilities, and nuclear magnetic resonance shielding constants, focusing on the impact of current-density functionals on the accuracy of the results. Existing current-density functionals based on the gauge-invariant vorticity are tested and found to be sensitive to numerical details of their implementation. Furthermore, when appropriately regularized, the resulting magnetic properties show no improvement over standard density-functional results. An advantage of the present implementation is the ability to apply density-functional theory to molecules in very strong magnetic fields, where the perturbative approach breaks down. Comparison with high accuracy full-configuration-interaction results show that the inadequacies of current-density approximations are exacerbated with increasing magnetic field strength. Standard density-functionals remain well behaved but fail to deliver high accuracy. The need for improved current-dependent density-functionals, and how they may be tested using the presented implementation, is discussed in light of our findings.

  16. Time-dependent quantum fluid density functional theory of hydrogen molecule under intense laser fields

    Indian Academy of Sciences (India)

    Amita Wadehra; B M Deb

    2007-09-01

    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 the femtosecond dynamics of the electron density in the hydrogen molecule interacting with high-intensity laser fields. For this purpose, the GNLSE is solved numerically for many time-steps over a total interaction time of 100 fs, by employing a finite-difference scheme. Various time-dependent (TD) quantities, namely, electron density, ground-state survival probability and dipole moment have been obtained for two laser wavelengths and four different intensities. The high-order harmonics generation (HHG) is also examined. The present approach goes beyond the linear response formalism and, in principle, calculates the TD electron density to all orders of change.

  17. Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

    Energy Technology Data Exchange (ETDEWEB)

    Moradian, Rostam [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Science and Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Computational Physical Science Research Laboratory, Department of Nano Science, Institute for Studies in Theoretical Physics and Mathematics (IPM), PO Box 19395-5531, Tehran (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)

    2009-06-15

    We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

  18. Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, DaDi [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zheng, Xiao, E-mail: xz58@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Li, Chen [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Yang, Weitao, E-mail: weitao.yang@duke.edu [Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States); Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China)

    2015-04-21

    We explore effects of orbital relaxation on Kohn–Sham frontier orbital energies in density functional theory by using a nonempirical scaling correction approach developed in Zheng et al. [J. Chem. Phys. 138, 174105 (2013)]. Relaxation of Kohn–Sham orbitals upon addition/removal of a fractional number of electrons to/from a finite system is determined by a systematic perturbative treatment. The information of orbital relaxation is then used to improve the accuracy of predicted Kohn–Sham frontier orbital energies by Hartree–Fock, local density approximation, and generalized gradient approximation methods. The results clearly highlight the significance of capturing the orbital relaxation effects. Moreover, the proposed scaling correction approach provides a useful way of computing derivative gaps and Fukui quantities of N-electron finite systems (N is an integer), without the need to perform self-consistent-field calculations for (N ± 1)-electron systems.

  19. Polymorphs of 4-isopropylbenzylidine thiophene-2-carbohydrazide: Crystal growth and density functional theory computations

    Science.gov (United States)

    Rajavel, A.; Aditya Prasad, A.; Jeyakumar, T.

    2017-02-01

    The structural features of conformational isomerism in 4-isopropylbenzylidine thiophene-2-carbohydrazide (ITC) polymorphs have been investigated to conquer distinguishable strong Nsbnd H⋯O and weak Csbnd H⋯S hydrogen bond interactions. The single crystals were grown at constant temperature and have characterized by density functional theory computations using B3LYP method by 3-21G basis set. The conformational isomers of ITC were compared and spectroscopically characterized by FT-IR and Raman spectroscopy. The bulk phases were studied by the powder X-ray diffraction patterns. External morphology of ITC was discussed using scanning electron microscopic and transmission electron microscopic studies. Comparisons between various types of intermolecular interactions in the two polymorphic forms have been quantified via Fingerprint and Hirshfeld surface analysis. DFT computations were used to illustrate molecular electrostatic potential, HOMO-LUMO, mulliken atomic charges and electron density of states.

  20. Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

    Science.gov (United States)

    Brorsen, Kurt R; Yang, Yang; Pak, Michael V; Hammes-Schiffer, Sharon

    2017-05-04

    The development of approximate exchange-correlation functionals is critical for modern density functional theory. A recent analysis of atomic systems suggested that some modern functionals are straying from the path toward the exact functional because electron densities are becoming less accurate while energies are becoming more accurate since the year 2000. To investigate this trend for more chemically relevant systems, the electron densities in the bonding regions and the atomization energies are analyzed for a series of diatomic molecules with 90 different functionals. For hybrid generalized gradient approximation functionals developed since the year 2000, the errors in densities and atomization energies are decoupled; the accuracy of the energies remains relatively consistent while the accuracy of the densities varies significantly. Such decoupling is not observed for generalized gradient and meta-generalized gradient approximation functionals. Analysis of electron densities in bonding regions is found to be important for the evaluation of functionals for chemical systems.

  1. Density functional theory is straying from the path toward the exact functional.

    Science.gov (United States)

    Medvedev, Michael G; Bushmarinov, Ivan S; Sun, Jianwei; Perdew, John P; Lyssenko, Konstantin A

    2017-01-06

    The theorems at the core of density functional theory (DFT) state that the energy of a many-electron system in its ground state is fully defined by its electron density distribution. This connection is made via the exact functional for the energy, which minimizes at the exact density. For years, DFT development focused on energies, implicitly assuming that functionals producing better energies become better approximations of the exact functional. We examined the other side of the coin: the energy-minimizing electron densities for atomic species, as produced by 128 historical and modern DFT functionals. We found that these densities became closer to the exact ones, reflecting theoretical advances, until the early 2000s, when this trend was reversed by unconstrained functionals sacrificing physical rigor for the flexibility of empirical fitting. Copyright © 2017, American Association for the Advancement of Science.

  2. Modified interfacial statistical associating fluid theory: a perturbation density functional theory for inhomogeneous complex fluids.

    Science.gov (United States)

    Jain, Shekhar; Dominik, Aleksandra; Chapman, Walter G

    2007-12-28

    A density functional theory based on Wertheim's first order perturbation theory is developed for inhomogeneous complex fluids. The theory is derived along similar lines as interfacial statistical associating fluid theory [S. Tripathi and W. G. Chapman, J. Chem. Phys. 122, 094506 (2005)]. However, the derivation is more general and applies broadly to a range of systems, retaining the simplicity of a segment density based theory. Furthermore, the theory gives the exact density profile for ideal chains in an external field. The general avail of the theory has been demonstrated by applying the theory to lipids near surfaces, lipid bilayers, and copolymer thin films. The theoretical results show excellent agreement with the results from molecular simulations.

  3. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sosa Vazquez, Xochitl A.; Isborn, Christine M., E-mail: cisborn@ucmerced.edu [Chemistry and Chemical Biology, School of Natural Sciences, University of California, Merced, 5200 North Lake Road, Merced, California 95343 (United States)

    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.

  5. Modelling excited states of weakly bound complexes with density functional theory.

    Science.gov (United States)

    Briggs, Edward A; Besley, Nicholas A

    2014-07-28

    The binding within the ethene-argon and formaldehyde-methane complexes in the ground and electronically excited states is studied with equation of motion coupled cluster theory (EOM-CCSD), second-order Møller-Plesset perturbation theory (MP2) and density functional theory with dispersion corrections (DFT-D). Electronically excited states are studied within MP2 and Kohn-Sham DFT formalisms by exploiting a procedure called the maximum overlap method that allows convergence of the relevant self-consistent field equations to higher energy (or excited state) solutions. Potential energy curves computed using MP2 are in good agreement with the EOM-CCSD calculations for both the valence and Rydberg excited states studied. For the DFT-D approach, B3LYP-D3/aug-cc-pVTZ calculations are found to be in agreement with EOM-CCSD for the ground and valence excited states. However, for the π3s Rydberg state of ethene-argon and the n3s Rydberg state of formaldehyde-methane significant deviation is observed, and this disagreement with EOM-CCSD is present for a variety of DFT-D based approaches. Variation of the parameters within the D2 dispersion correction results in closer agreement with EOM-CCSD for the Rydberg states but demonstrates that a different parameterisation from the ground state is required for these states. This indicates that time-dependent density functional theory calculations based upon a DFT-D reference may be satisfactory for excitations to valence states, but will potentially be inaccurate for excitations to Rydberg states, or more generally states where the nature of the electron density is significantly different from the ground state.

  6. Density Functional Theory Simulations of Semiconductors for Photovoltaic Applications: Hybrid Organic-Inorganic Perovskites and III/V Heterostructures

    Directory of Open Access Journals (Sweden)

    Jacky Even

    2014-01-01

    Full Text Available Potentialities of density functional theory (DFT based methodologies are explored for photovoltaic materials through the modeling of the structural and optoelectronic properties of semiconductor hybrid organic-inorganic perovskites and GaAs/GaP heterostructures. They show how the properties of these bulk materials, as well as atomistic relaxations, interfaces, and electronic band-lineups in small heterostructures, can be thoroughly investigated. Some limitations of available standard DFT codes are discussed. Recent improvements able to treat many-body effects or based on density-functional perturbation theory are also reviewed in the context of issues relevant to photovoltaic technologies.

  7. Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

    Science.gov (United States)

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-10-15

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

  8. Localized operator partitioning method for electronic excitation energies in the time-dependent density functional formalism

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul; Izmaylov, Artur F

    2016-01-01

    We extend the localized operator partitioning method (LOPM) [J. Nagesh, A.F. Izmaylov, and P. Brumer, J. Chem. Phys. 142, 084114 (2015)] to the time-dependent density functional theory (TD-DFT) framework to partition molecular electronic energies of excited states in a rigorous manner. A molecular fragment is defined as a collection of atoms using Stratman-Scuseria-Frisch atomic partitioning. A numerically efficient scheme for evaluating the fragment excitation energy is derived employing a resolution of the identity to preserve standard one- and two-electron integrals in the final expressions. The utility of this partitioning approach is demonstrated by examining several excited states of two bichromophoric compounds: 9-((1-naphthyl)-methyl)-anthracene and 4-((2-naphthyl)-methyl)-benzaldehyde. The LOPM is found to provide nontrivial insights into the nature of electronic energy localization that are not accessible using simple density difference analysis.

  9. Structural and electronic properties of small silver-sulfur clusters: A density functional study

    Science.gov (United States)

    Li, Yan-Fang; Li, Yang; Li, Ying; Tan, Jia-Jin; Li, Hui-Li

    2016-10-01

    Density functional theory calculations have been performed to systematically investigate the structural and electronic properties of neutral and anionic AgnSm (2≤n+m≤6) clusters. The results show that the ground-state structures of neutral clusters are different from those of anionic clusters. Theoretical electron detachment energies (both vertical and adiabatic) are compared with the experimental measurements to verify the ground states of silver-sulfur clusters obtained in the present study. For both neutral and anionic systems, the highest occupied-lowest unoccupied molecular orbital energy gaps exhibit an odd-even oscillation as a function of the cluster size. In addition, the natural population analysis reveals that the charges transfer from Ag atoms to S atoms in AgnSm clusters, and the extra electron of AgnSm- clusters is mainly localized on the 3p subshells of S atoms.

  10. Local control theory using trajectory surface hopping and linear-response time-dependent density functional theory.

    Science.gov (United States)

    Curchod, Basile F E; Penfold, Thomas J; Rothlisberger, Ursula; Tavernelli, Ivano

    2013-01-01

    The implementation of local control theory using nonadiabatic molecular dynamics within the framework of linear-response time-dependent density functional theory is discussed. The method is applied to study the photoexcitation of lithium fluoride, for which we demonstrate that this approach can efficiently generate a pulse, on-the-fly, able to control the population transfer between two selected electronic states. Analysis of the computed control pulse yields insights into the photophysics of the process identifying the relevant frequencies associated to the curvature of the initial and final state potential energy curves and their energy differences. The limitations inherent to the use of the trajectory surface hopping approach are also discussed.

  11. Patching the Exchange-Correlation Potential in Density Functional Theory.

    Science.gov (United States)

    Huang, Chen

    2016-05-10

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

  12. Density Functional Theory in Surface Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Norskov, Jens

    2011-05-19

    Recent advances in the understanding of reactivity trends for chemistry at transition metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. Current status of the field is discussed with an emphasis on the role of coupling between theory and experiment and future challenges.

  13. Density functional theory in surface chemistry and catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

    2011-01-01

    Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future...

  14. A first-principles density functional theory study of the electronic structural and thermodynamic properties of M2ZrO3 and M2CO3 (M=Na, K) and their capabilities for CO2 capture

    Energy Technology Data Exchange (ETDEWEB)

    Yuhua Duan

    2012-01-01

    Alkali metal zirconates could be used as solid sorbents for CO{sub 2} capture. The structural, electronic, and phonon properties of Na{sub 2}ZrO{sub 3}, K{sub 2}ZrO{sub 3}, Na{sub 2}CO{sub 3}, and K{sub 2}CO{sub 3} are investigated by combining the density functional theory with lattice phonon dynamics. The thermodynamics of CO{sub 2} absorption/desorption reactions of these two zirconates are analyzed. The calculated results show that their optimized structures are in a good agreement with experimental measurements. The calculated band gaps are 4.339 eV (indirect), 3.641 eV (direct), 3.935 eV (indirect), and 3.697 eV (direct) for Na{sub 2}ZrO{sub 3}, K{sub 2}ZrO{sub 3}, Na{sub 2}CO{sub 3}, and K{sub 2}CO{sub 3}, respectively.The calculated phonon dispersions and phonon density of states for M{sub 2}ZrO{sub 3} and M{sub 2}CO{sub 3} (M = K, Na, Li) revealed that from K to Na to Li, their frequency peaks are shifted to high frequencies due to the molecular weight decreased from K to Li. From the calculated reaction heats and relationships of free energy change versus temperatures and CO{sub 2} pressures of the M{sub 2}ZrO{sub 3} (M = K, Na, Li) reacting with CO{sub 2}, we found that the performance of Na{sub 2}ZrO{sub 3} capturing CO{sub 2} is similar to that of Li{sub 2}ZrO{sub 3} and is better than that of K{sub 2}ZrO{sub 3}. Therefore, Na{sub 2}ZrO{sub 3} and Li{sub 2}ZrO{sub 3} are good candidates of high temperature CO{sub 2} sorbents and could be used for post combustion CO{sub 2} capture technologies.

  15. Non-perturbative calculation of molecular magnetic properties within current-density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Tellgren, E. I., E-mail: erik.tellgren@kjemi.uio.no; Lange, K. K.; Ekström, U.; Helgaker, T. [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo (Norway); Teale, A. M., E-mail: andrew.teale@nottingham.ac.uk [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo (Norway); School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom); Furness, J. W. [School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2014-01-21

    We present a novel implementation of Kohn–Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic fields are treated non-perturbatively, which enable the study of both magnetic response properties and the effects of strong fields, using either standard density functionals or current-density functionals—the implementation is the first fully self-consistent implementation of the latter for molecules. Pilot applications are presented for the finite-field calculation of molecular magnetizabilities, hypermagnetizabilities, and nuclear magnetic resonance shielding constants, focusing on the impact of current-density functionals on the accuracy of the results. Existing current-density functionals based on the gauge-invariant vorticity are tested and found to be sensitive to numerical details of their implementation. Furthermore, when appropriately regularized, the resulting magnetic properties show no improvement over standard density-functional results. An advantage of the present implementation is the ability to apply density-functional theory to molecules in very strong magnetic fields, where the perturbative approach breaks down. Comparison with high accuracy full-configuration-interaction results show that the inadequacies of current-density approximations are exacerbated with increasing magnetic field strength. Standard density-functionals remain well behaved but fail to deliver high accuracy. The need for improved current-dependent density-functionals, and how they may be tested using the presented implementation, is discussed in light of our findings.

  16. Calculation of the electron density distribution in silicon by the density-functional method. Comparison with X-ray results

    NARCIS (Netherlands)

    Velders, G.J.M.; Feil, D.

    1989-01-01

    Quantum-chemical density-functional theory (DFT) calculations, using the local-density approximation (LDA), have been performed for hydrogen-bounded silicon clusters to determine the electron density distribution of the Si-Si bond. The density distribution in the bonding region is compared with calc

  17. On extending Kohn-Sham density functionals to systems with fractional number of electrons.

    Science.gov (United States)

    Li, Chen; Lu, Jianfeng; Yang, Weitao

    2017-06-07

    We analyze four ways of formulating the Kohn-Sham (KS) density functionals with a fractional number of electrons, through extending the constrained search space from the Kohn-Sham and the generalized Kohn-Sham (GKS) non-interacting v-representable density domain for integer systems to four different sets of densities for fractional systems. In particular, these density sets are (I) ensemble interacting N-representable densities, (II) ensemble non-interacting N-representable densities, (III) non-interacting densities by the Janak construction, and (IV) non-interacting densities whose composing orbitals satisfy the Aufbau occupation principle. By proving the equivalence of the underlying first order reduced density matrices associated with these densities, we show that sets (I), (II), and (III) are equivalent, and all reduce to the Janak construction. Moreover, for functionals with the ensemble v-representable assumption at the minimizer, (III) reduces to (IV) and thus justifies the previous use of the Aufbau protocol within the (G)KS framework in the study of the ground state of fractional electron systems, as defined in the grand canonical ensemble at zero temperature. By further analyzing the Aufbau solution for different density functional approximations (DFAs) in the (G)KS scheme, we rigorously prove that there can be one and only one fractional occupation for the Hartree Fock functional, while there can be multiple fractional occupations for general DFAs in the presence of degeneracy. This has been confirmed by numerical calculations using the local density approximation as a representative of general DFAs. This work thus clarifies important issues on density functional theory calculations for fractional electron systems.

  18. Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory.

    Science.gov (United States)

    Klimeš, Jirí; Michaelides, Angelos

    2012-09-28

    Electron dispersion forces play a crucial role in determining the structure and properties of biomolecules, molecular crystals, and many other systems. However, an accurate description of dispersion is highly challenging, with the most widely used electronic structure technique, density functional theory (DFT), failing to describe them with standard approximations. Therefore, applications of DFT to systems where dispersion is important have traditionally been of questionable accuracy. However, the last decade has seen a surge of enthusiasm in the DFT community to tackle this problem and in so-doing to extend the applicability of DFT-based methods. Here we discuss, classify, and evaluate some of the promising schemes to emerge in recent years. A brief perspective on the outstanding issues that remain to be resolved and some directions for future research are also provided.

  19. Density-functional theory cannot be constrained to completely overcome self-interaction error

    CERN Document Server

    Moynihan, Glenn; O'Regan, David D

    2016-01-01

    In approximate density functional theory (DFT), the self-interaction error is a pervasive electron delocalization associated with underestimated insulating gaps. It exhibits a predominantly quadratic energy-density curve that is amenable to correction using computationally efficient, constraint-resembling methods such as DFT + Hubbard U (DFT+U). Constrained DFT (cDFT) exactly enforces conditions on DFT by means of self-consistently optimized Lagrange multipliers, and its use to automate DFT+U type corrections is a compelling possibility. We show that constraints beyond linear order are incompatible with cDFT. For DFT+U, we overcome this by separating its Hubbard U parameters into linear and quadratic terms. For a one-electron system, the resulting generalized DFT+U method can recover the exact subspace occupancy and free-energy, but neither the exact total-energy nor the exact ionization potential, for reasonable parameters. Approximate functionals thus cannot be systematically corrected by constraining their...

  20. Photoemission and density functional theory study of Ir(111); energy band gap mapping.

    Science.gov (United States)

    Pletikosić, I; Kralj, M; Sokčević, D; Brako, R; Lazić, P; Pervan, P

    2010-04-07

    We have performed combined angle-resolved photoemission spectroscopy (ARPES) experiments and density functional theory (DFT) calculations of the electronic structure of the Ir(111) surface, with the focus on the existence of energy band gaps. The investigation was motivated by the experimental results suggesting Ir(111) as an ideal support for the growth of weakly bonded graphene. Therefore, our prime interest was electronic structure around the [Formula: see text] symmetry point. In accordance with DFT calculations, ARPES has shown a wide energy band gap with the shape of a parallelogram centred around the [Formula: see text] point. Within the gap three surface states were identified; one just below the Fermi level and two spin-orbit split surface states at the bottom of the gap.

  1. Oxygen vacancy in N-doped Cu2O crystals:A density functional theory study

    Institute of Scientific and Technical Information of China (English)

    Li Min; Zhang Jun-Ying; Zhang Yue; Wang Tian-Min

    2012-01-01

    The N-doping effects on the electronic properties of Cu2O crystals are investigated using density functional theory.The calculated results show that N-doped Cu2O with or without oxygen vacancy exhibits different modifications of electronic band structure.In N anion-doped Cu2O,some N 2p states overlap and mix with the O 2p valence band,leading to a slight narrowing of band gap compared with the undoped Cu2O.However,it is found that the coexistence of both N impurity and oxygen vacancy contributes to band gap widening which may account for the experimentally observed optical band gap widening by N doping.

  2. Theoretical modelling of photoactive molecular systems: insights using the Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Ciofini, I.; Adamo, C. [Ecole Nationale Superieure de Chimie de Paris, Lab. d' Electrochimie et Chimie Analytique, CNRS UMR 7575, 75 - Paris (France); Laine, Ph.P. [Universite Rene-Descartes, Lab. de Chimie et Biochimie Pharmacologiques et Toxicologiques, CNRS UMR 8601, 75 - Paris (France); Bedioui, F. [Ecole Nationale Superieure de Chimie de Paris, Lab. de Pharmacologie Chimique et Genetique, CNRS FRE 2463 and INSERM U 640, 75 - Paris (France); Daul, C.A. [Fribourg Univ., Dept. de Chimie (Switzerland)

    2006-02-15

    An account of the performance of a modern and efficient approach to Density Functional Theory (DFT) for the prediction of the photophysical behavior of a series of Ru(II) and Os(II) complexes is given. The time-dependent-DFT method was used to interpret their electronic spectra. Two different types of compounds have been analyzed: (1) a complex undergoing a light induced isomerization of one of its coordination bonds; (2) an inorganic dyads expected to undergo intramolecular photoinduced electron transfer to form a charge separated (CS) sate. Besides the noticeable quantitative agreement between computed and experimental absorption spectra, our results allow to clarify, by first principles, both the nature of the excited states and the photochemical behavior of these complex systems, thus underlying the predictive character of the theoretical approach. (authors)

  3. A comparative study of atomic oxygen adsorption at Pd surfaces from Density Functional Theory

    Science.gov (United States)

    Bukas, Vanessa J.; Reuter, Karsten

    2017-04-01

    Based on density functional theory, we present a detailed investigation into the on-surface adsorption of atomic oxygen at all three low-index Pd facets in the low-coverage regime. Relying on one consistent computational framework allows for a systematic comparison with respect to surface symmetry, while discerning trends in the adsorption geometries, energies, work functions, and electron densities. We overall find a persisting degree of O-Pd hybridization that is accompanied by minimal charge transfer from the substrate to the adsorbate, thereby resulting in comparable binding energies and diffusion barriers at the three surfaces. Small differences in reactivity are nevertheless reflected in subtle variations of the underlying electronic structure which do not, however, follow the expected order according to atom packing density.

  4. Higher-order adaptive finite-element methods for Kohn-Sham density functional theory

    CERN Document Server

    Motamarri, Phani; Leiter, Kenneth; Knap, Jaroslaw; Gavini, Vikram

    2012-01-01

    We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn-Sham density-functional theory (DFT).To this end, we develop an \\emph{a priori} mesh adaption technique to construct a close to optimal finite-element discretization of the problem. We further propose an efficient solution strategy for solving the discrete eigenvalue problem by using spectral finite-elements in conjunction with Gauss-Lobatto quadrature, and a Chebyshev acceleration technique for computing the occupied eigenspace. Using the proposed solution procedure, we investigate the computational efficiency afforded by higher-order finite-element discretizations of the Kohn-Sham DFT problem. Our studies suggest that staggering computational savings---of the order of $1000-$fold---can be realized, for both all-electron and pseudopotential calculations, by using higher-order finite-element discretizations. On all the benchmark systems stu...

  5. Vibrational spectroscopy and density functional theory analysis of 3-O-caffeoylquinic acid

    Science.gov (United States)

    Mishra, Soni; Tandon, Poonam; Eravuchira, Pinkie J.; El-Abassy, Rasha M.; Materny, Arnulf

    2013-03-01

    Density functional theory (DFT) calculations are being performed to investigate the geometric, vibrational, and electronic properties of the chlorogenic acid isomer 3-CQA (1R,3R,4S,5R)-3-{[(2E)-3-(3,4-dihydroxyphenyl)prop-2-enoyl]oxy}-1,4,5-trihydroxycyclohexanecarboxylic acid), a major phenolic compound in coffee. DFT calculations with the 6-311G(d,p) basis set produce very good results. The electrostatic potential mapped onto an isodensity surface has been obtained. A natural bond orbital analysis (NBO) has been performed in order to study intramolecular bonding, interactions among bonds, and delocalization of unpaired electrons. HOMO-LUMO studies give insights into the interaction of the molecule with other species. The calculated HOMO and LUMO energies indicate that a charge transfer occurs within the molecule.

  6. Density functional theory calculations of charge transport properties of ‘plate-like’ coronene topological structures

    Indian Academy of Sciences (India)

    ZIRAN CHEN; ZHANRONG HE; YOUHUI XU; WENHAO YU

    2017-09-01

    Charge transport rate is one of the key parameters determining the performance of organic electronic devices. In this paper, we used density functional theory (DFT) at the M06-2X/6−31+G(d) level to compute the charge transport rates of nine coronene topological structures. The results show that the energy gap of these nine coronene derivatives is in the range 2.90–3.30 eV, falling into the organic semiconductor category. The size of the conjugate ring has a large influence on the charge transport properties. Incorporation of methyl groupson the rigid core of tetrabenzocoronene and hexabenzocoronene is more conducive to the hole transport of the molecule than incorporating methoxyl groups. The derivatisation of a ‘long plate-like’ coronene with methoxylgroups facilitates both hole and electron transport. This class of molecules can thus be used in the design of ambipolar transport semiconductor materials.

  7. Challenging Density Functional Theory Calculations with Hemes and Porphyrins

    Directory of Open Access Journals (Sweden)

    Sam P. de Visser

    2016-04-01

    Full Text Available In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol−1. This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties.

  8. Hybrid density functional theory description of N- and C-doping of NiO.

    Science.gov (United States)

    Nolan, Michael; Long, Run; English, Niall J; Mooney, Damian A

    2011-06-14

    The large intrinsic bandgap of NiO hinders its potential application as a photocatalyst under visible-light irradiation. In this study, we have performed first-principles screened exchange hybrid density functional theory with the HSE06 functional calculations of N- and C-doped NiO to investigate the effect of doping on the electronic structure of NiO. C-doping at an oxygen site induces gap states due to the dopant, the positions of which suggest that the top of the valence band is made up primarily of C 2p-derived states with some Ni 3d contributions, and the lowest-energy empty state is in the middle of the gap. This leads to an effective bandgap of 1.7 eV, which is of potential interest for photocatalytic applications. N-doping induces comparatively little dopant-Ni 3d interactions, but results in similar positions of dopant-induced states, i.e., the top of the valence band is made up of dopant 2p states and the lowest unoccupied state is the empty gap state derived from the dopant, leading to bandgap narrowing. With the hybrid density functional theory (DFT) results available, we discuss issues with the DFT corrected for on-site Coulomb description of these systems.

  9. Oligomeric synthesis and density functional theory of leucoemeraldine base form of polyaniline

    Science.gov (United States)

    Ullah, Rizwan; Ullah, Habib; Shah, Anwar-ul-Haq Ali; Bilal, Salma; Ali, Khurshid

    2017-01-01

    Oligomeric synthesis of phenyl-end-capped oligoaniline (4PANI LB) has been carried out through a weak oxidizing agent, CuCl2, using chemical oxidative polymerization protocol. The sample was characterized by mass spectrometry, UV-vis, IR, and CHN elemental analysis. The experimental results are counterchecked with the aid of Quantum mechanical calculations such as density functional theory (DFT). DFT at B3LYP/6-31 G (d) level of theory was used for the geometric and electronic properties simulations which also confirm the existence of 4PANI LB. Excellent correlation is observed between the experiment and theory, particularly in the UV-vis spectra which conclude the formation of tetramer (fully reduced form) 4PANI LB (C24H20.06N4.07). Electronic properties such as Ionization Potential (I.P), Electron Affinities (E.A), the coefficient of highest occupied molecular orbital (HOMO), the coefficient of lowest unoccupied molecular orbital (LUMO) of 4PANI LB were evaluated at the above-mentioned level of theory.

  10. Density functional theory calculations on dipeptide gallic acid interaction

    Science.gov (United States)

    Madhan, B.; Parthasarathi, R.; Subramanian, V.; Raghava Rao, J.; Nair, Balachandran Unni; Ramasami, T.

    2003-02-01

    In the present investigation, an attempt has been made to study the interaction of dipeptides with gallic acid, using Becke3 parameter Lee Yang Parr (B3LYP) method employing 3-21G*, 6-31G* and 6-31+G* basis sets. The interaction energies of the dipeptide-gallic acid complexes are in the range of -5 to -18 kcal/mol depending on the mode of intermolecular complexation. Calculated molecular electrostatic potential (MESP) for the various intermolecular complexes revealed the electrostatic nature of the interaction. Qualitative estimations based on chemical hardness and chemical potential demonstrated fractional electron transfer from dipeptide to gallic acid.

  11. Covalent bonding from alchemical linear response density functional theory

    CERN Document Server

    Chang, K Y Samuel; Ramakrishnan, Raghunathan; von Lilienfeld, O Anatole

    2015-01-01

    We assess the predictive accuracy of linear response based estimates of changes in covalent bonding due to linear alchemical interpolations among molecules. We have investigated single bonds to hydrogen, as well as single, double, and triple bonds between main-group elements, occurring in small iso-electronic molecular spaces with atomic elements drawn from rows 2-3 in the $p$-block of the periodic table. Numerical evidence suggests that first order estimates of bonding potentials can achieve chemical accuracy if the alchemical interpolation connects molecules containing late elements in the periodic table (3$^{rd}$ and 4$^{th}$ row) and identical number of atoms and molecular geometries. For these interpolations, changes in bonding potential are near-linear in the coupling parameter, resulting in accurate Hellmann-Feynman predictions. Second order estimates for such interpolations yield worse predictions. The predictions become substantially worse if initial and final molecules differ not only in composition...

  12. Scaling properties of information-theoretic quantities in density functional reactivity theory.

    Science.gov (United States)

    Rong, Chunying; Lu, Tian; Ayers, Paul W; Chattaraj, Pratim K; Liu, Shubin

    2015-02-21

    Density functional reactivity theory (DFRT) employs the electron density and its related quantities to describe reactivity properties of a molecular system. Quantities from information theory such as Shannon entropy, Fisher information, and Ghosh-Berkowitz-Parr entropy are natural descriptors within the DFRT framework. They have been previously employed to quantify electrophilicity, nucleophilicity and the steric effect. In this work, we examine their scaling properties with respect to the total number of electrons. To that end, we considered their representations in terms of both the electron density and the shape function for isolated atoms and neutral molecules. We also investigated their atomic behaviors in different molecules with three distinct partitioning schemes: Bader's zero-flux, Becke's fuzzy atom, and Hirshfeld's stockholder partitioning. Strong linear relationships of these quantities as a function of the total electron population are reported for atoms, molecules, and atoms in molecules. These relationships reveal how these information-theoretic quantities depend on the molecular environment and the electron population. These trends also indicate how these quantities can be used to explore chemical reactivity for real chemical processes.

  13. Density functional study of $\\rm{AgScO_2}$: Electronic and optical properties

    Indian Academy of Sciences (India)

    K C BHAMU; JAGRATI SAHARIYA; RISHI VYAS; K R PRIOLKAR

    2017-07-01

    This paper focusses on the electronic and optical properties of scandium-based silver delafossite $\\rm{(AgScO_2)}$ semiconductor. The density functional theory (DFT) in the framework of full potential linearized augmented plane wave (FP-LAPW) scheme has been used for the present calculations with local densityapproximation (LDA) and generalized gradient approximation (GGA). Electronic properties deal with energy bands and density of states (DOSs), while optical properties describe refractive index and absorption coefficient.The energy bands are interpreted in terms of DOSs. The computed value of band gap is in agreement with that reported in the literature. Our results predict $\\rm{AgScO_2}$ as indirect band-gap semiconductor. Our calculated value of the refractive index in zero frequency limits is 2.42. The absorption coefficient predicts the applicability of $\\rm{AgScO_2}$ in solar cells and flat panel liquid crystal display as a transparent top window layer.

  14. Density functional Studies of structural, electronic and vibrational properties of palladium oxide

    Science.gov (United States)

    Kansara, Shivam; Singh, Deobrat; Gupta, Sanjeev K.; Sonvane, Yogesh

    2016-11-01

    In the present paper, structural properties, electronic properties, phonon dispersion curve and Raman spectra at different pressure of the tetragonal palladium oxide (PdO) using density functional theory are discussed. The electronic band structure and density of states (DOS) show the poor metallic behavior of the system but through the hybrid potential calculation show 0.71 eV band gap. The phonon dispersion curve and Raman spectra confirm the stability of the structure while Raman peaks are slightly shifted toward higher frequency due to the applied pressure. Phonon calculations indicate that the PdO structure is stable up to 10 GPa and slightly unstable at 15 GPa pressure. There is no change of the crystallinity with applied pressure which is observed from the intensities of Raman active mode. Palladium oxides are mainly used as a catalysts for catalytic hydrogenation in organic synthesis.

  15. Density functional calculation of equilibrium geometry and electronic structure of pyrite

    Institute of Scientific and Technical Information of China (English)

    邱冠周; 肖奇; 胡岳华; 徐竞

    2001-01-01

    The equilibrium geometry and electronic structure of pyrite has been studied using self-consistent density-functional theory within the local density approximation (LDA). The optimum bulk geometry is in good agreement with crystallographic data. The calculated band structure and density of states in the region around the Fermi energy show that valence-band maximum (VBM) is at X (100), and the conduction-band minimum (CBM) is at G (000). The indirect and direct band gaps are 0.6eV and 0.74eV, respectively. The calculated contour map of difference of charge density shows excess charge in nonbonding d electron states on the Fe sites. The density increases between sulfur nuclei and between iron and sulfur nuclei qualitatively reveal that S-S bond and Fe-S bond are covalent binding.

  16. Density functional study of AgScO_2: Electronic and optical properties

    Science.gov (United States)

    Bhamu, K. C.; Sahariya, Jagrati; Vyas, Rishi; Priolkar, K. R.

    2017-07-01

    This paper focusses on the electronic and optical properties of scandium-based silver delafossite (AgScO_2) semiconductor. The density functional theory (DFT) in the framework of full potential linearized augmented plane wave (FP-LAPW) scheme has been used for the present calculations with local density approximation (LDA) and generalized gradient approximation (GGA). Electronic properties deal with energy bands and density of states (DOSs), while optical properties describe refractive index and absorption coefficient. The energy bands are interpreted in terms of DOSs. The computed value of band gap is in agreement with that reported in the literature. Our results predict AgScO_2 as indirect band-gap semiconductor. Our calculated value of the refractive index in zero frequency limits is 2.42. The absorption coefficient predicts the applicability of AgScO_2 in solar cells and flat panel liquid crystal display as a transparent top window layer.

  17. Crystal and electronic structures of substituted halide perovskites based on density functional calculation and molecular dynamics

    Science.gov (United States)

    Takaba, Hiromitsu; Kimura, Shou; Alam, Md. Khorshed

    2017-03-01

    Durability of organo-lead halide perovskite are important issue for its practical application in a solar cells. In this study, using density functional theory (DFT) and molecular dynamics, we theoretically investigated a crystal structure, electronic structure, and ionic diffusivity of the partially substituted cubic MA0.5X0.5PbI3 (MA = CH3NH3+, X = NH4+ or (NH2)2CH+ or Cs+). Our calculation results indicate that a partial substitution of MA induces a lattice distortion, resulting in preventing MA or X from the diffusion between A sites in the perovskite. DFT calculations show that electronic structures of the investigated partially substituted perovskites were similar with that of MAPbI3, while their bandgaps slightly decrease compared to that of MAPbI3. Our results mean that partial substitution in halide perovskite is effective technique to suppress diffusion of intrinsic ions and tune the band gap.

  18. Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes

    CERN Document Server

    Chai, Jeng-Da

    2016-01-01

    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 H2 dissociation 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 TAO-DFAs (i.e., TAO-DFT with the conventional density functional approximations), global hybrid...

  19. Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

    Science.gov (United States)

    Sun, Jianwei; Perdew, John P.; Yang, Zenghui; Peng, Haowei

    2016-05-01

    The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

  20. 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.