WorldWideScience

Sample records for dependent density functional

  1. Density dependence of the nuclear energy-density functional

    Science.gov (United States)

    Papakonstantinou, Panagiota; Park, Tae-Sun; Lim, Yeunhwan; Hyun, Chang Ho

    2018-01-01

    Background: The explicit density dependence in the coupling coefficients entering the nonrelativistic nuclear energy-density functional (EDF) is understood to encode effects of three-nucleon forces and dynamical correlations. The necessity for the density-dependent coupling coefficients to assume the form of a preferably small fractional power of the density ρ is empirical and the power is often chosen arbitrarily. Consequently, precision-oriented parametrizations risk overfitting in the regime of saturation and extrapolations in dilute or dense matter may lose predictive power. Purpose: Beginning with the observation that the Fermi momentum kF, i.e., the cubic root of the density, is a key variable in the description of Fermi systems, we first wish to examine if a power hierarchy in a kF expansion can be inferred from the properties of homogeneous matter in a domain of densities, which is relevant for nuclear structure and neutron stars. For subsequent applications we want to determine a functional that is of good quality but not overtrained. Method: For the EDF, we fit systematically polynomial and other functions of ρ1 /3 to existing microscopic, variational calculations of the energy of symmetric and pure neutron matter (pseudodata) and analyze the behavior of the fits. We select a form and a set of parameters, which we found robust, and examine the parameters' naturalness and the quality of resulting extrapolations. Results: A statistical analysis confirms that low-order terms such as ρ1 /3 and ρ2 /3 are the most relevant ones in the nuclear EDF beyond lowest order. It also hints at a different power hierarchy for symmetric vs. pure neutron matter, supporting the need for more than one density-dependent term in nonrelativistic EDFs. The functional we propose easily accommodates known or adopted properties of nuclear matter near saturation. More importantly, upon extrapolation to dilute or asymmetric matter, it reproduces a range of existing microscopic

  2. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

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

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

    Indian Academy of Sciences (India)

    A time-dependent generalized non-linear Schrödinger equation (GNLSE) of motion was earlier derived in our laboratory by combining density functional theory and quantum fluid dynamics in threedimensional space. In continuation of the work reported previously, the GNLSE is applied to provide additional knowledge on ...

  5. Computational complexity of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Whitfield, J D; Yung, M-H; Tempel, D G; Aspuru-Guzik, A; Boixo, S

    2014-01-01

    Time-dependent density functional theory (TDDFT) is rapidly emerging as a premier method for solving dynamical many-body problems in physics and chemistry. The mathematical foundations of TDDFT are established through the formal existence of a fictitious non-interacting system (known as the Kohn–Sham system), which can reproduce the one-electron reduced probability density of the actual system. We build upon these works and show that on the interior of the domain of existence, the Kohn–Sham system can be efficiently obtained given the time-dependent density. We introduce a V-representability parameter which diverges at the boundary of the existence domain and serves to quantify the numerical difficulty of constructing the Kohn-Sham potential. For bounded values of V-representability, we present a polynomial time quantum algorithm to generate the time-dependent Kohn–Sham potential with controllable error bounds. (paper)

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

    Energy Technology Data Exchange (ETDEWEB)

    Maitra, Neepa T. [Department of Physics and Astronomy, Hunter College and the Physics Program at the Graduate Center of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States)

    2016-06-14

    In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.

  7. 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

  8. 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.

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

    Indian Academy of Sciences (India)

    WINTEC

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

  10. Multiscale time-dependent density functional theory: Demonstration for plasmons.

    Science.gov (United States)

    Jiang, Jiajian; Abi Mansour, Andrew; Ortoleva, Peter J

    2017-08-07

    Plasmon properties are of significant interest in pure and applied nanoscience. While time-dependent density functional theory (TDDFT) can be used to study plasmons, it becomes impractical for elucidating the effect of size, geometric arrangement, and dimensionality in complex nanosystems. In this study, a new multiscale formalism that addresses this challenge is proposed. This formalism is based on Trotter factorization and the explicit introduction of a coarse-grained (CG) structure function constructed as the Weierstrass transform of the electron wavefunction. This CG structure function is shown to vary on a time scale much longer than that of the latter. A multiscale propagator that coevolves both the CG structure function and the electron wavefunction is shown to bring substantial efficiency over classical propagators used in TDDFT. This efficiency follows from the enhanced numerical stability of the multiscale method and the consequence of larger time steps that can be used in a discrete time evolution. The multiscale algorithm is demonstrated for plasmons in a group of interacting sodium nanoparticles (15-240 atoms), and it achieves improved efficiency over TDDFT without significant loss of accuracy or space-time resolution.

  11. Fundamentals of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Marques, Miguel A.L.; Rubio, Angel

    2012-01-01

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

  12. 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.

  13. Density-dependence of functional spiking networks in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Ham, Michael I [Los Alamos National Laboratory; Gintautuas, Vadas [Los Alamos National Laboratory; Rodriguez, Marko A [Los Alamos National Laboratory; Bettencourt, Luis M A [Los Alamos National Laboratory; Bennett, Ryan [UNIV OF NORTH TEXAS; Santa Maria, Cara L [UNIV OF NORTH TEXAS

    2008-01-01

    During development, the mammalian brain differentiates into specialized regions with unique functional abilities. While many factors contribute to this functional specialization, we explore the effect neuronal density can have on neuronal interactions. Two types of networks, dense (50,000 neurons and glia support cells) and sparse (12,000 neurons and glia support cells), are studied. A competitive first response model is applied to construct activation graphs that represent pairwise neuronal interactions. By observing the evolution of these graphs during development in vitro we observe that dense networks form activation connections earlier than sparse networks, and that link-!llltropy analysis of the resulting dense activation graphs reveals that balanced directional connections dominate. Information theoretic measures reveal in addition that early functional information interactions (of order 3) are synergetic in both dense and sparse networks. However, during development in vitro, such interactions become redundant in dense, but not sparse networks. Large values of activation graph link-entropy correlate strongly with redundant ensembles observed in the dense networks. Results demonstrate differences between dense and sparse networks in terms of informational groups, pairwise relationships, and activation graphs. These differences suggest that variations in cell density may result in different functional specialization of nervous system tissue also in vivo.

  14. 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...

  15. Time-dependent density functional theory for multi-component systems

    International Nuclear Information System (INIS)

    Tiecheng Li; Peiqing Tong

    1985-10-01

    The Runge-Gross version of Hohenberg-Kohn-Sham's density functional theory is generalized to multi-component systems, both for arbitrary time-dependent pure states and for arbitrary time-dependent ensembles. (author)

  16. Exponential integrators in time-dependent density-functional calculations

    Science.gov (United States)

    Kidd, Daniel; Covington, Cody; Varga, Kálmán

    2017-12-01

    The integrating factor and exponential time differencing methods are implemented and tested for solving the time-dependent Kohn-Sham equations. Popular time propagation methods used in physics, as well as other robust numerical approaches, are compared to these exponential integrator methods in order to judge the relative merit of the computational schemes. We determine an improvement in accuracy of multiple orders of magnitude when describing dynamics driven primarily by a nonlinear potential. For cases of dynamics driven by a time-dependent external potential, the accuracy of the exponential integrator methods are less enhanced but still match or outperform the best of the conventional methods tested.

  17. Time dependentdensity functional theory characterization of organic dyes for dye-sensitized solar cells

    KAUST Repository

    Hilal, Rifaat; Aziz, Saadullah G.; Osman, Osman I.; Bredas, Jean-Luc

    2017-01-01

    We aim at providing better insight into the parameters that govern the intramolecular charge transfer (ICT) and photo-injection processes in dyes for dye-sensitised solar cells (DSSC). Density functional theory (DFT) and time-dependent DFT (TD

  18. Optical properties of Al nanostructures from time dependent density functional theory

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2016-01-01

    The optical properties of Al nanostructures are investigated by means of time dependent density functional theory, considering chains of varying length and ladders/stripes of varying aspect ratio. The absorption spectra show redshifting

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

    Science.gov (United States)

    Nishimoto, Yoshio

    2015-09-07

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

  20. Natural excitation orbitals from linear response theories : Time-dependent density functional theory, time-dependent Hartree-Fock, and time-dependent natural orbital functional theory

    NARCIS (Netherlands)

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

    2017-01-01

    Straightforward interpretation of excitations is possible if they can be described as simple single orbital-to-orbital (or double, etc.) transitions. In linear response time-dependent density functional theory (LR-TDDFT), the (ground state) Kohn-Sham orbitals prove to be such an orbital basis. In

  1. 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.

  2. Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory

    Science.gov (United States)

    2017-04-23

    Our approach represents a full solid-state calculation, allowing for polarization ef- fects while still capable of capturing inter-molecular dis...AFRL-AFOSR-UK-TR-2017-0030 Optical absorption in molecular crystals from time-dependent density functional theory Leeor Kronik WEIZMANN INSTITUTE OF...from time-dependent density functional theory 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-15-1-0290 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S

  3. Maitra-Burke example of initial-state dependence in time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Holas, A.; Balawender, R.

    2002-01-01

    In a recent paper, Maitra and Burke [Phys. Rev. A 63, 042501 (2001); 64, 039901(E) (2001)] have given an interesting and instructive example that illustrates a specific feature of the time-dependent density-functional theory--the dependence of the reconstructed time-dependent potential not only on the electron density, but also on the initial state of the system. However, a concise form of its presentation by these authors is insufficient to reveal all its peculiarities. Our paper represents a very detailed study of this valuable example, intended to facilitate a better understanding and appreciation

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

    Energy Technology Data Exchange (ETDEWEB)

    Sissay, Adonay [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Lopata, Kenneth, E-mail: klopata@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)

    2016-09-07

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  6. Time-dependent density-functional theory in the projector augmented-wave method

    DEFF Research Database (Denmark)

    Walter, Michael; Häkkinen, Hannu; Lehtovaara, Lauri

    2008-01-01

    We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we...

  7. Vibrationally resolved UV/Vis spectroscopy with time-dependent density functional based tight binding

    NARCIS (Netherlands)

    Ruger, R.; Niehaus, T.; van Lenthe, E.; Heine, T.; Visscher, L.

    2016-01-01

    We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nu- clear wavefunction.

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

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Rubio, Angel; Olsen, Thomas

    2009-01-01

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

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

    Science.gov (United States)

    Panholzer, Martin; Gatti, Matteo; Reining, Lucia

    2018-04-01

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

  10. Spatially heterogeneous dynamics investigated via a time-dependent four-point density correlation function

    DEFF Research Database (Denmark)

    Lacevic, N.; Starr, F. W.; Schrøder, Thomas

    2003-01-01

    correlation function g4(r,t) and corresponding "structure factor" S4(q,t) which measure the spatial correlations between the local liquid density at two points in space, each at two different times, and so are sensitive to dynamical heterogeneity. We study g4(r,t) and S4(q,t) via molecular dynamics......Relaxation in supercooled liquids above their glass transition and below the onset temperature of "slow" dynamics involves the correlated motion of neighboring particles. This correlated motion results in the appearance of spatially heterogeneous dynamics or "dynamical heterogeneity." Traditional...... two-point time-dependent density correlation functions, while providing information about the transient "caging" of particles on cooling, are unable to provide sufficiently detailed information about correlated motion and dynamical heterogeneity. Here, we study a four-point, time-dependent density...

  11. Decay of hollow states in time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Varun; Bauer, Dieter [Institut fuer Physik, Wismarsche Str. 43-45, Universitaet Rostock, Rostock-18051 (Germany)

    2012-07-01

    Hollow or multiply excited states are inaccessible in time dependent density functional theory (TDDFT) using adiabatic Kohn-Sham potentials. We determine the exact Kohn Sham (KS) potential for doubly excited states in an exactly solvable model Helium atom. The exact single-particle density corresponds to the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose origin is traced back to phase of the exact KS orbital. The potential controls the barrier height and width in order for the density to tunnel out and decay with the same rate as the doubly excited state in the ab initio time-dependent Schroedinger calculation. Instead, adiabatic KS potentials only show direct photoionization but no autoionization. A frequency-dependent linear response kernel would be necessary in order to capture the decay of autoionizing states.

  12. Multi-configuration time-dependent density-functional theory based on range separation

    DEFF Research Database (Denmark)

    Fromager, E.; Knecht, S.; Jensen, Hans Jørgen Aagaard

    2013-01-01

    Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range Multi-Configuration- Self-Consistent Field (MCSCF) treatment with an adiabatic short...... (srGGA) approximations. As expected, when modeling long-range interactions with the MCSCF model instead of the adiabatic Buijse-Baerends density-matrix functional as recently proposed by Pernal [J. Chem. Phys. 136, 184105 (2012)10.1063/1.4712019], the description of both the 1D doubly-excited state...

  13. Sensitivity and uncertainty analysis for functionals of the time-dependent nuclide density field

    International Nuclear Information System (INIS)

    Williams, M.L.; Weisbin, C.R.

    1978-04-01

    An approach to extend the present ORNL sensitivity program to include functionals of the time-dependent nuclide density field is developed. An adjoint equation for the nuclide field was derived previously by using generalized perturbation theory; the present derivation makes use of a variational principle and results in the same equation. The physical significance of this equation is discussed and compared to that of the time-dependent neutron adjoint equation. Computational requirements for determining sensitivity profiles and uncertainties for functionals of the time-dependent nuclide density vector are developed within the framework of the existing FORSS system; in this way the current capability is significantly extended. The development, testing, and use of an adjoint version of the ORIGEN isotope generation and depletion code are documented. Finally, a sample calculation is given which estimates the uncertainty in the plutonium inventory at shutdown of a PWR due to assumed uncertainties in uranium and plutonium cross sections. 8 figures, 4 tables

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

    International Nuclear Information System (INIS)

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

    1986-10-01

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

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

    International Nuclear Information System (INIS)

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

    1985-02-01

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

  16. Time-dependent density functional theory for open quantum systems with unitary propagation.

    Science.gov (United States)

    Yuen-Zhou, Joel; Tempel, David G; Rodríguez-Rosario, César A; Aspuru-Guzik, Alán

    2010-01-29

    We extend the Runge-Gross theorem for a very general class of open quantum systems under weak assumptions about the nature of the bath and its coupling to the system. We show that for Kohn-Sham (KS) time-dependent density functional theory, it is possible to rigorously include the effects of the environment within a bath functional in the KS potential. A Markovian bath functional inspired by the theory of nonlinear Schrödinger equations is suggested, which can be readily implemented in currently existing real-time codes. Finally, calculations on a helium model system are presented.

  17. Optical properties of Al nanostructures from time dependent density functional theory

    KAUST Repository

    Mokkath, Junais Habeeb

    2016-04-05

    The optical properties of Al nanostructures are investigated by means of time dependent density functional theory, considering chains of varying length and ladders/stripes of varying aspect ratio. The absorption spectra show redshifting for increasing length and aspect ratio. For the chains the absorption is dominated by HOMO → LUMO transitions, whereas ladders and stripes reveal more complex spectra of plasmonic nature above a specific aspect ratio.

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  19. Stopping of deuterium in warm dense deuterium from Ehrenfest time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Magyar, R.J.; Shulenburger, L.; Baczewski, A.D. [Sandia National Laboratories - Multi-scale Physics 1444 MS 1322, Albuquerque, NM (United States)

    2016-06-15

    In these proceedings, we show that time-dependent density functional theory is capable of stopping calculations at the extreme conditions of temperature and pressure seen in warm dense matter. The accuracy of the stopping curves tends to be up to about 20% lower than empirical models that are in use. However, TDDFT calculations are free from fitting parameters and assumptions about the model form of the dielectric function. This work allows the simulation of ion stopping in many materials that are difficult to study experimentally. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

    Science.gov (United States)

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

    2018-04-05

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

  2. Time-dependent current-density functional theory for generalized open quantum systems.

    Science.gov (United States)

    Yuen-Zhou, Joel; Rodríguez-Rosario, César; Aspuru-Guzik, Alán

    2009-06-14

    In this article, we prove the one-to-one correspondence between vector potentials and particle and current densities in the context of master equations with arbitrary memory kernels, therefore extending time-dependent current-density functional theory (TD-CDFT) to the domain of generalized many-body open quantum systems (OQS). We also analyse the issue of A-representability for the Kohn-Sham (KS) scheme proposed by D'Agosta and Di Ventra for Markovian OQS [Phys. Rev. Lett. 2007, 98, 226403] and discuss its domain of validity. We suggest ways to expand their scheme, but also propose a novel KS scheme where the auxiliary system is both closed and non-interacting. This scheme is tested numerically with a model system, and several considerations for the future development of functionals are indicated. Our results formalize the possibility of practising TD-CDFT in OQS, hence expanding the applicability of the theory to non-Hamiltonian evolutions.

  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. Remarks on time-dependent [current]-density functional theory for open quantum systems.

    Science.gov (United States)

    Yuen-Zhou, Joel; Aspuru-Guzik, Alán

    2013-08-14

    Time-dependent [current]-density functional theory for open quantum systems (OQS) has emerged as a formalism that can incorporate dissipative effects in the dynamics of many-body quantum systems. Here, we review and clarify some formal aspects of these theories that have been recently questioned in the literature. In particular, we provide theoretical support for the following conclusions: (1) contrary to what we and others had stated before, within the master equation framework, there is in fact a one-to-one mapping between vector potentials and current densities for fixed initial state, particle-particle interaction, and memory kernel; (2) regardless of the first conclusion, all of our recently suggested Kohn-Sham (KS) schemes to reproduce the current and particle densities of the original OQS, and in particular, the use of a KS closed driven system, remains formally valid; (3) the Lindblad master equation maintains the positivity of the density matrix regardless of the time-dependence of the Hamiltonian or the dissipation operators; (4) within the stochastic Schrödinger equation picture, a one-to-one mapping from stochastic vector potential to stochastic current density for individual trajectories has not been proven so far, except in the case where the vector potential is the same for every member of the ensemble, in which case, it reduces to the Lindblad master equation picture; (5) master equations may violate certain desired properties of the density matrix, such as positivity, but they remain as one of the most useful constructs to study OQS when the environment is not easily incorporated explicitly in the calculation. The conclusions support our previous work as formally rigorous, offer new insights into it, and provide a common ground to discuss related theories.

  5. Time-dependent density functional calculation of the energy loss of antiprotons colliding with metallic nanoshells

    International Nuclear Information System (INIS)

    Quijada, M.; Borisov, A.G.; Muino, R.D.

    2008-01-01

    Time-dependent density functional theory is used to study the interaction between antiprotons and metallic nanoshells. The ground state electronic properties of the nanoshell are obtained in the jellium approximation. The energy lost by the antiproton during the collision is calculated and compared to that suffered by antiprotons traveling in metal clusters. The resulting energy loss per unit path length of material in thin nanoshells is larger than the corresponding quantity for clusters. It is shown that the collision process can be interpreted as the antiproton crossing of two nearly bi-dimensional independent metallic systems. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  6. Sequential double excitations from linear-response time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Mosquera, Martín A.; Ratner, Mark A.; Schatz, George C., E-mail: g-schatz@northwestern.edu [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chen, Lin X. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

    2016-05-28

    Traditional UV/vis and X-ray spectroscopies focus mainly on the study of excitations starting exclusively from electronic ground states. However there are many experiments where transitions from excited states, both absorption and emission, are probed. In this work we develop a formalism based on linear-response time-dependent density functional theory to investigate spectroscopic properties of excited states. We apply our model to study the excited-state absorption of a diplatinum(II) complex under X-rays, and transient vis/UV absorption of pyrene and azobenzene.

  7. Time-dependent density functional theory description of total photoabsorption cross sections

    Science.gov (United States)

    Tenorio, Bruno Nunes Cabral; Nascimento, Marco Antonio Chaer; Rocha, Alexandre Braga

    2018-02-01

    The time-dependent version of the density functional theory (TDDFT) has been used to calculate the total photoabsorption cross section of a number of molecules, namely, benzene, pyridine, furan, pyrrole, thiophene, phenol, naphthalene, and anthracene. The discrete electronic pseudo-spectra, obtained in a L2 basis set calculation were used in an analytic continuation procedure to obtain the photoabsorption cross sections. The ammonia molecule was chosen as a model system to compare the results obtained with TDDFT to those obtained with the linear response coupled cluster approach in order to make a link with our previous work and establish benchmarks.

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

    Science.gov (United States)

    Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

    2018-04-01

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

  9. Critique of the foundations of time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Schirmer, J.; Dreuw, A.

    2007-01-01

    The general expectation that, in principle, the time-dependent density-functional theory (TDDFT) is an exact formulation of the time evolution of an interacting N-electron system is critically reexamined. It is demonstrated that the previous TDDFT foundation, resting on four theorems by Runge and Gross (RG) [Phys. Rev. Lett. 52, 997 (1984)], is invalid because undefined phase factors corrupt the RG action integral functionals. Our finding confirms much of a previous analysis by van Leeuwen [Int. J. Mod. Phys. B 15, 1969 (2001)]. To analyze the RG theorems and other aspects of TDDFT, an utmost simplification of the Kohn-Sham (KS) concept has been introduced, in which the ground-state density is obtained from a single KS equation for one spatial (spinless) orbital. The time-dependent (TD) form of this radical Kohn-Sham (rKS) scheme, which has the same validity status as the ordinary KS version, has proved to be a valuable tool for analysis. The rKS concept is used to clarify also the alternative nonvariational formulation of TD KS theory. We argue that it is just a formal theory, allowing one to reproduce but not predict the time development of the exact density of the interacting N-electron system. Besides the issue of the formal exactness of TDDFT, it is shown that both the static and time-dependent KS linear response equations neglect the particle-particle (p-p) and hole-hole (h-h) matrix elements of the perturbing operator. For a local (multiplicative) operator this does not lead to a loss of information due to a remarkable general property of local operators. Accordingly, no logical inconsistency arises with respect to DFT, because DFT requires any external potential to be local. For a general nonlocal operator the error resulting from the neglected matrix elements is of second order in the electronic repulsion

  10. Excitonic effects in solids : time-dependent density functional theory versus the Bethe-Salpeter equation

    International Nuclear Information System (INIS)

    Sagmeister, S.

    2009-01-01

    The aim of this work is to compare two state-of-the-art methods for the investigation of excitonic effects in solids, namely Time-Dependent Density Functional Theory (TDDFT) and Many-Body Perturbation Theory (MBPT), for selected simple gap systems as well as semiconducting polymers. Within TDDFT, the linear response framework is used and the Dyson equation for the density-density response function is solved, whereas within MBPT, the Bethe-Salpeter equation (BSE) for the electron-hole correlation function is solved. The dielectric function is obtained as a last step. Both techniques take into account the excitonic effects caused by the interaction of electron-hole pairs. In the former these effects are included in the exchange-correlation (xc) kernel, whereas in the latter they are located in the interaction kernel of the BSE. Kohn-Sham single-particle wave functions obtained from Density Functional Theory within the linearized augmented planewave (LAPW) method are used to calculate all relevant quantities of the formalism. For the simple systems GaAs, Si and LiF are chosen. The role of several approximations to the xc kernel is studied and it is found that for GaAs and Si simple semi-empirical models provide a dielectric function in accordance with the BSE. For the case of LiF, being a system with a weak screening and a strongly bound exciton, only an xc kernel derived from MBPT yields reasonable results but still a slight discrepancy to the BSE is observed. Finally, the semiconducting polymers poly-acetylene and poly(phenylene-vinylene) (PPV) are studied. For both materials the concept of semi-empirical approximations to the xc kernel turns out to be ambiguous due to their low-dimensional character. In the case of poly-acetylene, the xc kernel derived from MBPT yields a dielectric function which is in close but not exact agreement with the one obtained from the BSE. (author) [de

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

    International Nuclear Information System (INIS)

    Thiele, M.; Kuemmel, S.

    2009-01-01

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

  12. A time-dependent density functional theory investigation of plasmon resonances of linear Au atomic chains

    International Nuclear Information System (INIS)

    Liu Dan-Dan; Zhang Hong

    2011-01-01

    We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time-dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  13. Optical rotation calculated with time-dependent density functional theory: the OR45 benchmark.

    Science.gov (United States)

    Srebro, Monika; Govind, Niranjan; de Jong, Wibe A; Autschbach, Jochen

    2011-10-13

    Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and three transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 × 10(4) deg cm(2) dmol(-1). The performances of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LC-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LC-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.

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

    Science.gov (United States)

    Chen, Shuguang; Kwok, YanHo; Chen, GuanHua

    2018-02-20

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

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

    Science.gov (United States)

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

    2012-06-01

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

  16. 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.

  17. Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

    Science.gov (United States)

    Sears, John S.; Koerzdoerfer, Thomas; Zhang, Cai-Rong; Brédas, Jean-Luc

    2011-10-01

    Long-range corrected hybrids represent an increasingly popular class of functionals for density functional theory (DFT) that have proven to be very successful for a wide range of chemical applications. In this Communication, we examine the performance of these functionals for time-dependent (TD)DFT descriptions of triplet excited states. Our results reveal that the triplet energies are particularly sensitive to the range-separation parameter; this sensitivity can be traced back to triplet instabilities in the ground state coming from the large effective amounts of Hartree-Fock exchange included in these functionals. As such, the use of standard long-range corrected functionals for the description of triplet states at the TDDFT level is not recommended.

  18. Why Density Dependent Propulsion?

    Science.gov (United States)

    Robertson, Glen A.

    2011-01-01

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

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

    International Nuclear Information System (INIS)

    Thiele, Mark

    2009-01-01

    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.)

  20. 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.)

  1. Time-dependent internal density functional theory formalism and Kohn-Sham scheme for self-bound systems

    International Nuclear Information System (INIS)

    Messud, Jeremie

    2009-01-01

    The stationary internal density functional theory (DFT) formalism and Kohn-Sham scheme are generalized to the time-dependent case. It is proven that, in the time-dependent case, the internal properties of a self-bound system (such as an atomic nuclei or a helium droplet) are all defined by the internal one-body density and the initial state. A time-dependent internal Kohn-Sham scheme is set up as a practical way to compute the internal density. The main difference from the traditional DFT formalism and Kohn-Sham scheme is the inclusion of the center-of-mass correlations in the functional.

  2. Time-dependent density functional methods for Raman spectra in open-shell systems.

    Science.gov (United States)

    Aquino, Fredy W; Schatz, George C

    2014-01-16

    We present an implementation of a time-dependent density functional theory (TD-DFT) linear response module in NWChem for unrestricted DFT calculations and apply it to the calculation of resonant Raman spectra in open-shell molecular systems using the short-time approximation. The new source code was validated and applied to simulate Raman spectra on several doublet organic radicals (e.g., benzyl, benzosemiquinone, TMPD, trans-stilbene anion and cation, and methyl viologen) and the metal complex copper phthalocyanine. We also introduce a divide-and-conquer approach for the evaluation of polarizabilities in relatively large systems (e.g., copper phthalocyanine). The implemented tool gives comparisons with experiment that are similar to what is commonly found for closed-shell systems, with good agreement for most features except for small frequency shifts, and occasionally large deviations for some modes that depend on the molecular system studied, experimental conditions not being accounted in the modeling such as solvation effects and extra solvent-based peaks, and approximations in the underlying theory. The approximations used in the quantum chemical modeling include (i) choice of exchange-correlation functional and basis set; (ii) harmonic approximation used in the frequency analysis to determine vibrational normal modes; and (iii) short-time approximation (omission of nuclear motion effects) used in calculating resonant Raman spectra.

  3. Orbital-dependent exchange-correlation functionals in density-functional theory realized by the FLAPW method

    Energy Technology Data Exchange (ETDEWEB)

    Betzinger, Markus

    2011-12-14

    In this thesis, we extended the applicability of the full-potential linearized augmented-plane-wave (FLAPW) method, one of the most precise, versatile and generally applicable electronic structure methods for solids working within the framework of density-functional theory (DFT), to orbital-dependent functionals for the exchange-correlation (xc) energy. Two different schemes that deal with orbital-dependent functionals, the Kohn-Sham (KS) and the generalized Kohn-Sham (gKS) formalism, have been realized. Hybrid functionals, combining some amount of the orbital-dependent exact exchange energy with local or semi-local functionals of the density, are implemented within the gKS scheme. We work in particular with the PBE0 hybrid of Perdew, Burke, and Ernzerhof. Our implementation relies on a representation of the non-local exact exchange potential - its calculation constitutes the most time consuming step in a practical calculation - by an auxiliary mixed product basis (MPB). In this way, the matrix elements of the Hamiltonian corresponding to the non-local potential become a Brillouin-zone (BZ) sum over vector-matrix-vector products. Several techniques are developed and explored to further accelerate our numerical scheme. We show PBE0 results for a variety of semiconductors and insulators. In comparison with experiment, the PBE0 functional leads to improved band gaps and an improved description of localized states. Even for the ferromagnetic semiconductor EuO with localized 4f electrons, the electronic and magnetic properties are correctly described by the PBE0 functional. Subsequently, we discuss the construction of the local, multiplicative exact exchange (EXX) potential from the non-local, orbital-dependent exact exchange energy. For this purpose we employ the optimized effective potential (OEP) method. Central ingredients of the OEP equation are the KS wave-function response and the single-particle density response function. We show that a balance between the LAPW

  4. Orbital-dependent exchange-correlation functionals in density-functional theory realized by the FLAPW method

    International Nuclear Information System (INIS)

    Betzinger, Markus

    2011-01-01

    In this thesis, we extended the applicability of the full-potential linearized augmented-plane-wave (FLAPW) method, one of the most precise, versatile and generally applicable electronic structure methods for solids working within the framework of density-functional theory (DFT), to orbital-dependent functionals for the exchange-correlation (xc) energy. Two different schemes that deal with orbital-dependent functionals, the Kohn-Sham (KS) and the generalized Kohn-Sham (gKS) formalism, have been realized. Hybrid functionals, combining some amount of the orbital-dependent exact exchange energy with local or semi-local functionals of the density, are implemented within the gKS scheme. We work in particular with the PBE0 hybrid of Perdew, Burke, and Ernzerhof. Our implementation relies on a representation of the non-local exact exchange potential - its calculation constitutes the most time consuming step in a practical calculation - by an auxiliary mixed product basis (MPB). In this way, the matrix elements of the Hamiltonian corresponding to the non-local potential become a Brillouin-zone (BZ) sum over vector-matrix-vector products. Several techniques are developed and explored to further accelerate our numerical scheme. We show PBE0 results for a variety of semiconductors and insulators. In comparison with experiment, the PBE0 functional leads to improved band gaps and an improved description of localized states. Even for the ferromagnetic semiconductor EuO with localized 4f electrons, the electronic and magnetic properties are correctly described by the PBE0 functional. Subsequently, we discuss the construction of the local, multiplicative exact exchange (EXX) potential from the non-local, orbital-dependent exact exchange energy. For this purpose we employ the optimized effective potential (OEP) method. Central ingredients of the OEP equation are the KS wave-function response and the single-particle density response function. We show that a balance between the LAPW

  5. Relativistic Adiabatic Time-Dependent Density Functional Theory Using Hybrid Functionals and Noncollinear Spin Magnetization

    DEFF Research Database (Denmark)

    Bast, Radovan; Jensen, Hans Jørgen Aagaard; Saue, Trond

    2009-01-01

    into reduction of algebra from quaternion to complex or real. For hybrid GGAs with noncollinear spin magnetization we derive a new computationally advantageous equation for the full second variational derivatives of such exchange-correlation functionals. We apply our implementation to calculations on the ns2...... → ns1np1 excitation energies in the Zn, Cd, and Hg atoms (n = 4-6) and (vertical) excitation energies of UO2+ 2 ; and we test the performance of various functionals by comparison with experimental data (group 12 atoms) or higher-level computational results (UO2+2 ). The results indicate...

  6. Time-dependent density functional theory beyond Kohn-Sham Slater determinants.

    Science.gov (United States)

    Fuks, Johanna I; Nielsen, Søren E B; Ruggenthaler, Michael; Maitra, Neepa T

    2016-08-03

    When running time-dependent density functional theory (TDDFT) calculations for real-time simulations of non-equilibrium dynamics, the user has a choice of initial Kohn-Sham state, and typically a Slater determinant is used. We explore the impact of this choice on the exchange-correlation potential when the physical system begins in a 50 : 50 superposition of the ground and first-excited state of the system. We investigate the possibility of judiciously choosing a Kohn-Sham initial state that minimizes errors when adiabatic functionals are used. We find that if the Kohn-Sham state is chosen to have a configuration matching the one that dominates the interacting state, this can be achieved for a finite time duration for some but not all such choices. When the Kohn-Sham system does not begin in a Slater determinant, we further argue that the conventional splitting of the exchange-correlation potential into exchange and correlation parts has limited value, and instead propose a decomposition into a "single-particle" contribution that we denote v, and a remainder. The single-particle contribution can be readily computed as an explicit orbital-functional, reduces to exchange in the Slater determinant case, and offers an alternative to the adiabatic approximation as a starting point for TDDFT approximations.

  7. Curvature Dependence of Interfacial Properties for Associating Lennard—Jones Fluids: A Density Functional Study

    International Nuclear Information System (INIS)

    Sun Zong-Li; Kang Yan-Shuang

    2011-01-01

    Classical density functional theory is used to study the associating Lennard—Jones fluids in contact with spherical hard wall of different curvature radii. The interfacial properties including contact density and fluid-solid interfacial tension are investigated. The influences of associating energy, curvature of hard wall and the bulk density of fluids on these properties are analyzed in detail. The results may provide helpful clues to understand the interfacial properties of other complex fluids. (condensed matter: structure, mechanical and thermal properties)

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  9. Time-dependent density-functional theory in massively parallel computer architectures: the OCTOPUS project.

    Science.gov (United States)

    Andrade, Xavier; Alberdi-Rodriguez, Joseba; Strubbe, David A; Oliveira, Micael J T; Nogueira, Fernando; Castro, Alberto; Muguerza, Javier; Arruabarrena, Agustin; Louie, Steven G; Aspuru-Guzik, Alán; Rubio, Angel; Marques, Miguel A L

    2012-06-13

    Octopus is a general-purpose density-functional theory (DFT) code, with a particular emphasis on the time-dependent version of DFT (TDDFT). In this paper we present the ongoing efforts to achieve the parallelization of octopus. We focus on the real-time variant of TDDFT, where the time-dependent Kohn-Sham equations are directly propagated in time. This approach has great potential for execution in massively parallel systems such as modern supercomputers with thousands of processors and graphics processing units (GPUs). For harvesting the potential of conventional supercomputers, the main strategy is a multi-level parallelization scheme that combines the inherent scalability of real-time TDDFT with a real-space grid domain-partitioning approach. A scalable Poisson solver is critical for the efficiency of this scheme. For GPUs, we show how using blocks of Kohn-Sham states provides the required level of data parallelism and that this strategy is also applicable for code optimization on standard processors. Our results show that real-time TDDFT, as implemented in octopus, can be the method of choice for studying the excited states of large molecular systems in modern parallel architectures.

  10. Time-dependent density-functional theory in massively parallel computer architectures: the octopus project

    Science.gov (United States)

    Andrade, Xavier; Alberdi-Rodriguez, Joseba; Strubbe, David A.; Oliveira, Micael J. T.; Nogueira, Fernando; Castro, Alberto; Muguerza, Javier; Arruabarrena, Agustin; Louie, Steven G.; Aspuru-Guzik, Alán; Rubio, Angel; Marques, Miguel A. L.

    2012-06-01

    Octopus is a general-purpose density-functional theory (DFT) code, with a particular emphasis on the time-dependent version of DFT (TDDFT). In this paper we present the ongoing efforts to achieve the parallelization of octopus. We focus on the real-time variant of TDDFT, where the time-dependent Kohn-Sham equations are directly propagated in time. This approach has great potential for execution in massively parallel systems such as modern supercomputers with thousands of processors and graphics processing units (GPUs). For harvesting the potential of conventional supercomputers, the main strategy is a multi-level parallelization scheme that combines the inherent scalability of real-time TDDFT with a real-space grid domain-partitioning approach. A scalable Poisson solver is critical for the efficiency of this scheme. For GPUs, we show how using blocks of Kohn-Sham states provides the required level of data parallelism and that this strategy is also applicable for code optimization on standard processors. Our results show that real-time TDDFT, as implemented in octopus, can be the method of choice for studying the excited states of large molecular systems in modern parallel architectures.

  11. Time-dependent density-functional theory in massively parallel computer architectures: the octopus project

    International Nuclear Information System (INIS)

    Andrade, Xavier; Aspuru-Guzik, Alán; Alberdi-Rodriguez, Joseba; Rubio, Angel; Strubbe, David A; Louie, Steven G; Oliveira, Micael J T; Nogueira, Fernando; Castro, Alberto; Muguerza, Javier; Arruabarrena, Agustin; Marques, Miguel A L

    2012-01-01

    Octopus is a general-purpose density-functional theory (DFT) code, with a particular emphasis on the time-dependent version of DFT (TDDFT). In this paper we present the ongoing efforts to achieve the parallelization of octopus. We focus on the real-time variant of TDDFT, where the time-dependent Kohn-Sham equations are directly propagated in time. This approach has great potential for execution in massively parallel systems such as modern supercomputers with thousands of processors and graphics processing units (GPUs). For harvesting the potential of conventional supercomputers, the main strategy is a multi-level parallelization scheme that combines the inherent scalability of real-time TDDFT with a real-space grid domain-partitioning approach. A scalable Poisson solver is critical for the efficiency of this scheme. For GPUs, we show how using blocks of Kohn-Sham states provides the required level of data parallelism and that this strategy is also applicable for code optimization on standard processors. Our results show that real-time TDDFT, as implemented in octopus, can be the method of choice for studying the excited states of large molecular systems in modern parallel architectures. (topical review)

  12. 2007 Time_Dependent Density-Functional Therory (July 15-20, 2007 Colby College, Maine)

    Energy Technology Data Exchange (ETDEWEB)

    Ullrich Carsten

    2008-09-19

    Time-dependent density-functional theory (TDDFT) provides an efficient, elegant, and formally exact way of describing the dynamics of interacting many-body quantum systems, circumventing the need for solving the full time-dependent Schroedinger equation. In the 20 years since it was first rigorously established in 1984, the field of TDDFT has made rapid and significant advances both formally as well as in terms of successful applications in chemistry, physics and materials science. Today, TDDFT has become the method of choice for calculating excitation energies of complex molecules, and is becoming increasingly popular for describing optical and spectroscopic properties of a variety of materials such as bulk solids, clusters and nanostructures. Other growing areas of applications of TDDFT are nonlinear dynamics of strongly excited electronic systems and molecular electronics. The purpose and scope of this Gordon Research Conference is to provide a platform for discussing the current state of the art of the rapidly progressing, highly interdisciplinary field of TDDFT, to identify and debate open questions, and to point out new promising research directions. The conference will bring together experts with a diverse background in chemistry, physics, and materials science.

  13. Time-Dependent Density Functional Theory Analysis of Triphenylamine-Functionalized Graphene Doped with Transition Metals for Photocatalytic Hydrogen Production.

    Science.gov (United States)

    Mota, Elder A V; Neto, Abel F G; Marques, Francisco C; Mota, Gunar V S; Martins, Marcelo G; Costa, Fabio L P; Borges, Rosivaldo S; Neto, Antonio M J C

    2018-07-01

    The electronic structures and optical properties of triphenylamine-functionalized graphene (G-TPA) doped with transition metals, using water as a solvent, were theoretically investigated to verify the efficiency of photocatalytic hydrogen production with the use of transition metals. This study was performed by Density Functional Theory and Time-dependent Density Functional Theory through Gaussian 09W software, adopting the B3LYP functional for all structures. The 6-31g(d) basis set was used for H, C and N atoms, and the LANL2DZ basis set for transition metals using the Effective Core Potentials method. Two approaches were adopted: (1) using single metallic dopants (Ni, Pd, Fe, Os and Pt) and (2) using combinations of Ni with the other dopants (NiPd, NiPt, NiFe and NiOs). The DOS spectra reveal an increase of accessible states in the valence shell, in addition to a gap decrease for all dopants. This doping also increases the absorption in the visible region of solar radiation where sunlight is most intense (400 nm to 700 nm), with additional absorption peaks. The results lead us to propose the G-TPA structures doped with Ni, Pd, Pt, NiPt or NiPd to be novel catalysts for the conversion of solar energy for photocatalytic hydrogen production, since they improve the absorption of solar energy in the range of interest for solar radiation; and act as reaction centers, reducing the required overpotential for hydrogen production from water.

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

    International Nuclear Information System (INIS)

    Attarian Shandiz, M.; Gauvin, R.

    2014-01-01

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

  15. Time-dependent density functional theory for open systems with a positivity-preserving decomposition scheme for environment spectral functions

    International Nuclear Information System (INIS)

    Wang, RuLin; Zheng, Xiao; Kwok, YanHo; Xie, Hang; Chen, GuanHua; Yam, ChiYung

    2015-01-01

    Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene

  16. Time-dependent density functional theory for open systems with a positivity-preserving decomposition scheme for environment spectral functions.

    Science.gov (United States)

    Wang, RuLin; Zheng, Xiao; Kwok, YanHo; Xie, Hang; Chen, GuanHua; Yam, ChiYung

    2015-04-14

    Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene.

  17. Density dependent hadron field theory

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  18. Simulating Excitons in MoS2 with Time-Dependent Density Functional Theory

    Science.gov (United States)

    Flamant, Cedric; Kolesov, Grigory; Kaxiras, Efthimios

    Monolayer molybdenum disulfide, owing to its graphene-like two-dimensional geometry whilst still having a finite bandgap, is a material of great interest in condensed matter physics and for potential application in electronic devices. In particular, MoS2 exhibits significant excitonic effects, a desirable quality for fundamental many-body research. Time-dependent density functional theory (TD-DFT) allows us to simulate dynamical effects as well as temperature-based effects in a natural way given the direct treatment of the time evolution of the system. We present a TD-DFT study of monolayer MoS2 exciton dynamics, examining various qualitative and quantitative predictions in pure samples and in the presence of defects. In particular, we generate an absorption spectrum through simulated pulse excitation for comparison to experiment and also analyze the response of the exciton in an external electric field.In this work we also discuss the electronic structure of the exciton in MoS2 with and without vacancies.

  19. Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation

    Energy Technology Data Exchange (ETDEWEB)

    Franco de Carvalho, F. [Centre Européen de Calcul Atomique et Moléculaire, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Tavernelli, I. [IBM Research GmbH, Zurich Research Laboratory, 8803 Ruschlikon (Switzerland)

    2015-12-14

    In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO{sub 2}) in gas and liquid phases.

  20. Time dependentdensity functional theory characterization of organic dyes for dye-sensitized solar cells

    KAUST Repository

    Hilal, Rifaat

    2017-06-19

    We aim at providing better insight into the parameters that govern the intramolecular charge transfer (ICT) and photo-injection processes in dyes for dye-sensitised solar cells (DSSC). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are utilized to study the geometry, electronic structure, electrostatic potential (ESP) and absorption spectrum, for a representative donor-π bridge-acceptor (D–π–A) dye for DSSC. The coplanar geometry of the dye (D1) facilitates strong conjugation and considerable delocalization originating the π CT interaction from donor to acceptor orbitals and the hyper-conjugative interactions involving Rydberg states. A model simulating the adsorption of the dye on the TiO surface is utilized to estimate binding energies. The effect of fluorine substituents in the π-spacer on the quantum efficiency of DSSCs was investigated. Gibb’s free energy values, redox potentials, excited state lifetime, non-linear optical properties (NLO) and driving forces for D1 and its fluorinated derivatives were computed.

  1. Efficient block preconditioned eigensolvers for linear response time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Vecharynski, Eugene [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Brabec, Jiri [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Shao, Meiyue [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Govind, Niranjan [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab.; Yang, Chao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division

    2017-12-01

    We present two efficient iterative algorithms for solving the linear response eigen- value problem arising from the time dependent density functional theory. Although the matrix to be diagonalized is nonsymmetric, it has a special structure that can be exploited to save both memory and floating point operations. In particular, the nonsymmetric eigenvalue problem can be transformed into a product eigenvalue problem that is self-adjoint with respect to a K-inner product. This product eigenvalue problem can be solved efficiently by a modified Davidson algorithm and a modified locally optimal block preconditioned conjugate gradient (LOBPCG) algorithm that make use of the K-inner product. The solution of the product eigenvalue problem yields one component of the eigenvector associated with the original eigenvalue problem. However, the other component of the eigenvector can be easily recovered in a postprocessing procedure. Therefore, the algorithms we present here are more efficient than existing algorithms that try to approximate both components of the eigenvectors simultaneously. The efficiency of the new algorithms is demonstrated by numerical examples.

  2. Trajectory-based nonadiabatic dynamics with time-dependent density functional theory.

    Science.gov (United States)

    Curchod, Basile F E; Rothlisberger, Ursula; Tavernelli, Ivano

    2013-05-10

    Understanding the fate of an electronically excited molecule constitutes an important task for theoretical chemistry, and practical implications range from the interpretation of atto- and femtosecond spectroscopy to the development of light-driven molecular machines, the control of photochemical reactions, and the possibility of capturing sunlight energy. However, many challenging conceptual and technical problems are involved in the description of these phenomena such as 1) the failure of the well-known Born-Oppenheimer approximation; 2) the need for accurate electronic properties such as potential energy surfaces, excited nuclear forces, or nonadiabatic coupling terms; and 3) the necessity of describing the dynamics of the photoexcited nuclear wavepacket. This review provides an overview of the current methods to address points 1) and 3) and shows how time-dependent density functional theory (TDDFT) and its linear-response extension can be used for point 2). First, the derivation of Ehrenfest dynamics and nonadiabatic Bohmian dynamics is discussed and linked to Tully's trajectory surface hopping. Second, the coupling of these trajectory-based nonadiabatic schemes with TDDFT is described in detail with special emphasis on the derivation of the required electronic structure properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Two-electron Rabi oscillations in real-time time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Habenicht, Bradley F.; Tani, Noriyuki P.; Provorse, Makenzie R.; Isborn, Christine M.

    2014-01-01

    We investigate the Rabi oscillations of electrons excited by an applied electric field in several simple molecular systems using time-dependent configuration interaction (TDCI) and real-time time-dependent density-functional theory (RT-TDDFT) dynamics. While the TDCI simulations exhibit the expected single-electron Rabi oscillations at a single resonant electric field frequency, Rabi oscillations in the RT-TDDFT simulations are a two-electron process. The existence of two-electron Rabi oscillations is determined both by full population inversion between field-free molecular orbitals and the behavior of the instantaneous dipole moment during the simulations. Furthermore, the Rabi oscillations in RT-TDDFT are subject to an intensity threshold of the electric field, below which Rabi oscillations do not occur and above which the two-electron Rabi oscillations occur at a broad range of frequencies. It is also shown that at field intensities near the threshold intensity, the field frequency predicted to induce Rabi oscillations by linear response TDDFT only produces detuned Rabi oscillations. Instead, the field frequency that yields the full two-electron population inversion and Rabi oscillation behavior is shown to be the average of single-electron transition frequencies from the ground S 0 state and the doubly-excited S 2 state. The behavior of the two-electron Rabi oscillations is rationalized via two possible models. The first model is a multi-photon process that results from the electric field interacting with the three level system such that three level Rabi oscillations may occur. The second model suggests that the mean-field nature of RT-TDDFT induces paired electron propagation

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

    Directory of Open Access Journals (Sweden)

    Guo-Jun Kang

    2016-11-01

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

  5. A (time-dependent) density functional theory study of the optoelectronic properties of bis-triisopropylsilylethynyl-functionalized acenes

    International Nuclear Information System (INIS)

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

    2013-01-01

    We report a comparative study of the optoelectronic properties of small acenes (benzene, anthracene, and pentacene) and their bis-triisopropylsilylethynyl (TIPS) functionalized counterparts. We computed the fundamental gap using density functional theory (DFT) in the framework of the ΔSCF scheme, and the optical absorption spectra by means of time-dependent DFT. Upon TIPS functionalization we observed a lowering of the ionization energy and a rise of the electron affinity; we consequently predict a systematic reduction of the fundamental electronic gap which decreases from ∼ 40% for benzene to ∼ 16% for pentacene. This trend is reflected in the computed optical absorption spectra: for all TIPS-molecules the onset of absorption is red-shifted as compared to their plain precursors. In the case of TIPS-pentacene, in particular, the computed spectrum agrees with the available experimental data. - Highlights: • We evaluate the effect of triisopropylsilylethynyl (TIPS)-substitution on acenes. • We compared the fundamental gap and the optical absorption as a function of size. • We found a general gap reduction following TIPS functionalization. • The gap reduction decreases at increasing size, from 40% for n = 1 to 16% for n = 5. • The onset of absorption is red-shifted as compared to TIPS precursors

  6. A (time-dependent) density functional theory study of the optoelectronic properties of bis-triisopropylsilylethynyl-functionalized acenes

    Energy Technology Data Exchange (ETDEWEB)

    Malloci, G., E-mail: giuliano.malloci@dsf.unica.it [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Cappellini, G. [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Mulas, G. [INAF-Osservatorio Astronomico di Cagliari, Strada 54, Località Poggio dei Pini, I-09012 Capoterra (Italy); Mattoni, A. [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy)

    2013-09-30

    We report a comparative study of the optoelectronic properties of small acenes (benzene, anthracene, and pentacene) and their bis-triisopropylsilylethynyl (TIPS) functionalized counterparts. We computed the fundamental gap using density functional theory (DFT) in the framework of the ΔSCF scheme, and the optical absorption spectra by means of time-dependent DFT. Upon TIPS functionalization we observed a lowering of the ionization energy and a rise of the electron affinity; we consequently predict a systematic reduction of the fundamental electronic gap which decreases from ∼ 40% for benzene to ∼ 16% for pentacene. This trend is reflected in the computed optical absorption spectra: for all TIPS-molecules the onset of absorption is red-shifted as compared to their plain precursors. In the case of TIPS-pentacene, in particular, the computed spectrum agrees with the available experimental data. - Highlights: • We evaluate the effect of triisopropylsilylethynyl (TIPS)-substitution on acenes. • We compared the fundamental gap and the optical absorption as a function of size. • We found a general gap reduction following TIPS functionalization. • The gap reduction decreases at increasing size, from 40% for n = 1 to 16% for n = 5. • The onset of absorption is red-shifted as compared to TIPS precursors.

  7. Evaluation of exchange-correlation functionals for time-dependent density functional theory calculations on metal complexes.

    Science.gov (United States)

    Holland, Jason P; Green, Jennifer C

    2010-04-15

    The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) 0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes. 2009 Wiley Periodicals, Inc.

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

    Science.gov (United States)

    Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

    2018-03-01

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

  9. Time-dependent density functional theory study of the luminescence properties of gold phosphine thiolate complexes.

    Science.gov (United States)

    Guidez, Emilie B; Aikens, Christine M

    2015-04-09

    The origin of the emission of the gold phosphine thiolate complex (TPA)AuSCH(CH3)2 (TPA = 1,3,5-triaza-7-phosphaadamantanetriylphosphine) is investigated using time-dependent density functional theory (TDDFT). This system absorbs light at 3.6 eV, which corresponds mostly to a ligand-to-metal transition with some interligand character. The P-Au-S angle decreases upon relaxation in the S1 and T1 states. Our calculations show that these two states are strongly spin-orbit coupled at the ground state geometry. Ligand effects on the optical properties of this complex are also discussed by looking at the simple AuP(CH3)3SCH3 complex. The excitation energies differ by several tenths of an electronvolt. Excited state optimizations show that the excited singlet and triplet of the (TPA)AuSCH(CH3)2 complex are bent. On the other hand, the Au-S bond breaks in the excited state for the simple complex, and TDDFT is no longer an adequate method. The excited state energy landscape of gold phosphine thiolate systems is very complex, with several state crossings. This study also shows that the formation of the [(TPA)AuSCH(CH3)2]2 dimer is favorable in the ground state. The inclusion of dispersion interactions in the calculations affects the optimized geometries of both ground and excited states. Upon excitation, the formation of a Au-Au bond occurs, which results in an increase in energy of the low energy excited states in comparison to the monomer. The experimentally observed emission of the (TPA)AuSCH(CH3)2 complex at 1.86 eV cannot be unambiguously assigned and may originate from several excited states.

  10. Quantum computing without wavefunctions: time-dependent density functional theory for universal quantum computation.

    Science.gov (United States)

    Tempel, David G; Aspuru-Guzik, Alán

    2012-01-01

    We prove that the theorems of TDDFT can be extended to a class of qubit Hamiltonians that are universal for quantum computation. The theorems of TDDFT applied to universal Hamiltonians imply that single-qubit expectation values can be used as the basic variables in quantum computation and information theory, rather than wavefunctions. From a practical standpoint this opens the possibility of approximating observables of interest in quantum computations directly in terms of single-qubit quantities (i.e. as density functionals). Additionally, we also demonstrate that TDDFT provides an exact prescription for simulating universal Hamiltonians with other universal Hamiltonians that have different, and possibly easier-to-realize two-qubit interactions. This establishes the foundations of TDDFT for quantum computation and opens the possibility of developing density functionals for use in quantum algorithms.

  11. Density dependent effective interactions

    International Nuclear Information System (INIS)

    Dortmans, P.J.; Amos, K.

    1994-01-01

    An effective nucleon-nucleon interaction is defined by an optimal fit to select on-and half-off-of-the-energy shell t-and g-matrices determined by solutions of the Lippmann-Schwinger and Brueckner-Bethe-Goldstone equations with the Paris nucleon-nucleon interaction as input. As such, it is seen to better reproduce the interaction on which it is based than other commonly used density dependent effective interactions. The new (medium modified) effective interaction when folded with appropriate density matrices, has been used to define proton- 12 C and proton- 16 O optical potentials. With them elastic scattering data are well fit and the medium effects identifiable. 23 refs., 8 figs

  12. Time-dependent occupation numbers in reduced-density-matrix-functional theory: Application to an interacting Landau-Zener model

    International Nuclear Information System (INIS)

    Requist, Ryan; Pankratov, Oleg

    2011-01-01

    We prove that if the two-body terms in the equation of motion for the one-body reduced density matrix are approximated by ground-state functionals, the eigenvalues of the one-body reduced density matrix (occupation numbers) remain constant in time. This deficiency is related to the inability of such an approximation to account for relative phases in the two-body reduced density matrix. We derive an exact differential equation giving the functional dependence of these phases in an interacting Landau-Zener model and study their behavior in short- and long-time regimes. The phases undergo resonances whenever the occupation numbers approach the boundaries of the interval [0,1]. In the long-time regime, the occupation numbers display correlation-induced oscillations and the memory dependence of the functionals assumes a simple form.

  13. Determining the functional form of density dependence: deductive approaches for consumer-resource systems having a single resource.

    Science.gov (United States)

    Abrams, Peter A

    2009-09-01

    Consumer-resource models are used to deduce the functional form of density dependence in the consumer population. A general approach to determining the form of consumer density dependence is proposed; this involves determining the equilibrium (or average) population size for a series of different harvest rates. The relationship between a consumer's mortality and its equilibrium population size is explored for several one-consumer/one-resource models. The shape of density dependence in the resource and the shape of the numerical and functional responses all tend to be "inherited" by the consumer's density dependence. Consumer-resource models suggest that density dependence will very often have both concave and convex segments, something that is impossible under the commonly used theta-logistic model. A range of consumer-resource models predicts that consumer population size often declines at a decelerating rate with mortality at low mortality rates, is insensitive to or increases with mortality over a wide range of intermediate mortalities, and declines at a rapidly accelerating rate with increased mortality when mortality is high. This has important implications for management and conservation of natural populations.

  14. Environment-dependent crystal-field tight-binding based on density-functional theory

    International Nuclear Information System (INIS)

    Urban, Alexander

    2012-01-01

    Electronic structure calculations based on Kohn-Sham density-functional theory (DFT) allow the accurate prediction of chemical bonding and materials properties. Due to the high computational demand DFT calculations are, however, restricted to structures containing at most several hundreds of atoms, i.e., to length scales of a few nanometers. Though, many processes of technological relevance, for example in the field of nanoelectronics, are governed by phenomena that occur on a slightly larger length scale of up to 100 nanometers, which corresponds to tens of thousands of atoms. The semiempirical Slater-Koster tight-binding (TB) method makes it feasible to calculate the electronic structure of such large systems. In contrast to first-principles-based DFT, which is universally applicable to almost all chemical species, the TB method is based on parametrized models that are usually specialized for a particular application or for one certain class of compounds. Usually the model parameters (Slater-Koster tables) are empirically adjusted to reproduce either experimental reference data (e.g., geometries, elastic constants) or data from first-principles methods such as DFT. The construction of a new TB model is therefore connected with a considerable effort that is often contrasted by a low transferability of the parametrization. In this thesis we develop a systematic methodology for the derivation of accurate and transferable TB models from DFT calculations. Our procedure exploits the formal relationship between the two methods, according to which the TB total energy can be understood as a direct approximation of the Kohn--Sham energy functional. The concept of our method is different to previous approaches such as the DFTB method, since it allows to extract TB parameters from converged DFT wave functions and Hamiltonians of arbitrary reference structures. In the following the different subjects of this thesis are briefly summarized. We introduce a new technique for the

  15. Numerical implementation of time-dependent density functional theory for extended systems in extreme environments

    Energy Technology Data Exchange (ETDEWEB)

    Baczewski, Andrew David; Shulenburger, Luke; Desjarlais, Michael Paul; Magyar, Rudolph J.

    2014-02-01

    In recent years, DFT-MD has been shown to be a useful computational tool for exploring the properties of WDM. These calculations achieve excellent agreement with shock compression experiments, which probe the thermodynamic parameters of the Hugoniot state. New X-ray Thomson Scattering diagnostics promise to deliver independent measurements of electronic density and temperature, as well as structural information in shocked systems. However, they require the development of new levels of theory for computing the associated observables within a DFT framework. The experimentally observable x-ray scattering cross section is related to the electronic density-density response function, which is obtainable using TDDFT - a formally exact extension of conventional DFT that describes electron dynamics and excited states. In order to develop a capability for modeling XRTS data and, more generally, to establish a predictive capability for rst principles simulations of matter in extreme conditions, real-time TDDFT with Ehrenfest dynamics has been implemented in an existing PAW code for DFT-MD calculations. The purpose of this report is to record implementation details and benchmarks as the project advances from software development to delivering novel scienti c results. Results range from tests that establish the accuracy, e ciency, and scalability of our implementation, to calculations that are veri ed against accepted results in the literature. Aside from the primary XRTS goal, we identify other more general areas where this new capability will be useful, including stopping power calculations and electron-ion equilibration.

  16. Time-dependent reduced density matrix functional theory applied to laser-driven, correlated two-electron dynamics

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-07-01

    Time-dependent density functional theory (TDDFT) with known and practicable exchange-correlation potentials does not capture highly correlated electron dynamics such as single-photon double ionization, autoionization, or nonsequential ionization. Time-dependent reduced density matrix functional theory (TDRDMFT) may remedy these problems. The key ingredients in TDRDMFT are the natural orbitals (NOs), i.e., the eigenfunctions of the one-body reduced density matrix (1-RDM), and the occupation numbers (OCs), i.e., the respective eigenvalues. The two-body reduced density matrix (2-RDM) is then expanded in NOs, and equations of motion for the NOs can be derived. If the expansion coefficients of the 2-RDM were known exactly, the problem at hand would be solved. In practice, approximations have to be made. We study the prospects of TDRDMFT following a top-down approach. We solve the exact two-electron time-dependent Schroedinger equation for a model Helium atom in intense laser fields in order to study highly correlated phenomena such as the population of autoionizing states or single-photon double ionization. From the exact wave function we calculate the exact NOs, OCs, the exact expansion coefficients of the 2-RDM, and the exact potentials in the equations of motion. In that way we can identify how many NOs and which level of approximations are necessary to capture such phenomena.

  17. Pressure-Dependent Electronic and Transport Properties of Bulk Platinum Oxide by Density Functional Theory

    Science.gov (United States)

    Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh; Nekrasov, Kirill A.; Kichigina, Natalia V.

    2018-02-01

    The structural, electronic, and vibrational properties of bulk platinum oxide (PtO) at compressive pressures in the interval from 0 GPa to 35 GPa are investigated using the density functional theory. The calculated electronic band structure of PtO shows poor metallicity at very low density of states on the Fermi level. However, the hybrid pseudopotential calculation yielded 0.78 eV and 1.30 eV direct band and indirect gap, respectively. Importantly, our results predict that PtO has a direct band gap within the framework of HSE06, and it prefers equally zero magnetic order at different pressures. In the Raman spectra, peaks are slightly shifted towards higher frequency with the decrease in pressure. We have also calculated the thermoelectric properties, namely the electronic thermal conductivity and electrical conductivity, with respect to temperature and thermodynamic properties such as entropy, specific heat at constant volume, enthalpy and Gibbs free energy with respect to pressure. The result shows that PtO is a promising candidate for use as a catalyst, in sensors, as a photo-cathode in water electrolysis, for thermal decomposition of inorganic salt and fuel cells.

  18. Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

    Science.gov (United States)

    Guido, Ciro A; Jacquemin, Denis; Adamo, Carlo; Mennucci, Benedetta

    2015-12-08

    We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.

  19. Time-dependent density functional theory for nonlinear properties of open-shell systems.

    Science.gov (United States)

    Rinkevicius, Zilvinas; Jha, Prakash Chandra; Oprea, Corneliu I; Vahtras, Olav; Agren, Hans

    2007-09-21

    This paper presents response theory based on a spin-restricted Kohn-Sham formalism for computation of time-dependent and time-independent nonlinear properties of molecules with a high spin ground state. The developed approach is capable to handle arbitrary perturbations and constitutes an efficient procedure for evaluation of electric, magnetic, and mixed properties. Apart from presenting the derivation of the proposed approach, we show results from illustrating calculations of static and dynamic hyperpolarizabilities of small Si(3n+1)H(6n+3) (n=0,1,2) clusters which mimic Si(111) surfaces with dangling bond defects. The results indicate that the first hyperpolarizability tensor components of Si(3n+1)H(6n+3) have an ordering compatible with the measurements of second harmonic generation in SiO2/Si(111) interfaces and, therefore, support the hypothesis that silicon surface defects with dangling bonds are responsible for this phenomenon. The results exhibit a strong dependence on the quality of basis set and exchange-correlation functional, showing that an appropriate set of diffuse functions is required for reliable predictions of the first hyperpolarizability of open-shell compounds.

  20. Approximate spin projected spin-unrestricted density functional theory method: Application to diradical character dependences of second hyperpolarizabilities

    Energy Technology Data Exchange (ETDEWEB)

    Nakano, Masayoshi, E-mail: mnaka@cheng.es.osaka-u.ac.jp; Minami, Takuya, E-mail: mnaka@cheng.es.osaka-u.ac.jp; Fukui, Hitoshi, E-mail: mnaka@cheng.es.osaka-u.ac.jp; Yoneda, Kyohei, E-mail: mnaka@cheng.es.osaka-u.ac.jp; Shigeta, Yasuteru, E-mail: mnaka@cheng.es.osaka-u.ac.jp; Kishi, Ryohei, E-mail: mnaka@cheng.es.osaka-u.ac.jp [Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan); Champagne, Benoît; Botek, Edith [Laboratoire de Chimie Théorique, Facultés Universitaires Notre-Dame de la Paix (FUNDP), rue de Bruxelles, 61, 5000 Namur (Belgium)

    2015-01-22

    We develop a novel method for the calculation and the analysis of the one-electron reduced densities in open-shell molecular systems using the natural orbitals and approximate spin projected occupation numbers obtained from broken symmetry (BS), i.e., spin-unrestricted (U), density functional theory (DFT) calculations. The performance of this approximate spin projection (ASP) scheme is examined for the diradical character dependence of the second hyperpolarizability (γ) using several exchange-correlation functionals, i.e., hybrid and long-range corrected UDFT schemes. It is found that the ASP-LC-UBLYP method with a range separating parameter μ = 0.47 reproduces semi-quantitatively the strongly-correlated [UCCSD(T)] result for p-quinodimethane, i.e., the γ variation as a function of the diradical character.

  1. 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...

  2. 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.

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

    Science.gov (United States)

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

    2015-02-10

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

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

    International Nuclear Information System (INIS)

    Mundt, Michael; Kuemmel, Stephan

    2006-01-01

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

  5. Self-consistent DFT +U method for real-space time-dependent density functional theory calculations

    Science.gov (United States)

    Tancogne-Dejean, Nicolas; Oliveira, Micael J. T.; Rubio, Angel

    2017-12-01

    We implemented various DFT+U schemes, including the Agapito, Curtarolo, and Buongiorno Nardelli functional (ACBN0) self-consistent density-functional version of the DFT +U method [Phys. Rev. X 5, 011006 (2015), 10.1103/PhysRevX.5.011006] within the massively parallel real-space time-dependent density functional theory (TDDFT) code octopus. We further extended the method to the case of the calculation of response functions with real-time TDDFT+U and to the description of noncollinear spin systems. The implementation is tested by investigating the ground-state and optical properties of various transition-metal oxides, bulk topological insulators, and molecules. Our results are found to be in good agreement with previously published results for both the electronic band structure and structural properties. The self-consistent calculated values of U and J are also in good agreement with the values commonly used in the literature. We found that the time-dependent extension of the self-consistent DFT+U method yields improved optical properties when compared to the empirical TDDFT+U scheme. This work thus opens a different theoretical framework to address the nonequilibrium properties of correlated systems.

  6. Time-dependent density-functional theory simulation of local currents in pristine and single-defect zigzag graphene nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    He, Shenglai, E-mail: shenglai.he@vanderbilt.edu; Russakoff, Arthur; Li, Yonghui; Varga, Kálmán, E-mail: kalman.varga@vanderbilt.edu [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235 (United States)

    2016-07-21

    The spatial current distribution in H-terminated zigzag graphene nanoribbons (ZGNRs) under electrical bias is investigated using time-dependent density-functional theory solved on a real-space grid. A projected complex absorbing potential is used to minimize the effect of reflection at simulation cell boundary. The calculations show that the current flows mainly along the edge atoms in the hydrogen terminated pristine ZGNRs. When a vacancy is introduced to the ZGNRs, loop currents emerge at the ribbon edge due to electrons hopping between carbon atoms of the same sublattice. The loop currents hinder the flow of the edge current, explaining the poor electric conductance observed in recent experiments.

  7. Universal Exciton Size in Organic Polymers is Determined by Nonlocal Orbital Exchange in Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Mewes, Stefanie A; Plasser, Felix; Dreuw, Andreas

    2017-03-16

    The exciton size of the lowest singlet excited state in a diverse set of organic π-conjugated polymers is studied and found to be a universal, system-independent quantity of approximately 7 Å in the single-chain picture. With time-dependent density functional theory (TDDFT), its value as well as the overall description of the exciton is almost exclusively governed by the amount of nonlocal orbital exchange. This is traced back to the lack of the Coulomb attraction between the electron and hole quasiparticles in pure TDDFT, which is reintroduced only with the admixture of nonlocal orbital exchange.

  8. Optimal control theory for quantum-classical systems: Ehrenfest molecular dynamics based on time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Castro, A; Gross, E K U

    2014-01-01

    We derive the fundamental equations of an optimal control theory for systems containing both quantum electrons and classical ions. The system is modeled with Ehrenfest dynamics, a non-adiabatic variant of molecular dynamics. The general formulation, that needs the fully correlated many-electron wavefunction, can be simplified by making use of time-dependent density-functional theory. In this case, the optimal control equations require some modifications that we will provide. The abstract general formulation is complemented with the simple example of the H 2 + molecule in the presence of a laser field. (paper)

  9. Localized surface plasmon resonance in silver nanoparticles: Atomistic first-principles time-dependent density-functional theory calculations

    OpenAIRE

    Kuisma, Mikael; Sakko, Arto; Rossi, Tuomas P.; Larsen, Ask H.; Enkovaara, Jussi; Lehtovaara, Lauri; Rantala, Tapio T.

    2015-01-01

    We observe using ab initio methods that localized surface plasmon resonances in icosahedral silver nanoparticles enter the asymptotic region already between diameters of 1 and 2 nm, converging close to the classical quasistatic limit around 3.4 eV. We base the observation on time-dependent density-functional theory simulations of the icosahedral silver clusters Ag$_{55}$ (1.06 nm), Ag$_{147}$ (1.60 nm), Ag$_{309}$ (2.14 nm), and Ag$_{561}$ (2.68 nm). The simulation method combines the adiabat...

  10. Laboratory Density Functionals

    OpenAIRE

    Giraud, B. G.

    2007-01-01

    We compare several definitions of the density of a self-bound system, such as a nucleus, in relation with its center-of-mass zero-point motion. A trivial deconvolution relates the internal density to the density defined in the laboratory frame. This result is useful for the practical definition of density functionals.

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

    Science.gov (United States)

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

    2018-02-01

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

  12. A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

    International Nuclear Information System (INIS)

    Liu Xuan; Ito, Haruhiko; Torikai, Eiko

    2012-01-01

    We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li n , Na n , K n , Rb n , and Cs n with n = 2–8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

  13. Fast Time-Dependent Density Functional Theory Calculations of the X-ray Absorption Spectroscopy of Large Systems.

    Science.gov (United States)

    Besley, Nicholas A

    2016-10-11

    The computational cost of calculations of K-edge X-ray absorption spectra using time-dependent density functional (TDDFT) within the Tamm-Dancoff approximation is significantly reduced through the introduction of a severe integral screening procedure that includes only integrals that involve the core s basis function of the absorbing atom(s) coupled with a reduced quality numerical quadrature for integrals associated with the exchange and correlation functionals. The memory required for the calculations is reduced through construction of the TDDFT matrix within the absorbing core orbitals excitation space and exploiting further truncation of the virtual orbital space. The resulting method, denoted fTDDFTs, leads to much faster calculations and makes the study of large systems tractable. The capability of the method is demonstrated through calculations of the X-ray absorption spectra at the carbon K-edge of chlorophyll a, C 60 and C 70 .

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-03-07

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

  16. Spin-adapted open-shell time-dependent density functional theory. II. Theory and pilot application.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian; Zhang, Yong; Suo, Bingbing

    2011-04-07

    The excited states of open-shell systems calculated by unrestricted Kohn-Sham-based time-dependent density functional theory (U-TD-DFT) are often heavily spin-contaminated and hence meaningless. This is solved ultimately by the recently proposed spin-adapted time-dependent density functional theory (TD-DFT) (S-TD-DFT) [J. Chem. Phys. 133, 064106 (2010)]. Unlike the standard restricted open-shell Kohn-Sham-based TD-DFT (R-TD-DFT) which can only access the singlet-coupled single excitations, the S-TD-DFT can capture both the singlet- and triplet-coupled single excitations with the same computational effort as the U-TD-DFT. The performances of the three approaches (U-TD-DFT, R-TD-DFT, and S-TD-DFT) are compared for both the spin-conserving and spin-flip excitations of prototypical open-shell systems, the nitrogen (N(2)(+)) and naphthalene (C(10)H(8)(+)) cations. The results show that the S-TD-DFT gives rise to balanced descriptions of excited states of open-shell systems.

  17. 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.

  18. Efficient exact-exchange time-dependent density-functional theory methods and their relation to time-dependent Hartree-Fock.

    Science.gov (United States)

    Hesselmann, Andreas; Görling, Andreas

    2011-01-21

    A recently introduced time-dependent exact-exchange (TDEXX) method, i.e., a response method based on time-dependent density-functional theory that treats the frequency-dependent exchange kernel exactly, is reformulated. In the reformulated version of the TDEXX method electronic excitation energies can be calculated by solving a linear generalized eigenvalue problem while in the original version of the TDEXX method a laborious frequency iteration is required in the calculation of each excitation energy. The lowest eigenvalues of the new TDEXX eigenvalue equation corresponding to the lowest excitation energies can be efficiently obtained by, e.g., a version of the Davidson algorithm appropriate for generalized eigenvalue problems. Alternatively, with the help of a series expansion of the new TDEXX eigenvalue equation, standard eigensolvers for large regular eigenvalue problems, e.g., the standard Davidson algorithm, can be used to efficiently calculate the lowest excitation energies. With the help of the series expansion as well, the relation between the TDEXX method and time-dependent Hartree-Fock is analyzed. Several ways to take into account correlation in addition to the exact treatment of exchange in the TDEXX method are discussed, e.g., a scaling of the Kohn-Sham eigenvalues, the inclusion of (semi)local approximate correlation potentials, or hybrids of the exact-exchange kernel with kernels within the adiabatic local density approximation. The lowest lying excitations of the molecules ethylene, acetaldehyde, and pyridine are considered as examples.

  19. Polarization Dependent Bulk-sensitive Valence Band Photoemission Spectroscopy and Density Functional Theory Calculations: Part I. 3d Transition Metals

    Science.gov (United States)

    Ueda, Shigenori; Hamada, Ikutaro

    2017-12-01

    The X-ray polarization dependent valence band HAXPES spectra of 3d transition metals (TMs) of Ti-Zn were measured to investigate the orbital resolved electronic structures by utilizing that the fact the photoionization cross-section of the atomic orbitals strongly depends on the experimental geometry. We have calculated the HAXPES spectra, which correspond to the cross-section weighted densities of states (CSW-DOSs), where the DOSs were obtained by the density functional theory calculations, and we have determined the relative photoionization cross-sections of the 4s and 4p orbitals to the 3d orbital in the 3d TMs. The experimentally obtained bulk-sensitive 3d and 4s DOSs were good agreement with the calculated DOSs in Ti, V, Cr, and Cu. In contrast, the deviations between the experimental and calculated 3d DOSs for Mn, Fe, Co, Ni were found, suggesting that the electron correlation plays an important role in the electronic structures for these materials.

  20. Phosphorescence lifetimes of organic light-emitting diodes from two-component time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kühn, Michael [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Weigend, Florian, E-mail: florian.weigend@kit.edu [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany)

    2014-12-14

    “Spin-forbidden” transitions are calculated for an eight-membered set of iridium-containing candidate molecules for organic light-emitting diodes (OLEDs) using two-component time-dependent density functional theory. Phosphorescence lifetimes (obtained from averaging over relevant excitations) are compared to experimental data. Assessment of parameters like non-distorted and distorted geometric structures, density functionals, relativistic Hamiltonians, and basis sets was done by a thorough study for Ir(ppy){sub 3} focussing not only on averaged phosphorescence lifetimes, but also on the agreement of the triplet substate structure with experimental data. The most favorable methods were applied to an eight-membered test set of OLED candidate molecules; Boltzmann-averaged phosphorescence lifetimes were investigated concerning the convergence with the number of excited states and the changes when including solvent effects. Finally, a simple model for sorting out molecules with long averaged phosphorescence lifetimes is developed by visual inspection of computationally easily achievable one-component frontier orbitals.

  1. Excited states of ReO4-: A comprehensive time-dependent relativistic density functional theory study

    Science.gov (United States)

    Xu, Wenhua; Ma, Jianyi; Peng, Daoling; Zou, Wenli; Liu, Wenjian; Staemmler, Volker

    2009-02-01

    The perrhenate anion, ReO4-, is taken as a showcase of heavy transition metal complexes, to examine the performance of time-dependent relativistic density functional linear response theory for electronic excitations, which is based on a newly proposed exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. In total 30 scalar and 63 spinor excited states are investigated and the results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory. It is found that only a few scalar states of 3T1 and 3T2 symmetries are split significantly by the spin-orbit coupling, whereas only those excited states involving the Rydberg-type virtual orbital are affected by the solvent effects. The nature of the optical absorption spectra is also highlighted.

  2. Excited states of ReO4-: A comprehensive time-dependent relativistic density functional theory study

    International Nuclear Information System (INIS)

    Xu Wenhua; Ma Jianyi; Peng Daoling; Zou Wenli; Liu Wenjian; Staemmler, Volker

    2009-01-01

    The perrhenate anion, ReO 4 - , is taken as a showcase of heavy transition metal complexes, to examine the performance of time-dependent relativistic density functional linear response theory for electronic excitations, which is based on a newly proposed exact two-component Hamiltonian resulting from the symmetrized elimination of the small component. In total 30 scalar and 63 spinor excited states are investigated and the results are grossly in good agreement with those by the singles and doubles coupled-cluster linear response theory. It is found that only a few scalar states of 3 T 1 and 3 T 2 symmetries are split significantly by the spin-orbit coupling, whereas only those excited states involving the Rydberg-type virtual orbital are affected by the solvent effects. The nature of the optical absorption spectra is also highlighted

  3. Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids.

    Science.gov (United States)

    Lian, Cheng; Zhao, Shuangliang; Liu, Honglai; Wu, Jianzhong

    2016-11-28

    Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this work, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the duration of charging. Furthermore, we investigate the effects of van der Waals attraction between electrode/ionic-liquid interactions on the charging processes.

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

    Science.gov (United States)

    Heßelmann, Andreas

    2015-04-14

    Molecular excitation energies have been calculated with time-dependent density-functional theory (TDDFT) using random-phase approximation Hessians augmented with exact exchange contributions in various orders. It has been observed that this approach yields fairly accurate local valence excitations if combined with accurate asymptotically corrected exchange-correlation potentials used in the ground-state Kohn-Sham calculations. The inclusion of long-range particle-particle with hole-hole interactions in the kernel leads to errors of 0.14 eV only for the lowest excitations of a selection of three alkene, three carbonyl, and five azabenzene molecules, thus surpassing the accuracy of a number of common TDDFT and even some wave function correlation methods. In the case of long-range charge-transfer excitations, the method typically underestimates accurate reference excitation energies by 8% on average, which is better than with standard hybrid-GGA functionals but worse compared to range-separated functional approximations.

  5. Triplet state photochemistry and the three-state crossing of acetophenone within time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Huix-Rotllant, Miquel, E-mail: miquel.huix@gmail.com; Ferré, Nicolas, E-mail: nicolas.ferre@univ-amu.fr [Institut de Chimie Radicalaire (UMR-7273), Aix-Marseille Université, CNRS, 13397 Marseille Cedex 20 (France)

    2014-04-07

    Even though time-dependent density-functional theory (TDDFT) works generally well for describing excited states energies and properties in the Franck-Condon region, it can dramatically fail in predicting photochemistry, notably when electronic state crossings occur. Here, we assess the ability of TDDFT to describe the photochemistry of an important class of triplet sensitizers, namely, aromatic ketones. We take acetophenone as a test molecule, for which accurate ab initio results exist in the literature. Triplet acetophenone is generated thanks to an exotic three-state crossing involving one singlet and two triplets states (i.e., a simultaneous intersystem crossing and triplet conical intersection), thus being a stringent test for approximate TDDFT. We show that most exchange-correlation functionals can only give a semi-qualitative picture of the overall photochemistry, in which the three-state crossing is rather represented as a triplet conical intersection separated from the intersystem crossing. The best result overall is given by the double hybrid functional mPW2PLYP, which is even able to reproduce quantitatively the three-state crossing region. We rationalize this results by noting that double hybrid functionals include a larger portion of double excitation character to the excited states.

  6. Intrinsic-density functionals

    International Nuclear Information System (INIS)

    Engel, J.

    2007-01-01

    The Hohenberg-Kohn theorem and Kohn-Sham procedure are extended to functionals of the localized intrinsic density of a self-bound system such as a nucleus. After defining the intrinsic-density functional, we modify the usual Kohn-Sham procedure slightly to evaluate the mean-field approximation to the functional, and carefully describe the construction of the leading corrections for a system of fermions in one dimension with a spin-degeneracy equal to the number of particles N. Despite the fact that the corrections are complicated and nonlocal, we are able to construct a local Skyrme-like intrinsic-density functional that, while different from the exact functional, shares with it a minimum value equal to the exact ground-state energy at the exact ground-state intrinsic density, to next-to-leading order in 1/N. We briefly discuss implications for real Skyrme functionals

  7. Assessment of Real-Time Time-Dependent Density Functional Theory (RT-TDDFT) in Radiation Chemistry: Ionized Water Dimer.

    Science.gov (United States)

    Chalabala, Jan; Uhlig, Frank; Slavíček, Petr

    2018-03-29

    Ionization in the condensed phase and molecular clusters leads to a complicated chain of processes with coupled electron-nuclear dynamics. It is difficult to describe such dynamics with conventional nonadiabatic molecular dynamics schemes since the number of states swiftly increases as the molecular system grows. It is therefore attractive to use a direct electron and nuclear propagation such as the real-time time-dependent density functional theory (RT-TDDFT). Here we report a RT-TDDFT benchmark study on simulations of singly and doubly ionized states of a water monomer and dimer as a prototype for more complex processes in a condensed phase. We employed the RT-TDDFT based Ehrenfest molecular dynamics with a generalized gradient approximate (GGA) functional and compared it with wave-function-based surface hopping (SH) simulations. We found that the initial dynamics of a singly HOMO ionized water dimer is similar for both the RT-TDDFT/GGA and the SH simulations but leads to completely different reaction channels on a longer time scale. This failure is attributed to the self-interaction error in the GGA functionals and it can be avoided by using hybrid functionals with large fraction of exact exchange (represented here by the BHandHLYP functional). The simulations of doubly ionized states are reasonably described already at the GGA level. This suggests that the RT-TDDFT/GGA method could describe processes following the autoionization processes such as Auger emission, while its applicability to more complex processes such as intermolecular Coulombic decay remains limited.

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

    Energy Technology Data Exchange (ETDEWEB)

    Goings, Joshua J.; Li, Xiaosong, E-mail: xsli@uw.edu [Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States)

    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.

  9. A numerical study of spin-dependent organization of alkali-metal atomic clusters using density-functional method

    Energy Technology Data Exchange (ETDEWEB)

    Liu Xuan, E-mail: liu.x.ad@m.titech.ac.jp; Ito, Haruhiko [Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology (Japan); Torikai, Eiko [Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi (Japan)

    2012-08-15

    We calculate the different geometric isomers of spin clusters composed of a small number of alkali-metal atoms using the UB3LYP density-functional method. The electron density distribution of clusters changes according to the value of total spin. Steric structures as well as planar structures arise when the number of atoms increases. The lowest spin state is the most stable and Li{sub n}, Na{sub n}, K{sub n}, Rb{sub n}, and Cs{sub n} with n = 2-8 can be formed in higher spin states. In the highest spin state, the preparation of clusters depends on the kind and the number of constituent atoms. The interaction energy between alkali-metal atoms and rare-gas atoms is smaller than the binding energy of spin clusters. Consequently, it is possible to self-organize the alkali-metal-atom clusters on a non-wetting substrate coated with rare-gas atoms.

  10. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    Science.gov (United States)

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  11. Application of time-dependent current-density-functional theory to nonlocal exchange-correlation effects in polymers

    NARCIS (Netherlands)

    van Faassen, M; de Boeij, PL; van Leeuwen, R; Berger, JA; Snijders, JG

    2003-01-01

    We provide a successful approach towards the solution of the longstanding problem of the large overestimation of the static polarizability of conjugated oligomers obtained using the local density approximation within density-functional theory. The local approximation is unable to describe the highly

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

    International Nuclear Information System (INIS)

    Lee, Sang Uck

    2013-01-01

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

  13. density functional theory approach

    Indian Academy of Sciences (India)

    YOGESH ERANDE

    2017-07-27

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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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

  15. Analytic derivative couplings for spin-flip configuration interaction singles and spin-flip time-dependent density functional theory

    International Nuclear Information System (INIS)

    Zhang, Xing; Herbert, John M.

    2014-01-01

    We revisit the calculation of analytic derivative couplings for configuration interaction singles (CIS), and derive and implement these couplings for its spin-flip variant for the first time. Our algorithm is closely related to the CIS analytic energy gradient algorithm and should be straightforward to implement in any quantum chemistry code that has CIS analytic energy gradients. The additional cost of evaluating the derivative couplings is small in comparison to the cost of evaluating the gradients for the two electronic states in question. Incorporation of an exchange-correlation term provides an ad hoc extension of this formalism to time-dependent density functional theory within the Tamm-Dancoff approximation, without the need to invoke quadratic response theory or evaluate third derivatives of the exchange-correlation functional. Application to several different conical intersections in ethylene demonstrates that minimum-energy crossing points along conical seams can be located at substantially reduced cost when analytic derivative couplings are employed, as compared to use of a branching-plane updating algorithm that does not require these couplings. Application to H 3 near its D 3h geometry demonstrates that correct topology is obtained in the vicinity of a conical intersection involving a degenerate ground state

  16. Temperature-dependent study of isotropic-nematic transition for a Gay-Berne fluid using density-functional theory

    International Nuclear Information System (INIS)

    Singh, Ram Chandra

    2007-01-01

    We have used the density-functional theory to study the effect of varying temperature on the isotropic-nematic transition of a fluid of molecules interacting via the Gay-Berne intermolecular potential. The nematic phase is found to be stable with respect to isotropic phase in the temperature range 0.80≤T*≤1.25. Pair correlation functions needed as input information in density-functional theory is calculated using the Percus-Yevick integral equation theory. We find that the density-functional theory is good for studying the isotropic-nematic transition in molecular fluids if the values of the pair-correlation functions in the isotropic phase are known accurately. We have also compared our results with computer simulation results wherever they are available

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    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: →We present a systematic comparative study of families of PAHs. → We computed electronic, optical, and transport properties as a function of size. → We considered oligoacenes, phenacenes, circumacenes, and oligorylenes. → Circumacenes have the best transport properties compared to the other classes. → 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.

  18. density-dependent selection revisited

    Indian Academy of Sciences (India)

    Unknown

    is a more useful way of looking at density-dependent selection, and then go on ... these models was that the condition for maintenance of ... In a way, their formulation may be viewed as ... different than competition among species, and typical.

  19. Density functional theory

    International Nuclear Information System (INIS)

    Freyss, M.

    2015-01-01

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

  20. Density functional theory

    International Nuclear Information System (INIS)

    Das, M.P.

    1984-07-01

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

  1. Support of A Summer School Workshop and Workshop Focused on Theory and Applications of Time-Dependent Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Maitra, Neepa [City Univ. (CUNY), NY (United States). Dept. of Physics

    2017-08-31

    The first US-based summer school and workshop on Time-Dependent Density Functional Theory (TDDFT) was held July 11-21, 2017 in Telluride, CO. This grant provided funding to enable 33 students to attend the school, specifically with lodging and registration fee reductions. TDDFT is increasingly used in computational molecular and materials science to calculate electronic-excitation spectra and dynamics in a wide variety of applications, including photocatalysis, photo-controlled bond dissociation, and light-induced charge transfer. Software development in this community targets multiple software packages, many of which are open source, such as octopus, NWchem and Qb@ll, which are the ones our school focused on. The goal of this first iteration was to create a home for a national community of scholars, including users and developers, with a deep understanding of TDDFT, its capabilities, limitations, and high-performance computing context. We used this opportunity to explore interest in such an event in the future and based on overwhelmingly positive feedback from students and teachers, we intend to hold a similar school+workshop every two years in the US, in order to maintain the high level of interest that we witnessed and the enthusiasm amongst participants.

  2. 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.

  3. Spin-adapted open-shell time-dependent density functional theory. III. An even better and simpler formulation.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian

    2011-11-21

    The recently proposed spin-adapted time-dependent density functional theory (S-TD-DFT) [Z. Li and W. Liu, J. Chem. Phys. 133, 064106 (2010)] resolves the spin-contamination problem in describing singly excited states of high spin open-shell systems. It is an extension of the standard restricted open-shell Kohn-Sham-based TD-DFT which can only access those excited states due to singlet-coupled single excitations. It is also far superior over the unrestricted Kohn-Sham-based TD-DFT (U-TD-DFT) which suffers from severe spin contamination for those excited states due to triplet-coupled single excitations. Nonetheless, the accuracy of S-TD-DFT for high spin open-shell systems is still inferior to TD-DFT for well-behaved closed-shell systems. The reason can be traced back to the violation of the spin degeneracy conditions (SDC) by approximate exchange-correlation (XC) functionals. Noticing that spin-adapted random phase approximation (S-RPA) can indeed maintain the SDC by virtue of the Wigner-Eckart theorem, a hybrid ansatz combining the good of S-TD-DFT and S-RPA can immediately be envisaged. The resulting formalism, dubbed as X-TD-DFT, is free of spin contamination and can also be viewed as a S-RPA correction to the XC kernel of U-TD-DFT. Compared with S-TD-DFT, X-TD-DFT leads to much improved results for the low-lying excited states of, e.g., N(2)(+), yet with much reduced computational cost. Therefore, X-TD-DFT can be recommended for routine calculations of excited states of high spin open-shell systems.

  4. 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.

  5. Sulfur K-edge X-ray absorption spectroscopy and time-dependent density functional theory of arsenic dithiocarbamates.

    Science.gov (United States)

    Donahue, Courtney M; Pacheco, Juan S Lezama; Keith, Jason M; Daly, Scott R

    2014-06-28

    S K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT) calculations were performed on a series of As[S2CNR2]3 complexes, where R2 = Et2, (CH2)5 and Ph2, to determine how dithiocarbamate substituents attached to N affect As[S2CNR2]3 electronic structure. Complimentary [PPh4][S2CNR2] salts were also studied to compare dithiocarbamate bonding in the absence of As. The XAS results indicate that changing the orientation of the alkyl substituents from trans to cis (R2 = Et2vs. (CH2)5) yields subtle variations whereas differences associated with a change from alkyl to aryl are much more pronounced. For example, despite the differences in As 4p mixing, the first features in the S K-edge XAS spectra of [PPh4][S2CNPh2] and As[S2CNPh2]3 were both shifted by 0.3 eV compared to their alkyl-substituted derivatives. DFT calculations revealed that the unique shift observed for [PPh4][S2CNPh2] is due to phenyl-induced splitting of the π* orbitals delocalized over N, C and S. A similar phenomenon accounts for the shift observed for As[S2CNPh2]3, but the presence of two unique S environments (As-S and As···S) prevented reliable analysis of As-S covalency from the XAS data. In the absence of experimental values, DFT calculations revealed a decrease in As-S orbital mixing in As[S2CNPh2]3 that stems from a redistribution of electron density to S atoms participating in weaker As···S interactions. Simulated spectra obtained from TDDFT calculations reproduce the experimental differences in the S K-edge XAS data, which suggests that the theory is accurately modeling the experimental differences in As-S orbital mixing. The results highlight how S K-edge XAS and DFT can be used cooperatively to understand the electronic structure of low symmetry coordination complexes containing S atoms in different chemical environments.

  6. Calibration of the fine-structure constant of graphene by time-dependent density-functional theory

    Science.gov (United States)

    Sindona, A.; Pisarra, M.; Vacacela Gomez, C.; Riccardi, P.; Falcone, G.; Bellucci, S.

    2017-11-01

    One of the amazing properties of graphene is the ultrarelativistic behavior of its loosely bound electrons, mimicking massless fermions that move with a constant velocity, inversely proportional to a fine-structure constant αg of the order of unity. The effective interaction between these quasiparticles is, however, better controlled by the coupling parameter αg*=αg/ɛ , which accounts for the dynamic screening due to the complex permittivity ɛ of the many-valence electron system. This concept was introduced in a couple of previous studies [Reed et al., Science 330, 805 (2010) and Gan et al., Phys. Rev. B 93, 195150 (2016)], where inelastic x-ray scattering measurements on crystal graphite were converted into an experimentally derived form of αg* for graphene, over an energy-momentum region on the eV Å -1 scale. Here, an accurate theoretical framework is provided for αg*, using time-dependent density-functional theory in the random-phase approximation, with a cutoff in the interaction between excited electrons in graphene, which translates to an effective interlayer interaction in graphite. The predictions of the approach are in excellent agreement with the above-mentioned measurements, suggesting a calibration method to substantially improve the experimental derivation of αg*, which tends to a static limiting value of ˜0.14 . Thus, the ab initio calibration procedure outlined demonstrates the accuracy of perturbation expansion treatments for the two-dimensional gas of massless Dirac fermions in graphene, in parallel with quantum electrodynamics.

  7. Quantum fluid dynamics based current-density functional study of a helium atom in a strong time-dependent magnetic field

    International Nuclear Information System (INIS)

    Vikas

    2011-01-01

    Evolution of the helium atom in a strong time-dependent (TD) magnetic field (B) of strength up to 10 11 G is investigated through a quantum fluid dynamics (QFD) based current-density functional theory (CDFT). The TD-QFD-CDFT computations are performed through numerical solution of a single generalized nonlinear Schroedinger equation employing vector exchange-correlation potentials and scalar exchange-correlation density functionals that depend both on the electronic charge-density and the current-density. The results are compared with that obtained from a B-TD-QFD-DFT approach (based on conventional TD-DFT) under similar numerical constraints but employing only scalar exchange-correlation potential dependent on electronic charge-density only. The B-TD-QFD-DFT approach, at a particular TD magnetic field-strength, yields electronic charge- and current-densities as well as exchange-correlation potential resembling with that obtained from the time-independent studies involving static (time-independent) magnetic fields. However, TD-QFD-CDFT electronic charge- and current-densities along with the exchange-correlation potential and energy differ significantly from that obtained using B-TD-QFD-DFT approach, particularly at field-strengths >10 9 G, representing dynamical effects of a TD field. The work concludes that when a helium atom is subjected to a strong TD magnetic field of order >10 9 G, the conventional TD-DFT based approach differs 'dynamically' from the CDFT based approach under similar computational constraints. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-05-14

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

  9. Excited-state absorption in tetrapyridyl porphyrins: comparing real-time and quadratic-response time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, David N. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Asher, Jason C. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Fischer, Sean A. [William R. Wiley Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; P.O. Box 999; Richland; USA; Cramer, Christopher J. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Govind, Niranjan [William R. Wiley Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; P.O. Box 999; Richland; USA

    2017-01-01

    Threemeso-substituted tetrapyridyl porphyrins (free base, Ni(ii), and Cu(ii)) were investigated for their optical limiting (OL) capabilities using real-time (RT-), linear-response (LR-), and quadratic-response (QR-) time-dependent density functional theory (TDDFT) methods.

  10. Optical to ultraviolet spectra of sandwiches of benzene and transition metal atoms: Time dependent density functional theory and many-body calculations

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; García Lastra, Juan Maria; Lopez, M. J.

    2010-01-01

    The optical spectra of sandwich clusters formed by transition metal atoms (titanium, vanadium, and chromium) intercalated between parallel benzene molecules have been studied by time-dependent density functional theory (TDDFT) and many-body perturbation theory. Sandwiches with different number...

  11. Spin-adapted open-shell random phase approximation and time-dependent density functional theory. I. Theory.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian

    2010-08-14

    The spin-adaptation of single-reference quantum chemical methods for excited states of open-shell systems has been nontrivial. The primary reason is that the configuration space, generated by a truncated rank of excitations from only one component of a reference multiplet, is spin-incomplete. Those "missing" configurations are of higher ranks and can, in principle, be recaptured by a particular class of excitation operators. However, the resulting formalisms are then quite involved and there are situations [e.g., time-dependent density functional theory (TD-DFT) under the adiabatic approximation] that prevent one from doing so. To solve this issue, we propose here a tensor-coupling scheme that invokes all the components of a reference multiplet (i.e., a tensor reference) rather than increases the excitation ranks. A minimal spin-adapted n-tuply excited configuration space can readily be constructed by tensor products between the n-tuple tensor excitation operators and the chosen tensor reference. Further combined with the tensor equation-of-motion formalism, very compact expressions for excitation energies can be obtained. As a first application of this general idea, a spin-adapted open-shell random phase approximation is first developed. The so-called "translation rule" is then adopted to formulate a spin-adapted, restricted open-shell Kohn-Sham (ROKS)-based TD-DFT (ROKS-TD-DFT). Here, a particular symmetry structure has to be imposed on the exchange-correlation kernel. While the standard ROKS-TD-DFT can access only excited states due to singlet-coupled single excitations, i.e., only some of the singly excited states of the same spin (S(i)) as the reference, the new scheme can capture all the excited states of spin S(i)-1, S(i), or S(i)+1 due to both singlet- and triplet-coupled single excitations. The actual implementation and computation are very much like the (spin-contaminated) unrestricted Kohn-Sham-based TD-DFT. It is also shown that spin-contaminated spin

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

    Science.gov (United States)

    Li, Shaohong L; Truhlar, Donald G

    2015-07-14

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

  13. Density-Functional formalism

    International Nuclear Information System (INIS)

    Szasz, L.; Berrios-Pagan, I.; McGinn, G.

    1975-01-01

    A new Density-Functional formula is constructed for atoms. The kinetic energy of the electron is divided into two parts: the kinetic self-energy and the orthogonalization energy. Calculations were made for the total energies of neutral atoms, positive ions and for the He isoelectronic series. For neutral atoms the results match the Hartree-Fock energies within 1% for atoms with N 36 the results generally match the HF energies within 0.1%. For positive ions the results are fair; for the molecular applications a simplified model is developed in which the kinetic energy consists of the Weizsaecker term plus the Fermi energy reduced by a continuous function. (orig.) [de

  14. Multiphoton ionization of many-electron atoms and highly-charged ions in intense laser fields: a relativistic time-dependent density functional theory approach

    Science.gov (United States)

    Tumakov, Dmitry A.; Telnov, Dmitry A.; Maltsev, Ilia A.; Plunien, Günter; Shabaev, Vladimir M.

    2017-10-01

    We develop an efficient numerical implementation of the relativistic time-dependent density functional theory (RTDDFT) to study multielectron highly-charged ions subject to intense linearly-polarized laser fields. The interaction with the electromagnetic field is described within the electric dipole approximation. The resulting time-dependent relativistic Kohn-Sham (RKS) equations possess an axial symmetry and are solved accurately and efficiently with the help of the time-dependent generalized pseudospectral method. As a case study, we calculate multiphoton ionization probabilities of the neutral argon atom and argon-like xenon ion. Relativistic effects are assessed by comparison of our present results with existing non-relativistic data.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    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 C 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 simplest

  16. Excited state nuclear forces from the Tamm-Dancoff approximation to time-dependent density functional theory within the plane wave basis set framework

    Science.gov (United States)

    Hutter, Jürg

    2003-03-01

    An efficient formulation of time-dependent linear response density functional theory for the use within the plane wave basis set framework is presented. The method avoids the transformation of the Kohn-Sham matrix into the canonical basis and references virtual orbitals only through a projection operator. Using a Lagrangian formulation nuclear derivatives of excited state energies within the Tamm-Dancoff approximation are derived. The algorithms were implemented into a pseudo potential/plane wave code and applied to the calculation of adiabatic excitation energies, optimized geometries and vibrational frequencies of three low lying states of formaldehyde. An overall good agreement with other time-dependent density functional calculations, multireference configuration interaction calculations and experimental data was found.

  17. Quantum master equation method based on the broken-symmetry time-dependent density functional theory: application to dynamic polarizability of open-shell molecular systems.

    Science.gov (United States)

    Kishi, Ryohei; Nakano, Masayoshi

    2011-04-21

    A novel method for the calculation of the dynamic polarizability (α) of open-shell molecular systems is developed based on the quantum master equation combined with the broken-symmetry (BS) time-dependent density functional theory within the Tamm-Dancoff approximation, referred to as the BS-DFTQME method. We investigate the dynamic α density distribution obtained from BS-DFTQME calculations in order to analyze the spatial contributions of electrons to the field-induced polarization and clarify the contributions of the frontier orbital pair to α and its density. To demonstrate the performance of this method, we examine the real part of dynamic α of singlet 1,3-dipole systems having a variety of diradical characters (y). The frequency dispersion of α, in particular in the resonant region, is shown to strongly depend on the exchange-correlation functional as well as on the diradical character. Under sufficiently off-resonant condition, the dynamic α is found to decrease with increasing y and/or the fraction of Hartree-Fock exchange in the exchange-correlation functional, which enhances the spin polarization, due to the decrease in the delocalization effects of π-diradical electrons in the frontier orbital pair. The BS-DFTQME method with the BHandHLYP exchange-correlation functional also turns out to semiquantitatively reproduce the α spectra calculated by a strongly correlated ab initio molecular orbital method, i.e., the spin-unrestricted coupled-cluster singles and doubles.

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

    Science.gov (United States)

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

    2018-03-01

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

  19. 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)

    Energy Technology Data Exchange (ETDEWEB)

    Yokogawa, D., E-mail: d.yokogawa@chem.nagoya-u.ac.jp [Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602 (Japan); Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602 (Japan)

    2016-09-07

    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.

  20. A mechanistic analysis of density dependence in algal population dynamics

    Directory of Open Access Journals (Sweden)

    Adrian eBorlestean

    2015-04-01

    Full Text Available Population density regulation is a fundamental principle in ecology, but the specific process underlying functional expression of density dependence remains to be fully elucidated. One view contends that patterns of density dependence are largely fixed across a species irrespective of environmental conditions, whereas another is that the strength and expression of density dependence are fundamentally variable depending on the nature of exogenous or endogenous constraints acting on the population. We conducted a study investigating the expression of density dependence in Chlamydomonas spp. grown under a gradient from low to high nutrient density. We predicted that the relationship between per capita growth rate (pgr and population density would vary from concave up to concave down as nutrient density became less limiting and populations experienced weaker density regulation. Contrary to prediction, we found that the relationship between pgr and density became increasingly concave-up as nutrient levels increased. We also found that variation in pgr increased, and pgr levels reached higher maxima in nutrient-limited environments. Most likely, these results are attributable to population growth suppression in environments with high intraspecific competition due to limited nutrient resources. Our results suggest that density regulation is strongly variable depending on exogenous and endogenous processes acting on the population, implying that expression of density dependence depends extensively on local conditions. Additional experimental work should reveal the mechanisms influencing how the expression of density dependence varies across populations through space and time.

  1. Density functionals from deep learning

    OpenAIRE

    McMahon, Jeffrey M.

    2016-01-01

    Density-functional theory is a formally exact description of a many-body quantum system in terms of its density; in practice, however, approximations to the universal density functional are required. In this work, a model based on deep learning is developed to approximate this functional. Deep learning allows computational models that are capable of naturally discovering intricate structure in large and/or high-dimensional data sets, with multiple levels of abstraction. As no assumptions are ...

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

    DEFF Research Database (Denmark)

    Olsen, Thomas; Thygesen, Kristian Sommer

    2014-01-01

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

  3. Density-dependent Hartree-Fock response functions in quasi-elastic electron scattering on 12C and related sum rules

    International Nuclear Information System (INIS)

    Kohno, M.

    1983-01-01

    We report fully consistent calculations of the longitudinal and transverse response functions of the inclusive quasi-elastic electron scattering on 12 C in the Hartree-Fock approximation. The distorted wave for the outgoing nucleon is constructed from the same non-local Hartree-Fock field as in the ground-state description. Thus the orthogonality and Pauli principle requirements are naturally satisfied. The theoretical prediction, based on the standard density-dependent effective interaction (GO force), shows a good correspondence to the experimental data. Since the calculated response functions automatically satisfy the relevant sum rule, this work illuminates the well-known puzzle concerning the longitudinal part, which remains to be solved. We study the energy-weighted sum rules and discuss effects beyond the mean-field approximation. Meson-exchange-current contributions to the transverse response function are also estimated and found to be small due to cancellations among them. (orig.)

  4. Conventional and acoustic surface plasmons on noble metal surfaces: a time-dependent density functional theory study

    DEFF Research Database (Denmark)

    Yan, Jun; Jacobsen, Karsten W.; Thygesen, Kristian S.

    2012-01-01

    and an orbital-dependent exchange-correlation (xc) potential that improves the position and width of the d bands. The plasmon dispersions calculated with the latter xc potential agree well with electron energy loss spectroscopy (EELS) experiments. For both the CSP and ASP, the same trend of Cu

  5. Formation of Bonded Exciplex in the Excited States of Dicyanoanthracene-Pyridine System : Time Dependent Density Functional Theory Study

    NARCIS (Netherlands)

    Setiawan, D.; Sethio, D.; Martoprawiro, M.A.; Filatov, M.; Gaol, FL; Nguyen, QV

    2012-01-01

    Strong quenching of fluorescence was recently observed in pyridine solutions of 9,10-dicyanoanthracene chromophore. It was hypothesized that quenching may be attributed to the formation of bound charge transfer complexes in the excited states of the molecules. In this work, using time-dependent

  6. Vacancy migration energy dependence on local chemical environment in Fe–Cr alloys: A Density Functional Theory study

    Energy Technology Data Exchange (ETDEWEB)

    Costa, D., E-mail: davide.costa.ge@gmail.com [Unité Matériaux et Transformations, CNRS UMR8207, Université de Lille 1, F-59655 Villeneuve d’Ascq Cédex (France); EDF-R and D Département MMC, Les Renardières, F-77818 Moret sur Loing Cédex (France); Laboratoire commun (EDF–CNRS): Etude et Modélisation des Microstructures pour le Vieillissement des Matériaux (EM2VM) (France); Adjanor, G. [EDF-R and D Département MMC, Les Renardières, F-77818 Moret sur Loing Cédex (France); Laboratoire commun (EDF–CNRS): Etude et Modélisation des Microstructures pour le Vieillissement des Matériaux (EM2VM) (France); Becquart, C.S. [Unité Matériaux et Transformations, CNRS UMR8207, Université de Lille 1, F-59655 Villeneuve d’Ascq Cédex (France); Laboratoire commun (EDF–CNRS): Etude et Modélisation des Microstructures pour le Vieillissement des Matériaux (EM2VM) (France); Olsson, P. [Laboratoire commun (EDF–CNRS): Etude et Modélisation des Microstructures pour le Vieillissement des Matériaux (EM2VM) (France); KTH Royal Institute of Technology, Reactor Physics, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); and others

    2014-09-15

    The first step towards the understanding and the modelling of the Fe–Cr alloy kinetic properties consists in estimating the migration energies related to the processes that drive the microstructure evolution. The vacancy’s migration barrier is expected to depend on the vacancy–migrating atom pair atomic environment as pointed out by Nguyen-Manh et al. or Bonny et al. In this paper, we address the issue of the dependence on the vacancy’s local atomic environment of both the vacancy migration energy and the configurational energy change ΔE that occurs when the vacancy jumps towards one of its nearest neighbour sites. A DFT approach is used to determine the ground state energy associated to a given configuration of the system. The results are interpreted in the light of the chromium–chromium and chromium–vacancy binding energies as well as the substitutional chromium atoms magnetic properties.

  7. Density of states functions for photonic crystals

    International Nuclear Information System (INIS)

    McPhedran, R.C.; McOrist, J.; Sterke, C.M. de; Nicorovici, N.A.; Botten, L.C.; Asatryan, A.A.

    2004-01-01

    We discuss density of states functions for photonic crystals, in the context of the two-dimensional problem for arrays of cylinders of arbitrary cross section. We introduce the mutual density of states (MDOS), and show that this function can be used to calculate both the local density of states (LDOS), which gives position information for emission of radiation from photonic crystals, and the spectral density of states (SDOS), which gives angular information. We establish the connection between MDOS, LDOS, SDOS and the conventional density of states, which depends only on frequency. We relate all four functions to the band structure and propagating states within the crystal, and give numerical examples of the relation between band structure and density of states functions

  8. Scattering of a proton with the Li{sub 4} cluster: Non-adiabatic molecular dynamics description based on time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Castro, A., E-mail: acastro@bifi.es [Institute for Biocomputation and Physics of Complex Systems (BIFI) and Zaragoza Scientific Center for Advanced Modelling (ZCAM), University of Zaragoza, 50018 Zaragoza (Spain); Isla, M. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, 47005 Valladolid (Spain); Martinez, Jose I. [Departamento de Fisica Teorica de la Materia Condensada, Universidad Autonoma de Madrid, ES-28049 Madrid (Spain); Alonso, J.A. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, 47005 Valladolid (Spain)

    2012-05-03

    Graphical abstract: Two trajectories for the collision of a proton with the Lithium tetramer. On the left, the proton is scattered away, and a Li{sub 2} molecule plus two isolated Lithium atoms result. On the right, the proton is captured and a LiH molecule is created. Highlights: Black-Right-Pointing-Pointer Scattering of a proton with Lithium clusters described from first principles. Black-Right-Pointing-Pointer Description based on non-adiabatic molecular dynamics. Black-Right-Pointing-Pointer The electronic structure is described with time-dependent density-functional theory. Black-Right-Pointing-Pointer The method allows to discern reaction channels depending on initial parameters. - Abstract: We have employed non-adiabatic molecular dynamics based on time-dependent density-functional theory to characterize the scattering behavior of a proton with the Li{sub 4} cluster. This technique assumes a classical approximation for the nuclei, effectively coupled to the quantum electronic system. This time-dependent theoretical framework accounts, by construction, for possible charge transfer and ionization processes, as well as electronic excitations, which may play a role in the non-adiabatic regime. We have varied the incidence angles in order to analyze the possible reaction patterns. The initial proton kinetic energy of 10 eV is sufficiently high to induce non-adiabatic effects. For all the incidence angles considered the proton is scattered away, except in one interesting case in which one of the Lithium atoms captures it, forming a LiH molecule. This theoretical formalism proves to be a powerful, effective and predictive tool for the analysis of non-adiabatic processes at the nanoscale.

  9. Density-dependence as a size-independent regulatory mechanism

    NARCIS (Netherlands)

    De Vladar, H.P.

    2006-01-01

    The growth function of populations is central in biomathematics. The main dogma is the existence of density-dependence mechanisms, which can be modelled with distinct functional forms that depend on the size of the Population. One important class of regulatory functions is the theta-logistic, which

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

    International Nuclear Information System (INIS)

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

    1993-01-01

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

  11. 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.

  12. Magnetic fields and density functional theory

    International Nuclear Information System (INIS)

    Salsbury, Freddie Jr.

    1999-01-01

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

  13. Electron dynamics and optical properties modulation of monolayer MoS{sub 2} by femtosecond laser pulse: a simulation using time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Su, Xiaoxing; Jiang, Lan [Beijing Institute of Technology, Laser Micro/Nano Fabrication Laboratory, School of Mechanical Engineering, Beijing (China); Wang, Feng [Beijing Institute of Technology, School of Physics, Beijing (China); Su, Gaoshi [Beijing Institute of Technology, School of Mechatronical Engineering, Beijing (China); Qu, Liangti [Beijing Institute of Technology, Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry, Beijing (China); Lu, Yongfeng [University of Nebraska-Lincoln, Department of Electrical Engineering, Lincoln, NE (United States)

    2017-07-15

    In this study, we adopted time-dependent density functional theory to investigate the optical properties of monolayer MoS{sub 2} and the effect of intense few-cycle femtosecond laser pulses on these properties. The electron dynamics of monolayer MoS{sub 2} 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 MoS{sub 2} 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 MoS{sub 2} and has potential applications in direction-dependent optoelectronic devices. (orig.)

  14. Minimal nuclear energy density functional

    Science.gov (United States)

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

    2018-04-01

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

  15. SYNTHESIS, CHARACTERIZATION AND DENSITY FUNCTIONAL ...

    African Journals Online (AJOL)

    Preferred Customer

    We synthesized a number of aniline derivatives containing acyl groups to compare their barriers of rotation around ... KEY WORDS: Monoacyl aniline, Synthesis, Density functional theory, Rotation barrier. INTRODUCTION. Developments in ...

  16. Multicomponent density functional theory embedding formulation

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-07-28

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

  17. Optical properties of body-centered tetragonal C4: Insights from many-body perturbation and time-dependent density functional theories

    Science.gov (United States)

    Tarighi Ahmadpour, Mahdi; Rostamnejadi, Ali; Hashemifar, S. Javad

    2018-04-01

    We study the electronic structure and optical properties of a body-centered tetragonal phase of carbon (bct-C4) within the framework of time-dependent density functional theory and Bethe-Salpeter equation. The results indicate that the optical properties of bct-C4 are strongly affected by the electron-hole interaction. It is demonstrated that the long-range corrected exchange-correlation kernels could fairly reproduce the Bethe-Salpeter equation results. The effective carrier number reveals that at energies above 30 eV, the excitonic effects are not dominant any more and that the optical transitions originate mainly from electronic excitations. The emerged peaks in the calculated electron energy loss spectra are discussed in terms of plasmon excitations and interband transitions. The results of the research indicate that bct-C4 is an indirect wide-band-gap semiconductor, which is transparent in the visible region and opaque in the ultraviolet spectral range.

  18. Time-dependent broken-symmetry density functional theory simulation of the optical response of entangled paramagnetic defects: Color centers in lithium fluoride

    Science.gov (United States)

    Janesko, Benjamin G.

    2018-02-01

    Parameter-free atomistic simulations of entangled solid-state paramagnetic defects may aid in the rational design of devices for quantum information science. This work applies time-dependent density functional theory (TDDFT) embedded-cluster simulations to a prototype entangled-defect system, namely two adjacent singlet-coupled F color centers in lithium fluoride. TDDFT calculations accurately reproduce the experimental visible absorption of both isolated and coupled F centers. The most accurate results are obtained by combining spin symmetry breaking to simulate strong correlation, a large fraction of exact (Hartree-Fock-like) exchange to minimize the defect electrons' self-interaction error, and a standard semilocal approximation for dynamical correlations between the defect electrons and the surrounding ionic lattice. These results motivate application of two-reference correlated ab initio approximations to the M-center, and application of TDDFT in parameter-free simulations of more complex entangled paramagnetic defect architectures.

  19. Simulation of resonance hyper-Rayleigh scattering of molecules and metal clusters using a time-dependent density functional theory approach.

    Science.gov (United States)

    Hu, Zhongwei; Autschbach, Jochen; Jensen, Lasse

    2014-09-28

    Resonance hyper-Rayleigh scattering (HRS) of molecules and metal clusters have been simulated based on a time-dependent density functional theory approach. The resonance first-order hyperpolarizability (β) is obtained by implementing damped quadratic response theory using the (2n + 1) rule. To test this implementation, the prototypical dipolar molecule para-nitroaniline (p-NA) and the octupolar molecule crystal violet are used as benchmark systems. Moreover, small silver clusters Ag 8 and Ag 20 are tested with a focus on determining the two-photon resonant enhancement arising from the strong metal transition. Our results show that, on a per atom basis, the small silver clusters possess two-photon enhanced HRS comparable to that of larger nanoparticles. This finding indicates the potential interest of using small metal clusters for designing new nonlinear optical materials.

  20. Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

    2015-12-08

    Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment.

  1. Application of Time-Dependent Density Functional and Natural Bond Orbital Theories to the UV-vis Absorption Spectra of Some Phenolic Compounds.

    Science.gov (United States)

    Marković, Svetlana; Tošović, Jelena

    2015-09-03

    The UV-vis properties of 22 natural phenolic compounds, comprising anthraquinones, neoflavonoids, and flavonoids were systematically examined. The time-dependent density functional theory (TDDFT) approach in combination with the B3LYP, B3LYP-D2, B3P86, and M06-2X functionals was used to simulate the UV-vis spectra of the investigated compounds. It was shown that all methods exhibit very good (B3LYP slightly better) performance in reproducing the examined UV-vis spectra. However, the shapes of the Kohn-Sham molecular orbitals (MOs) involved in electronic transitions were misleading in constructing the MO correlation diagrams. To provide better understanding of redistribution of electron density upon excitation, the natural bond orbital (NBO) analysis was applied. Bearing in mind the spatial and energetic separations, as well as the character of the π bonding, lone pair, and π* antibonding natural localized molecular orbitals (NLMOs), the "NLMO clusters" were constructed. NLMO cluster should be understood as a part of a molecule characterized with distinguished electron density. It was shown that all absorption bands including all electronic transitions need to be inspected to fully understand the UV-vis spectrum of a certain compound, and, thus, to learn more about its UV-vis light absorption. Our investigation showed that the TDDFT and NBO theories are complementary, as the results from the two approaches can be combined to interpret the UV-vis spectra. Agreement between the predictions of the TDDFT approach and those based on the NLMO clusters is excellent in the case of major electronic transitions and long wavelengths. It should be emphasized that the approach for investigation of UV-vis light absorption based on the NLMO clusters is applied for the first time.

  2. Assignment of near-edge x-ray absorption fine structure spectra of metalloporphyrins by means of time-dependent density-functional calculations

    International Nuclear Information System (INIS)

    Schmidt, Norman; Fink, Rainer; Hieringer, Wolfgang

    2010-01-01

    The C 1s and N 1s near-edge x-ray absorption fine structure (NEXAFS) spectra of three prototype tetraphenyl porphyrin (TPP) molecules are discussed in the framework of a combined experimental and theoretical study. We employ time-dependent density-functional theory (TDDFT) to compute the NEXAFS spectra of the open- and closed-shell metalloporphyrins CoTPP and ZnTPP as well as the free-base 2HTPP in realistic nonplanar conformations. Using Becke's well-known half-and-half hybrid functional, the computed core excitation spectra are mostly in good agreement with the experimental data in the low-energy region below the appropriate ionization threshold. To make these calculations feasible, we apply a new, simple scheme based on TDDFT using a modified single-particle input spectrum. This scheme is very easy to implement in standard codes and allows one to compute core excitation spectra at a similar cost as ordinary UV/vis spectra even for larger molecules. We employ these calculations for a detailed assignment of the NEXAFS spectra including subtle shifts in certain peaks of the N 1s spectra, which depend on the central coordination of the TPP ligand. We furthermore assign the observed NEXAFS resonances to the individual molecular subunits of the investigated TPP molecules.

  3. Regarding the use and misuse of retinal protonated Schiff base photochemistry as a test case for time-dependent density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Valsson, Omar [Department of Chemistry and Applied Biosciences, ETH Zurich and Facoltà di Informatica, Instituto di Scienze Computationali, Università della Svizzera italiana, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Filippi, Claudia, E-mail: c.filippi@utwente.nl [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Casida, Mark E., E-mail: mark.casida@ujf-grenoble.fr [Laboratoire de Chimie Théorique, Département de Chimie Moléculaire (DCM), Institut de Chimie Moléculaire de Grenoble (ICMG), Université Joseph Fourier, Grenoble I, F-3801 Grenoble (France)

    2015-04-14

    The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.

  4. Path-dependent functions

    International Nuclear Information System (INIS)

    Khrapko, R.I.

    1985-01-01

    A uniform description of various path-dependent functions is presented with the help of expansion of the type of the Taylor series. So called ''path-integrals'' and ''path-tensor'' are introduced which are systems of many-component quantities whose values are defined for arbitrary paths in coordinated region of space in such a way that they contain a complete information on the path. These constructions are considered as elementary path-dependent functions and are used instead of power monomials in the usual Taylor series. Coefficients of such an expansion are interpreted as partial derivatives dependent on the order of the differentiations or else as nonstandard cavariant derivatives called two-point derivatives. Some examples of pathdependent functions are presented.Space curvature tensor is considered whose geometrica properties are determined by the (non-transitive) translator of parallel transport of a general type. Covariant operation leading to the ''extension'' of tensor fiels is pointed out

  5. Spectral function from Reduced Density Matrix Functional Theory

    Science.gov (United States)

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

    2015-03-01

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

  6. Wave-function functionals for the density

    International Nuclear Information System (INIS)

    Slamet, Marlina; Pan Xiaoyin; Sahni, Viraht

    2011-01-01

    We extend the idea of the constrained-search variational method for the construction of wave-function functionals ψ[χ] of functions χ. The search is constrained to those functions χ such that ψ[χ] reproduces the density ρ(r) while simultaneously leading to an upper bound to the energy. The functionals are thereby normalized and automatically satisfy the electron-nucleus coalescence condition. The functionals ψ[χ] are also constructed to satisfy the electron-electron coalescence condition. The method is applied to the ground state of the helium atom to construct functionals ψ[χ] that reproduce the density as given by the Kinoshita correlated wave function. The expectation of single-particle operators W=Σ i r i n , n=-2,-1,1,2, W=Σ i δ(r i ) are exact, as must be the case. The expectations of the kinetic energy operator W=-(1/2)Σ i ∇ i 2 , the two-particle operators W=Σ n u n , n=-2,-1,1,2, where u=|r i -r j |, and the energy are accurate. We note that the construction of such functionals ψ[χ] is an application of the Levy-Lieb constrained-search definition of density functional theory. It is thereby possible to rigorously determine which functional ψ[χ] is closer to the true wave function.

  7. Critical Assessment of Time-Dependent Density Functional Theory for Excited States of Open-Shell Systems: II. Doublet-Quartet Transitions.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian

    2016-06-14

    Compared with closed-shell systems, open-shell systems place three additional challenges to time-dependent density functional theory (TD-DFT) for electronically excited states: (a) the spin-contamination problem is a serious issue; (b) the exchange-correlation (XC) kernel may be numerically instable; and (c) the single-determinant description of open-shell ground states readily becomes energetically instable. Confined to flip-up single excitations, the spin-contamination problem can largely be avoided by using the spin-flip TD-DFT (SF-TD-DFT) formalism, provided that a noncollinear XC kernel is employed. As for the numerical instabilities associated with such a kernel, only an ad hoc scheme has been proposed so far, viz., the ALDA0 kernel, which amounts to setting the divergent components (arising from density gradients and kinetic energy density) simply to zero. The ground-state instability problem can effectively be avoided by introducing the Tamm-Dancoff approximation (TDA) to TD-DFT. Therefore, on a general basis, the SF-TDA/ALDA0 Ansatz is so far the only promising means within the TD-DFT framework for flip-up single excitations of open-shell systems. To assess systematically the performance of SF-TDA/ALDA0, in total 61 low-lying quartet excited states of the benchmark set of 11 small radicals [J. Chem. Theory Comput. 2016, 12, 238] are investigated with various XC functionals. Taking the MRCISD+Q (multireference configuration interaction with singles and doubles plus the Davidson correction) results as benchmark, it is found that the mean absolute errors of SF-TDA/ALDA0 with the SAOP (statistical averaging of model orbital potentials), global hybrid, and range-separated hybrid functionals are in the range of 0.2-0.4 eV. This is in line not only with the typical accuracy of TD-DFT for singlet and triplet excited states of closed-shell systems but also with the gross accuracy of spin-adapted TD-DFT for spin-conserving excited states of open-shell systems.

  8. Study of nuclear level density parameter and its temperature dependence

    International Nuclear Information System (INIS)

    Nasrabadi, M. N.; Behkami, A. N.

    2000-01-01

    The nuclear level density ρ is the basic ingredient required for theoretical studies of nuclear reaction and structure. It describes the statistical nuclear properties and is expressed as a function of various constants of motion such as number of particles, excitation energy and angular momentum. In this work the energy and spin dependence of nuclear level density will be presented and discussed. In addition the level density parameter α will be extracted from this level density information, and its temperature and mass dependence will be obtained

  9. Linear-scaling time-dependent density-functional theory beyond the Tamm-Dancoff approximation: Obtaining efficiency and accuracy with in situ optimised local orbitals

    Energy Technology Data Exchange (ETDEWEB)

    Zuehlsdorff, T. J., E-mail: tjz21@cam.ac.uk; Payne, M. C. [Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Hine, N. D. M. [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Haynes, P. D. [Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Department of Physics, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)

    2015-11-28

    We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.

  10. Simulating Ru L3-edge X-ray absorption spectroscopy with time-dependent density functional theory: model complexes and electron localization in mixed-valence metal dimers.

    Science.gov (United States)

    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 Ru(II) and Ru(III) 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 Ru(II) 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)5M(II)-CN-Ru(III)(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.

  11. and density-dependent quark mass model

    Indian Academy of Sciences (India)

    Since a fair proportion of such dense proto stars are likely to be ... the temperature- and density-dependent quark mass (TDDQM) model which we had em- ployed in .... instead of Tc ~170 MeV which is a favoured value for the ud matter [26].

  12. Assessment of time-dependent density functional theory with the restricted excitation space approximation for excited state calculations of large systems

    Science.gov (United States)

    Hanson-Heine, Magnus W. D.; George, Michael W.; Besley, Nicholas A.

    2018-06-01

    The restricted excitation subspace approximation is explored as a basis to reduce the memory storage required in linear response time-dependent density functional theory (TDDFT) calculations within the Tamm-Dancoff approximation. It is shown that excluding the core orbitals and up to 70% of the virtual orbitals in the construction of the excitation subspace does not result in significant changes in computed UV/vis spectra for large molecules. The reduced size of the excitation subspace greatly reduces the size of the subspace vectors that need to be stored when using the Davidson procedure to determine the eigenvalues of the TDDFT equations. Furthermore, additional screening of the two-electron integrals in combination with a reduction in the size of the numerical integration grid used in the TDDFT calculation leads to significant computational savings. The use of these approximations represents a simple approach to extend TDDFT to the study of large systems and make the calculations increasingly tractable using modest computing resources.

  13. Application of the Real-Time Time-Dependent Density Functional Theory to Excited-State Dynamics of Molecules and 2D Materials

    Science.gov (United States)

    Miyamoto, Yoshiyuki; Rubio, Angel

    2018-04-01

    We review our recent developments in the ab initio simulation of excited-state dynamics within the framework of time-dependent density functional theory (TDDFT). Our targets range from molecules to 2D materials, although the methods are general and can be applied to any other finite and periodic systems. We discuss examples of excited-state dynamics obtained by real-time TDDFT coupled with molecular dynamics (MD) and the Ehrenfest approximation, including photoisomerization in molecules, photoenhancement of the weak interatomic attraction of noble gas atoms, photoenhancement of the weak interlayer interaction of 2D materials, pulse-laser-induced local bond breaking of adsorbed atoms on 2D sheets, modulation of UV light intensity by graphene nanoribbons at terahertz frequencies, and collision of high-speed ions with the 2D material to simulate the images taken by He ion microscopy. We illustrate how the real-time TDDFT approach is useful for predicting and understanding non-equilibrium dynamics in condensed matter. We also discuss recent developments that address the excited-state dynamics of systems out of equilibrium and future challenges in this fascinating field of research.

  14. Derivation of the RPA (Random Phase Approximation) Equation of ATDDFT (Adiabatic Time Dependent Density Functional Ground State Response Theory) from an Excited State Variational Approach Based on the Ground State Functional.

    Science.gov (United States)

    Ziegler, Tom; Krykunov, Mykhaylo; Autschbach, Jochen

    2014-09-09

    The random phase approximation (RPA) equation of adiabatic time dependent density functional ground state response theory (ATDDFT) has been used extensively in studies of excited states. It extracts information about excited states from frequency dependent ground state response properties and avoids, thus, in an elegant way, direct Kohn-Sham calculations on excited states in accordance with the status of DFT as a ground state theory. Thus, excitation energies can be found as resonance poles of frequency dependent ground state polarizability from the eigenvalues of the RPA equation. ATDDFT is approximate in that it makes use of a frequency independent energy kernel derived from the ground state functional. It is shown in this study that one can derive the RPA equation of ATDDFT from a purely variational approach in which stationary states above the ground state are located using our constricted variational DFT (CV-DFT) method and the ground state functional. Thus, locating stationary states above the ground state due to one-electron excitations with a ground state functional is completely equivalent to solving the RPA equation of TDDFT employing the same functional. The present study is an extension of a previous work in which we demonstrated the equivalence between ATDDFT and CV-DFT within the Tamm-Dancoff approximation.

  15. Density functional theory of nuclei

    International Nuclear Information System (INIS)

    Terasaki, Jun

    2008-01-01

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

  16. Experimental and time-dependent density functional theory characterization of the UV-visible spectra of monomeric and μ-oxo dimeric ferriprotoporphyrin IX.

    Science.gov (United States)

    Kuter, David; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

    2012-10-01

    Speciation of ferriprotoporphyrin IX, Fe(III)PPIX, in aqueous solution is complex. Despite the use of its characteristic spectroscopic features for identification, the theoretical basis of the unique UV-visible absorbance spectrum of μ-[Fe(III)PPIX](2)O has not been explored. To investigate this and to establish a structural and spectroscopic model for Fe(III)PPIX species, density functional theory (DFT) calculations were undertaken for H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O. The models agreed with related Fe(III)porphyrin crystal structures and reproduced vibrational spectra well. The UV-visible absorbance spectra of H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O were calculated using time-dependent DFT and reproduced major features of the experimental spectra of both. Transitions contributing to calculated excitations have been identified. The features of the electronic spectrum calculated for μ-[Fe(III)PPIX](2)O were attributed to delocalization of electron density between the two porphyrin rings of the dimer, the weaker ligand field of the axial ligand, and antiferromagnetic coupling of the Fe(III) centers. Room temperature magnetic circular dichroism (MCD) spectra have been recorded and are shown to be useful in distinguishing between these two Fe(III)PPIX species. Bands underlying major spectroscopic features were identified through simultaneous deconvolution of UV-visible and MCD spectra. Computed UV-visible spectra were compared to deconvoluted spectra. Interpretation of the prominent bands of H(2)O-Fe(III)PPIX largely conforms to previous literature. Owing to the weak paramagnetism of μ-[Fe(III)PPIX](2)O at room temperature and the larger number of underlying excitations, interpretation of its experimental UV-visible spectrum was necessarily tentative. Nonetheless, comparison with the calculated spectra of antiferromagnetically coupled and paramagnetic forms of the μ-oxo dimer of Fe(III)porphine suggested that the composition of the Soret band involves

  17. 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

  18. Modeling L2,3-Edge X-ray Absorption Spectroscopy with Real-Time Exact Two-Component Relativistic Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Kasper, Joseph M; Lestrange, Patrick J; Stetina, Torin F; Li, Xiaosong

    2018-04-10

    X-ray absorption spectroscopy is a powerful technique to probe local electronic and nuclear structure. There has been extensive theoretical work modeling K-edge spectra from first principles. However, modeling L-edge spectra directly with density functional theory poses a unique challenge requiring further study. Spin-orbit coupling must be included in the model, and a noncollinear density functional theory is required. Using the real-time exact two-component method, we are able to variationally include one-electron spin-orbit coupling terms when calculating the absorption spectrum. The abilities of different basis sets and density functionals to model spectra for both closed- and open-shell systems are investigated using SiCl 4 and three transition metal complexes, TiCl 4 , CrO 2 Cl 2 , and [FeCl 6 ] 3- . Although we are working in the real-time framework, individual molecular orbital transitions can still be recovered by projecting the density onto the ground state molecular orbital space and separating contributions to the time evolving dipole moment.

  19. The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the x-ray emission spectroscopy of transition metal complexes.

    Science.gov (United States)

    Roper, Ian P E; Besley, Nicholas A

    2016-03-21

    The simulation of X-ray emission spectra of transition metal complexes with time-dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the relevant core orbital, and these calculations can be performed using the frozen orbital approximation or with the relaxation of the orbitals of the intermediate core-ionised state included. Both standard exchange-correlation functionals and functionals specifically designed for X-ray emission spectroscopy are studied, and it is shown that the computed spectral band profiles are sensitive to the exchange-correlation functional used. The computed intensities of the spectral bands can be rationalised by considering the metal p orbital character of the valence molecular orbitals. To compute X-ray emission spectra with the correct energy scale allowing a direct comparison with experiment requires the relaxation of the core-ionised state to be included and the use of specifically designed functionals with increased amounts of Hartree-Fock exchange in conjunction with high quality basis sets. A range-corrected functional with increased Hartree-Fock exchange in the short range provides transition energies close to experiment and spectral band profiles that have a similar accuracy to those from standard functionals.

  20. Density-functional expansion methods: Grand challenges.

    Science.gov (United States)

    Giese, Timothy J; York, Darrin M

    2012-03-01

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

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

    Science.gov (United States)

    Luo, Kai; Trickey, S. B.

    2018-03-01

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

  2. X-ray Absorption Spectroscopy Combined with Time-Dependent Density Functional Theory Elucidates Differential Substitution Pathways of Au(I) and Au(III) with Zinc Fingers.

    Science.gov (United States)

    Abbehausen, Camilla; de Paiva, Raphael Enoque Ferraz; Bjornsson, Ragnar; Gomes, Saulo Quintana; Du, Zhifeng; Corbi, Pedro Paulo; Lima, Frederico Alves; Farrell, Nicholas

    2018-01-02

    A combination of two elements' (Au, Zn) X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TD-DFT) allowed the elucidation of differential substitution pathways of Au(I) and Au(III) compounds reacting with biologically relevant zinc fingers (ZnFs). Gold L 3 -edge XAS probed the interaction of gold and the C-terminal Cys 2 HisCys finger of the HIV-1 nucleocapsid protein NCp7, and the Cys 2 His 2 human transcription factor Sp1. The use of model compounds helped assign oxidation states and the identity of the gold-bound ligands. The computational studies accurately reproduced the experimental XAS spectra and allowed the proposition of structural models for the interaction products at early time points. The direct electrophilic attack on the ZnF by the highly thiophilic Au(I) resulted in a linear P-Au-Cys coordination sphere after zinc ejection whereas for the Sp1, loss of PEt 3 results in linear Cys-Au-Cys or Cys-Au-His arrangements. Reactions with Au(III) compounds, on the other hand, showed multiple binding modes. Prompt reaction between [AuCl(dien)] 2+ and [Au(dien)(DMAP)] 3+ with Sp1 showed a partially reduced Au center and a final linear His-Au-His coordination. Differently, in the presence of NCp7, [AuCl(dien)] 2+ readily reduces to Au(I) and changes from square-planar to linear geometry with Cys-Au-His coordination, while [Au(dien)(DMAP)] 3+ initially maintains its Au(III) oxidation state and square-planar geometry and the same first coordination sphere. The latter is the first observation of a "noncovalent" interaction of a Au(III) complex with a zinc finger and confirms early hypotheses that stabilization of Au(III) occurs with N-donor ligands. Modification of the zinc coordination sphere, suggesting full or partial zinc ejection, is observed in all cases, and for [Au(dien)(DMAP)] 3+ this represents a novel mechanism for nucleocapsid inactivation. The combination of XAS and TD-DFT presents the first direct experimental

  3. Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

    Science.gov (United States)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

    2013-10-02

    Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

  4. Density-dependent cladogenesis in birds.

    Directory of Open Access Journals (Sweden)

    Albert B Phillimore

    2008-03-01

    Full Text Available A characteristic signature of adaptive radiation is a slowing of the rate of speciation toward the present. On the basis of molecular phylogenies, studies of single clades have frequently found evidence for a slowdown in diversification rate and have interpreted this as evidence for density dependent speciation. However, we demonstrated via simulation that large clades are expected to show stronger slowdowns than small clades, even if the probability of speciation and extinction remains constant through time. This is a consequence of exponential growth: clades, which, by chance, diversify at above the average rate early in their history, will tend to be large. They will also tend to regress back to the average diversification rate later on, and therefore show a slowdown. We conducted a meta-analysis of the distribution of speciation events through time, focusing on sequence-based phylogenies for 45 clades of birds. Thirteen of the 23 clades (57% that include more than 20 species show significant slowdowns. The high frequency of slowdowns observed in large clades is even more extreme than expected under a purely stochastic constant-rate model, but is consistent with the adaptive radiation model. Taken together, our data strongly support a model of density-dependent speciation in birds, whereby speciation slows as ecological opportunities and geographical space place limits on clade growth.

  5. Dependence of Excited State Potential Energy Surfaces on the Spatial Overlap of the Kohn-Sham Orbitals and the Amount of Nonlocal Hartree-Fock Exchange in Time-Dependent Density Functional Theory.

    Science.gov (United States)

    Plötner, Jürgen; Tozer, David J; Dreuw, Andreas

    2010-08-10

    Time-dependent density functional theory (TDDFT) with standard GGA or hybrid exchange-correlation functionals is not capable of describing the potential energy surface of the S1 state of Pigment Yellow 101 correctly; an additional local minimum is observed at a twisted geometry with substantial charge transfer (CT) character. To investigate the influence of nonlocal exact orbital (Hartree-Fock) exchange on the shape of the potential energy surface of the S1 state in detail, it has been computed along the twisting coordinate employing the standard BP86, B3LYP, and BHLYP xc-functionals as well as the long-range separated (LRS) exchange-correlation (xc)-functionals LC-BOP, ωB97X, ωPBE, and CAM-B3LYP and compared to RI-CC2 benchmark results. Additionally, a recently suggested Λ-parameter has been employed that measures the amount of CT in an excited state by calculating the spatial overlap of the occupied and virtual molecular orbitals involved in the transition. Here, the error in the calculated S1 potential energy curves at BP86, B3LYP, and BHLYP can be clearly related to the Λ-parameter, i.e., to the extent of charge transfer. Additionally, it is demonstrated that the CT problem is largely alleviated when the BHLYP xc-functional is employed, although it still exhibits a weak tendency to underestimate the energy of CT states. The situation improves drastically when LRS-functionals are employed within TDDFT excited state calculations. All tested LRS-functionals give qualitatively the correct potential energy curves of the energetically lowest excited states of P. Y. 101 along the twisting coordinate. While LC-BOP and ωB97X overcorrect the CT problem and now tend to give too large excitation energies compared to other non-CT states, ωPBE and CAM-B3LYP are in excellent agreement with the RI-CC2 results, with respect to both the correct shape of the potential energy curve as well as the absolute values of the calculated excitation energies.

  6. Watching excitons move: the time-dependent transition density matrix

    Science.gov (United States)

    Ullrich, Carsten

    2012-02-01

    Time-dependent density-functional theory allows one to calculate excitation energies and the associated transition densities in principle exactly. The transition density matrix (TDM) provides additional information on electron-hole localization and coherence of specific excitations of the many-body system. We have extended the TDM concept into the real-time domain in order to visualize the excited-state dynamics in conjugated molecules. The time-dependent TDM is defined as an implicit density functional, and can be approximately obtained from the time-dependent Kohn-Sham orbitals. The quality of this approximation is assessed in simple model systems. A computational scheme for real molecular systems is presented: the time-dependent Kohn-Sham equations are solved with the OCTOPUS code and the time-dependent Kohn-Sham TDM is calculated using a spatial partitioning scheme. The method is applied to show in real time how locally created electron-hole pairs spread out over neighboring conjugated molecular chains. The coupling mechanism, electron-hole coherence, and the possibility of charge separation are discussed.

  7. 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...

  8. Nuclear spectroscopy with density dependent effective interactions

    International Nuclear Information System (INIS)

    Krewald, S.

    1976-07-01

    The paper investigates excited nuclear states with density-dependent effective interactions. In the first part of the paper, the structure and the width of the multipole giant resonances discovered in 1972 are derived microscopically. Because of their high excitation energy, these giant resonances are unstable to particle emission and thus often have a considerable decay width. Due to their collective structure, the giant resonances can be described by RPA in good approximation. In this paper, the continuum RPA is applied to the spherical nuclei 16 O, 40 Ca, 90 Zr and 208 Pb. The experimental centroid energy are in very good agreement with the calculations performed in the paper. (orig./WL) [de

  9. Calculation of the RPA response function of nuclei to quasi-elastic electron scattering with a density-dependent NN interaction

    International Nuclear Information System (INIS)

    Caillon, J-C.; Labarsouque, J.

    1997-01-01

    So far, the non-relativistic longitudinal and transverse functions in electron quasi-elastic scattering on the nuclei failed in reproducing satisfactorily the existent experimental data. The calculations including relativistic RPA correlations utilize until now the relativistic Hartree approximation to describe the nuclear matter. But, this provides an incompressibility module two times higher than its experimental value what is an important drawback for the calculation of realistic relativistic RPA correlations. Hence, we have determined the RPA response functions of nuclei by utilising a description of the relativistic nuclear matter leading to an incompressibility module in agreement with the empirical value. To do that we have utilized an interaction in the relativistic Hartree approximation in which we have determined the coupling constants σ-N and ω-N as a function of the density in order to reproduce the saturation curve obtained by a Dirac-Brueckner calculation. The results which we have obtained show that the longitudinal response function and the Coulomb sum generally overestimated when one utilizes the pure relativistic Hartree approximation, are here in good agreement with the experimental data for several nuclei

  10. Intercohort density dependence drives brown trout habitat selection

    Science.gov (United States)

    Ayllón, Daniel; Nicola, Graciela G.; Parra, Irene; Elvira, Benigno; Almodóvar, Ana

    2013-01-01

    Habitat selection can be viewed as an emergent property of the quality and availability of habitat but also of the number of individuals and the way they compete for its use. Consequently, habitat selection can change across years due to fluctuating resources or to changes in population numbers. However, habitat selection predictive models often do not account for ecological dynamics, especially density dependent processes. In stage-structured population, the strength of density dependent interactions between individuals of different age classes can exert a profound influence on population trajectories and evolutionary processes. In this study, we aimed to assess the effects of fluctuating densities of both older and younger competing life stages on the habitat selection patterns (described as univariate and multivariate resource selection functions) of young-of-the-year, juvenile and adult brown trout Salmo trutta. We observed all age classes were selective in habitat choice but changed their selection patterns across years consistently with variations in the densities of older but not of younger age classes. Trout of an age increased selectivity for positions highly selected by older individuals when their density decreased, but this pattern did not hold when the density of younger age classes varied. It suggests that younger individuals are dominated by older ones but can expand their range of selected habitats when density of competitors decreases, while older trout do not seem to consider the density of younger individuals when distributing themselves even though they can negatively affect their final performance. Since these results may entail critical implications for conservation and management practices based on habitat selection models, further research should involve a wider range of river typologies and/or longer time frames to fully understand the patterns of and the mechanisms underlying the operation of density dependence on brown trout habitat

  11. Linear response at the 4-component relativistic density-functional level: application to the frequency-dependent dipole polarizability of Hg, AuH and PtH2

    International Nuclear Information System (INIS)

    Salek, Pawel; Helgaker, Trygve; Saue, Trond

    2005-01-01

    We report the implementation and application of linear response density-functional theory (DFT) based on the 4-component relativistic Dirac-Coulomb Hamiltonian. The theory is cast in the language of second quantization and is based on the quasienergy formalism (Floquet theory), replacing the initial state dependence of the Runge-Gross theorem by periodic boundary conditions. Contradictions in causality and symmetry of the time arguments are thereby avoided and the exchange-correlation potential and kernel can be expressed as functional derivatives of the quasienergy. We critically review the derivation of the quasienergy analogues of the Hohenberg-Kohn theorem and the Kohn-Sham formalism and discuss the nature of the quasienergy exchange-correlation functional. Structure is imposed on the response equations in terms of Hermiticity and time-reversal symmetry. It is observed that functionals of spin and current densities, corresponding to time-antisymmetric operators, contribute to frequency-dependent and not static electric properties. Physically, this follows from the fact that only a time-dependent electric field creates a magnetic field. It is furthermore observed that hybrid functionals enhance spin polarization since only exact exchange contributes to anti-Hermitian trial vectors. We apply 4-component relativistic linear response DFT to the calculation of the frequency-dependent polarizability of the isoelectronic series Hg, AuH and PtH 2 . Unlike for the molecules, the effect of electron correlation on the polarizability of the mercury atom is very large, about 25%. We observe a remarkable performance of the local-density approximation (LDA) functional in reproducing the experimental frequency-dependent polarizability of this atom, clearly superior to that of the BLYP and B3LYP functionals. This allows us to extract Cauchy moments (S(-4) = 382.82 and S(-6) = 6090.89 a.u.) that we believe are superior to experiment since we go to higher order in the Cauchy

  12. Wildlife disease elimination and density dependence

    KAUST Repository

    Potapov, A.

    2012-05-16

    Disease control by managers is a crucial response to emerging wildlife epidemics, yet the means of control may be limited by the method of disease transmission. In particular, it is widely held that population reduction, while effective for controlling diseases that are subject to density-dependent (DD) transmission, is ineffective for controlling diseases that are subject to frequency-dependent (FD) transmission. We investigate control for horizontally transmitted diseases with FD transmission where the control is via culling or harvest that is non-selective with respect to infection and the population can compensate through DD recruitment or survival. Using a mathematical model, we show that culling or harvesting can eradicate the disease, even when transmission dynamics are FD. Eradication can be achieved under FD transmission when DD birth or recruitment induces compensatory growth of new, healthy individuals, which has the net effect of reducing disease prevalence by dilution. We also show that if harvest is used simultaneously with vaccination, and there is high enough transmission coefficient, application of both controls may be less efficient than vaccination alone. We illustrate the effects of these control approaches on disease prevalence for chronic wasting disease in deer where the disease is transmitted directly among deer and through the environment.

  13. Dependence of the elastic properties of the early-transition-metal monoborides on their electronic structures: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xuewen, E-mail: xuxuewen@hebut.edu.cn [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Fu, Kun [School of Computer Science and Engineering, Hebei University of Technology, Tianjin 300130 (China); Li, Lanlan; Lu, Zunming; Zhang, Xinghua; Fan, Ying; Lin, Jing; Liu, Guodong; Luo, Hongzhi; Tang, Chengchun [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China)

    2013-06-15

    We systematically investigated the crystal structure, stability, elastic properties, chemical bonding and electronic properties of the early-transition-metal monoborides (TMBs, where TM=Sc, Ti, V, Cr, Y, Zr, Nb, Mo, Hf, Mo, and W) using the ab initio calculations based on the density functional theory. The results indicated that all 11 TMBs crystallized to a CrB-type structure are thermodynamically and mechanically stable. The elastic constants were calculated using the finite strain method. The correlation between the electronic structure and elastic properties was discussed. YB was found to have high machinability (B/C{sub 44}=1.73) and low hardness (C{sub 44}=43 GPa). The weak interaction between the interleaved yttrium planes and weak pd bonding resulted in the good machinability of YB.

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

    OpenAIRE

    Harbola, Manoj K.; Samal, Prasanjit

    2004-01-01

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

  15. Density functionals in the laboratory frame

    International Nuclear Information System (INIS)

    Giraud, B. G.

    2008-01-01

    We compare several definitions of the density of a self-bound system, such as a nucleus, in relation with its center-of-mass zero-point motion. A trivial deconvolution relates the internal density to the density defined in the laboratory frame. This result is useful for the practical definition of density functionals

  16. 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.)

  17. Covariant density functional theory for nuclear matter

    International Nuclear Information System (INIS)

    Badarch, U.

    2007-01-01

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

  18. Density functional study of gamma-aminopropyltriethoxysilane

    International Nuclear Information System (INIS)

    Bistricic, L; Volovsek, V; Daani, V; Leskovac, M

    2006-01-01

    Density functional theory calculations using Becke's three-parameter exchange functional in combination with the Lee-Young-Parr correlation functional (B3-LYP) and standard 6-311 + G(d,p) basis set were carried out to study the conformational stability and vibrational spectra of gamma-aminopropyltriethoxysilane. Calculations reveal the existence of two stable conformers trans and gauche. The calculated energy for the gauche conformation was found to be 608 cm -1 above the minimum energy of the trans conformation. Temperature dependence of Raman spectra of liquid APTES and DFT calculation enabled us to identify the vibrational bands characteristic for both conformers. It has been shown that there is an increase in the population of gauche conformer with increasing temperature

  19. Density-dependence as a size-independent regulatory mechanism.

    Science.gov (United States)

    de Vladar, Harold P

    2006-01-21

    The growth function of populations is central in biomathematics. The main dogma is the existence of density-dependence mechanisms, which can be modelled with distinct functional forms that depend on the size of the population. One important class of regulatory functions is the theta-logistic, which generalizes the logistic equation. Using this model as a motivation, this paper introduces a simple dynamical reformulation that generalizes many growth functions. The reformulation consists of two equations, one for population size, and one for the growth rate. Furthermore, the model shows that although population is density-dependent, the dynamics of the growth rate does not depend either on population size, nor on the carrying capacity. Actually, the growth equation is uncoupled from the population size equation, and the model has only two parameters, a Malthusian parameter rho and a competition coefficient theta. Distinct sign combinations of these parameters reproduce not only the family of theta-logistics, but also the van Bertalanffy, Gompertz and Potential Growth equations, among other possibilities. It is also shown that, except for two critical points, there is a general size-scaling relation that includes those appearing in the most important allometric theories, including the recently proposed Metabolic Theory of Ecology. With this model, several issues of general interest are discussed such as the growth of animal population, extinctions, cell growth and allometry, and the effect of environment over a population.

  20. Density functional theory and parallel processing

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  1. 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

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

    International Nuclear Information System (INIS)

    Luo Ji

    2006-01-01

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

  3. Nuclear symmetry energy in density dependent hadronic models

    International Nuclear Information System (INIS)

    Haddad, S.

    2008-12-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

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

    Science.gov (United States)

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

    2015-07-01

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

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

    Science.gov (United States)

    Kepp, Kasper P

    2018-03-14

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

  7. 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.

  8. A Safari Through Density Functional Theory

    Science.gov (United States)

    Dreizler, Reiner M.; Lüdde, Cora S.

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

  9. 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 ...

  10. Quantal density functional theory. 2. ed.

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2016-01-01

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

  11. 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.

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

    Science.gov (United States)

    Rabilloud, Franck

    2014-10-14

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Helbig, N

    2006-05-15

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

  14. Density dependence of dielectronic recombination in selenium

    International Nuclear Information System (INIS)

    Hagelstein, P.L.; Rosen, M.D.; Jacobs, V.L.

    1986-01-01

    Dielectronic recombination has been found to be the dominant recombination process in the determination of the ionization balance of selenium near the Ne-like sequence under conditions relevant to the exploding-foil EUV laser plasmas. The dielectronic recombination process tends to populate excited levels, and these levels in turn are more susceptible to subsequent excitation and ionization than are the ground-state ions. If one defines an effective recombination rate which includes, in addition to the primary recombination, the subsequent excitation and ionization of the additional excited-state population due to the primary recombination, then this effective recombination rate can be density-sensitive at relatively low electron density. We present results for this effective dielectronic recombination rate at an electron density of 3 x 10/sup 20/ electrons/cm 3 for recombination from Ne-like to Na-like selenium and from F-like to Ne-like selenium. In the former case, the effective recombination rate coefficient is found to be 1.8 x 10/sup -11/ cm 3 /sec at 1.0 keV, which is to be compared with the zero-density value of 2.8 x 10/sup -11/ cm 3 /sec. In the latter case (F-like to Ne-like), the effective recombination rate coefficient is found to be 1.3 x 10/sup -11/ cm 3 /sec, which is substantially reduced from the zero-density result of 3.3 x 10/sup -11/ cm 3 /sec. We have examined the effects of dielectronic recombination on the laser gain of the dominant Ne-like 3p-3s transitions and have compared our results with those presented by Whitten et al. [Phys. Rev. A 33, 2171 (1986)

  15. Modelling interactions of toxicants and density dependence in wildlife populations

    Science.gov (United States)

    Schipper, Aafke M.; Hendriks, Harrie W.M.; Kauffman, Matthew J.; Hendriks, A. Jan; Huijbregts, Mark A.J.

    2013-01-01

    1. A major challenge in the conservation of threatened and endangered species is to predict population decline and design appropriate recovery measures. However, anthropogenic impacts on wildlife populations are notoriously difficult to predict due to potentially nonlinear responses and interactions with natural ecological processes like density dependence. 2. Here, we incorporated both density dependence and anthropogenic stressors in a stage-based matrix population model and parameterized it for a density-dependent population of peregrine falcons Falco peregrinus exposed to two anthropogenic toxicants [dichlorodiphenyldichloroethylene (DDE) and polybrominated diphenyl ethers (PBDEs)]. Log-logistic exposure–response relationships were used to translate toxicant concentrations in peregrine falcon eggs to effects on fecundity. Density dependence was modelled as the probability of a nonbreeding bird acquiring a breeding territory as a function of the current number of breeders. 3. The equilibrium size of the population, as represented by the number of breeders, responded nonlinearly to increasing toxicant concentrations, showing a gradual decrease followed by a relatively steep decline. Initially, toxicant-induced reductions in population size were mitigated by an alleviation of the density limitation, that is, an increasing probability of territory acquisition. Once population density was no longer limiting, the toxicant impacts were no longer buffered by an increasing proportion of nonbreeders shifting to the breeding stage, resulting in a strong decrease in the equilibrium number of breeders. 4. Median critical exposure concentrations, that is, median toxicant concentrations in eggs corresponding with an equilibrium population size of zero, were 33 and 46 μg g−1 fresh weight for DDE and PBDEs, respectively. 5. Synthesis and applications. Our modelling results showed that particular life stages of a density-limited population may be relatively insensitive to

  16. Density dependence of line intensities and application to plasma diagnostics

    International Nuclear Information System (INIS)

    Masai, Kuniaki.

    1993-02-01

    Electron density dependence of spectral lines are discussed in view of application to density diagnostics of plasmas. The dependence arises from competitive level population processes, radiative and collisional transitions from the excited states. Results of the measurement on tokamak plasmas are presented to demonstrate the usefulness of line intensity ratios for density diagnostics. Also general characteristics related to density dependence are discussed with atomic-number scaling for H-like and He-like systems to be helpful for application to higher density plasmas. (author)

  17. Spin dependent photon structure functions

    International Nuclear Information System (INIS)

    Manohar, A.V.; Massachusetts Inst. of Tech., Cambridge

    1989-01-01

    Spin dependent structure functions of the photon are studied using the operator product expansion. There are new twist-two photon and gluon operators which contribute. The structure functions g 1 and F 3 are calculable in QCD, but differ from their free quark values. The corrections to F 3 are suppressed by 1/log Q 2 . The calculation is an extension of the analysis of Witten for the spin averaged structure functions F 1 and F 2 . (orig.)

  18. Relationship of Quantum Entanglement to Density Functional Theory

    OpenAIRE

    Rajagopal, A. K.; Rendell, R. W.

    2005-01-01

    The maximum von Neumann entropy principle subject to given constraints of mean values of some physical observables determines the density matrix. Similarly the stationary action principle in the case of time-dependent (dissipative) situations under similar constraints yields the density matrix. The free energy and measures of entanglement are expressed in terms of such a density matrix and thus define respective functionals of the mean values. In the light of several model calculations, it is...

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

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2018-01-01

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

  20. External field as the functional of inhomogeneous density and the density matrix functional approach

    NARCIS (Netherlands)

    Bobrov, V.B.; Trigger, S.A.; Vlasov, Y.P.

    2012-01-01

    Based on the Hohenberg-Kohn lemma and the hypotheses of the density functional existence for the external-field potential, it is shown that the strict result of the density functional theory is the equation of the external-field potential as the density functional. This result leads to the

  1. Can time-dependent density functional theory predict intersystem crossing in organic chromophores? A case study on benzo(bis)-X-diazole based donor-acceptor-donor type molecules.

    Science.gov (United States)

    Tam, Teck Lip Dexter; Lin, Ting Ting; Chua, Ming Hui

    2017-06-21

    Here we utilized new diagnostic tools in time-dependent density functional theory to explain the trend of intersystem crossing in benzo(bis)-X-diazole based donor-acceptor-donor type molecules. These molecules display a wide range of fluorescence quantum yields and triplet yields, making them excellent candidates for testing the validity of these diagnostic tools. We believe that these tools are cost-effective and can be applied to structurally similar organic chromophores to predict/explain the trends of intersystem crossing, and thus fluorescence quantum yields and triplet yields without the use of complex and expensive multireference configuration interaction or multireference pertubation theory methods.

  2. Locality of correlation in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-08-07

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

  3. Momentum and density dependence of the nuclear mean field

    International Nuclear Information System (INIS)

    Behera, B.; Routray, T.R.

    1999-01-01

    The purpose of this is to analyse the momentum, density and temperature dependence of the mean field in nuclear matter derived from finite range effective interactions and to examine the influence of the functional form of the interaction on the high momentum behaviour of the mean field. Emphasis will be given to use very simple parametrizations of the effective interaction with a minimum number of adjustable parameters and yet capable of giving a good description of the mean field in nuclear matter over a wide range of momentum, density and temperature. As an application of the calculated equation of state of nuclear matter, phase transitions to quark-gluon plasma is studied where the quark phase is described by a zeroth order bag model equation of state

  4. Excited-state density functional theory

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  5. Parity dependence of the nuclear level density at high excitation

    International Nuclear Information System (INIS)

    Rao, B.V.; Agrawal, H.M.

    1995-01-01

    The basic underlying assumption ρ(l+1, J)=ρ(l, J) in the level density function ρ(U, J, π) has been checked on the basis of high quality data available on individual resonance parameters (E 0 , Γ n , J π ) for s- and p-wave neutrons in contrast to the earlier analysis where information about p-wave resonance parameters was meagre. The missing level estimator based on the partial integration over a Porter-Thomas distribution of neutron reduced widths and the Dyson-Mehta Δ 3 statistic for the level spacing have been used to ascertain that the s- and p-wave resonance level spacings D(0) and D(1) are not in error because of spurious and missing levels. The present work does not validate the tacit assumption ρ(l+1, J)=ρ(l, J) and confirms that the level density depends upon parity at high excitation. The possible implications of the parity dependence of the level density on the results of statistical model calculations of nuclear reaction cross sections as well as on pre-compound emission have been emphasized. (orig.)

  6. Density-dependent growth in invasive Lionfish (Pterois volitans).

    Science.gov (United States)

    Benkwitt, Cassandra E

    2013-01-01

    Direct demographic density dependence is necessary for population regulation and is a central concept in ecology, yet has not been studied in many invasive species, including any invasive marine fish. The red lionfish (Pterois volitans) is an invasive predatory marine fish that is undergoing exponential population growth throughout the tropical western Atlantic. Invasive lionfish threaten coral-reef ecosystems, but there is currently no evidence of any natural population control. Therefore, a manipulative field experiment was conducted to test for density dependence in lionfish. Juvenile lionfish densities were adjusted on small reefs and several demographic rates (growth, recruitment, immigration, and loss) were measured throughout an 8-week period. Invasive lionfish exhibited direct density dependence in individual growth rates, as lionfish grew slower at higher densities throughout the study. Individual growth in length declined linearly with increasing lionfish density, while growth in mass declined exponentially with increasing density. There was no evidence, however, for density dependence in recruitment, immigration, or loss (mortality plus emigration) of invasive lionfish. The observed density-dependent growth rates may have implications for which native species are susceptible to lionfish predation, as the size and type of prey that lionfish consume is directly related to their body size. The absence of density-dependent loss, however, contrasts with many native coral-reef fish species and suggests that for the foreseeable future manual removals may be the only effective local control of this invasion.

  7. Density-dependent growth in invasive Lionfish (Pterois volitans.

    Directory of Open Access Journals (Sweden)

    Cassandra E Benkwitt

    Full Text Available Direct demographic density dependence is necessary for population regulation and is a central concept in ecology, yet has not been studied in many invasive species, including any invasive marine fish. The red lionfish (Pterois volitans is an invasive predatory marine fish that is undergoing exponential population growth throughout the tropical western Atlantic. Invasive lionfish threaten coral-reef ecosystems, but there is currently no evidence of any natural population control. Therefore, a manipulative field experiment was conducted to test for density dependence in lionfish. Juvenile lionfish densities were adjusted on small reefs and several demographic rates (growth, recruitment, immigration, and loss were measured throughout an 8-week period. Invasive lionfish exhibited direct density dependence in individual growth rates, as lionfish grew slower at higher densities throughout the study. Individual growth in length declined linearly with increasing lionfish density, while growth in mass declined exponentially with increasing density. There was no evidence, however, for density dependence in recruitment, immigration, or loss (mortality plus emigration of invasive lionfish. The observed density-dependent growth rates may have implications for which native species are susceptible to lionfish predation, as the size and type of prey that lionfish consume is directly related to their body size. The absence of density-dependent loss, however, contrasts with many native coral-reef fish species and suggests that for the foreseeable future manual removals may be the only effective local control of this invasion.

  8. Experimental evidence for density dependence of reproduction in great tits

    NARCIS (Netherlands)

    Both, Christiaan

    1998-01-01

    1.  Density dependence of avian reproduction has often been analysed using correlations between annual mean reproductive output and population density. Experiments are necessary to prove that density is the cause of the observed patterns, but so far, three out of four experimental studies do not

  9. Experimental evidence for density dependence of reproduction in great tits

    NARCIS (Netherlands)

    Both, C.

    1998-01-01

    1. Density dependence of avian reproduction has often been analysed using correlations between annual mean reproductive output and population density. Experiments are necessary to prove that density is the cause of the observed patterns, but so far, three out of four experimental studies do not

  10. Density-dependent electron scattering in photoexcited GaAs

    DEFF Research Database (Denmark)

    Mics, Zoltán; D'’Angio, Andrea; Jensen, Søren A.

    2013-01-01

    —In a series of systematic optical pump - terahertz probe experiments we study the density-dependent electron scattering rate in photoexcited GaAs in a large range of carrier densities. The electron scattering time decreases by as much as a factor of 4, from 320 to 60 fs, as the electron density...

  11. Prevalence and strength of density-dependent tree recruitment

    Science.gov (United States)

    Kai Zhu; Christopher W. Woodall; Joao V.D. Monteiro; James S. Clark

    2015-01-01

    Density dependence could maintain diversity in forests, but studies continue to disagree on its role. Part of the disagreement results from the fact that different studies have evaluated different responses (survival, recruitment, or growth) of different stages (seeds, seedlings, or adults) to different inputs (density of seedlings, density or distance to adults). Most...

  12. Relativistic density functional for nuclear structure

    CERN Document Server

    2016-01-01

    This book aims to provide a detailed introduction to the state-of-the-art covariant density functional theory, which follows the Lorentz invariance from the very beginning and is able to describe nuclear many-body quantum systems microscopically and self-consistently. Covariant density functional theory was introduced in nuclear physics in the 1970s and has since been developed and used to describe the diversity of nuclear properties and phenomena with great success. In order to provide an advanced and updated textbook of covariant density functional theory for graduate students and nuclear physics researchers, this book summarizes the enormous amount of material that has accumulated in the field of covariant density functional theory over the last few decades as well as the latest developments in this area. Moreover, the book contains enough details for readers to follow the formalism and theoretical results, and provides exhaustive references to explore the research literature.

  13. Synthesis, Crystal Structure, Density Function Theory, Molecular ...

    African Journals Online (AJOL)

    Tropical Journal of Pharmaceutical Research February 2016; 15 (2): 385-392 ... tested for its antimicrobial activities and computational studies including density function test (DFT) and docking ... agonists [4], selective dopamine D3 and D4 ...

  14. A classical density functional investigation of nucleation

    International Nuclear Information System (INIS)

    Ghosh, Satinath; Ghosh, Swapan K.

    2009-01-01

    Study of nucleation and growth phenomena in condensation is of prime importance in various applications such as crystal growth, nanoparticle synthesis, pattern formation etc. The knowledge of nucleation barrier in condensation is necessary to control the nucleation kinetics, size of the nanoparticles etc. Classical nucleation theory (CNT) assumes the density of the drop as bulk density irrespective of the size of the drop and overestimates the nucleation barrier. Here we are interested in solving the problem analytically using density functional theory (DFT) with square gradient approximation along the lines of Cahn and Hilliard. Nucleation barrier and density profile obtained in this work are consistent with other works based on nonclassical theory. (author)

  15. Effects of multiple electronic shells on strong-field multiphoton ionization and high-order harmonic generation of diatomic molecules with arbitrary orientation: An all-electron time-dependent density-functional approach

    International Nuclear Information System (INIS)

    Telnov, Dmitry A.; Chu, S.-I

    2009-01-01

    We present a time-dependent density-functional theory approach with proper long-range potential for an ab initio study of the effect of correlated multielectron responses on the multiphoton ionization (MPI) and high-order harmonic generation (HHG) of diatomic molecules N 2 and F 2 in intense short laser pulse fields with arbitrary molecular orientation. We show that the contributions of inner molecular orbitals to the total MPI probability can be sufficiently large or even dominant over the highest-occupied molecular orbital, depending on detailed electronic structure and symmetry, laser field intensity, and orientation angle. The multielectron effects in HHG are also very important. They are responsible for enhanced HHG at some orientations of the molecular axis. Even strongly bound electrons may have a significant influence on the HHG process.

  16. 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.

  17. Rational Density Functional Selection Using Game Theory.

    Science.gov (United States)

    McAnanama-Brereton, Suzanne; Waller, Mark P

    2018-01-22

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

  18. Postfragmentation density function for bacterial aggregates in laminar flow.

    Science.gov (United States)

    Byrne, Erin; Dzul, Steve; Solomon, Michael; Younger, John; Bortz, David M

    2011-04-01

    The postfragmentation probability density of daughter flocs is one of the least well-understood aspects of modeling flocculation. We use three-dimensional positional data of Klebsiella pneumoniae bacterial flocs in suspension and the knowledge of hydrodynamic properties of a laminar flow field to construct a probability density function of floc volumes after a fragmentation event. We provide computational results which predict that the primary fragmentation mechanism for large flocs is erosion. The postfragmentation probability density function has a strong dependence on the size of the original floc and indicates that most fragmentation events result in clumps of one to three bacteria eroding from the original floc. We also provide numerical evidence that exhaustive fragmentation yields a limiting density inconsistent with the log-normal density predicted in the literature, most likely due to the heterogeneous nature of K. pneumoniae flocs. To support our conclusions, artificial flocs were generated and display similar postfragmentation density and exhaustive fragmentation. ©2011 American Physical Society

  19. Time Dependent Density Functional Theory description of giant resonances in transition metal complexes: The photoionization dynamics of Cr(CO)6

    International Nuclear Information System (INIS)

    Stener, M.; Fronzoni, G.; Decleva, P.

    2009-01-01

    The photoionization dynamics of Cr(CO) 6 has been calculated at the TDDFT level, employing a basis set of multicentric B-spline functions with the explicit treatment of the photoelectron continuum. The cross section and the asymmetry parameter profiles of all the valence orbitals have been considered and compared with the available experimental data. The most interesting spectral feature is the intense autoionization resonance Cr 3p → Cr 3d observed in the experiment of band A, which is very well reproduced by present calculation at the TDDFT level. Other observed spectral features have been ascribed to shape resonances and assigned according to the dipole-prepared continuum orbital nature. The present TDDFT scheme proves accurate and practicable on large and complex systems containing transition metal compounds, for the description and the interpretation of the photoionization dynamics.

  20. Versatile Density Functionals for Computational Surface Science

    DEFF Research Database (Denmark)

    Wellendorff, Jess

    Density functional theory (DFT) emerged almost 50 years ago. Since then DFT has established itself as the central electronic structure methodology for simulating atomicscale systems from a few atoms to a few hundred atoms. This success of DFT is due to a very favorable accuracy-to-computational c......Density functional theory (DFT) emerged almost 50 years ago. Since then DFT has established itself as the central electronic structure methodology for simulating atomicscale systems from a few atoms to a few hundred atoms. This success of DFT is due to a very favorable accuracy...... resampling techniques, thereby systematically avoiding problems with overfitting. The first ever density functional presenting both reliable accuracy and convincing error estimation is generated. The methodology is general enough to be applied to more complex functional forms with higher-dimensional fitting...

  1. Nonlocal kinetic-energy-density functionals

    International Nuclear Information System (INIS)

    Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E.

    1996-01-01

    In this paper we present nonlocal kinetic-energy functionals T[n] within the average density approximation (ADA) framework, which do not require any extra input when applied to any electron system and recover the exact kinetic energy and the linear response function of a homogeneous system. In contrast with previous ADA functionals, these present good behavior of the long-range tail of the exact weight function. The averaging procedure for the kinetic functional (averaging the Fermi momentum of the electron gas, instead of averaging the electron density) leads to a functional without numerical difficulties in the calculation of extended systems, and it gives excellent results when applied to atoms and jellium surfaces. copyright 1996 The American Physical Society

  2. Density dependence of reactor performance with thermal confinement scalings

    International Nuclear Information System (INIS)

    Stotler, D.P.

    1992-03-01

    Energy confinement scalings for the thermal component of the plasma published thus far have a different dependence on plasma density and input power than do scalings for the total plasma energy. With such thermal scalings, reactor performance (measured by Q, the ratio of the fusion power to the sum of the ohmic and auxiliary input powers) worsens with increasing density. This dependence is the opposite of that found using scalings based on the total plasma energy, indicating that reactor operation concepts may need to be altered if this density dependence is confirmed in future research

  3. Periodic subsystem density-functional theory

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2014-01-01

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

  4. Periodic subsystem density-functional theory

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2014-11-01

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

  5. Time dependent-density functional theory (TD-DFT) and experimental studies of UV-Visible spectra and cyclic voltammetry for Cu(II) complex with Et2DTC

    Science.gov (United States)

    Valle, Eliana Maira A.; Maltarollo, Vinicius Gonçalves; Almeida, Michell O.; Honorio, Kathia Maria; dos Santos, Mauro Coelho; Cerchiaro, Giselle

    2018-04-01

    In this work, we studied the complexation mode between copper(II) ion and the specific ligand investigated as carriers of metals though biological membranes, diethyldithiocarbamate (Et2DTC). It is important to understand how this occurs because it is an important intracellular chelator with potential therapeutic applications. Theoretical and experimental UV visible studies were performed to investigate the complexation mode between copper and the ligand. Electrochemical studies were also performed to complement the spectroscopic analyses. According to the theoretical calculations, using TD-DFT (Time dependent density functional theory), with B3LYP functional and DGDVZP basis set, implemented in Gaussian 03 package, it was observed that the formation of the complex [Cu(Et2DTC)2] is favorable with higher electron density over the sulfur atoms of the ligand. UV/Vis spectra have a charge transfer band at 450 nm, with the DMSO-d6 band shift from 800 to 650 nm. The electrochemical experiments showed the formation of a new redox process, referring to the complex, where the reduction peak potential of copper is displaced to less positive region. Therefore, the results obtained from this study give important insights on possible mechanisms involved in several biological processes related to the studied system.

  6. Temperature and carrier density dependence of anisotropy in supercurrent density in layered cuprate superconductors

    International Nuclear Information System (INIS)

    Singh, M.P.; Tewari, B.S.; Ajay

    2006-01-01

    In the present work, we have studied the effect of temperature and carrier density on anisotropy in supercurrent density in bilayer cuprate superconductors. Here, we have considered a tight binding bilayered Hubbard Hamiltonian containing intra and interlayer attractive interactions. The situation considered here is similar to a SIS junction. We have got the expressions for the superconducting order parameters, carrier density and anisotropy in superconducting density (I ab /I c ) for such SIS junction. The numerical analysis show that the anisotropy in the supercurrent density depends on temperature and carrier density in layered high T c cuprates. (author)

  7. Density dependence of relaxation dynamics in glass formers, and ...

    Indian Academy of Sciences (India)

    Anshul D S Parmar

    formers, we study the variation of relaxation dynamics with density, rather than temperature, as a control ... stronger behaviour, the use of scaled variables involving temperature and ... of the temperature dependence of B as written defines.

  8. Density-dependent feedbacks can mask environmental drivers of populations

    DEFF Research Database (Denmark)

    Dahlgren, Johan Petter

    I present some results from studies identifying environmental drivers of vital rates and population dynamics when controlling for intraspecific density statistically or experimentally, show that density dependence can be strong even in populations of slow-growing species in stressful habitats, an...

  9. Anthropogenically-Mediated Density Dependence in a Declining Farmland Bird.

    Directory of Open Access Journals (Sweden)

    Jenny C Dunn

    Full Text Available Land management intrinsically influences the distribution of animals and can consequently alter the potential for density-dependent processes to act within populations. For declining species, high densities of breeding territories are typically considered to represent productive populations. However, as density-dependent effects of food limitation or predator pressure may occur (especially when species are dependent upon separate nesting and foraging habitats, high territory density may limit per-capita productivity. Here, we use a declining but widespread European farmland bird, the yellowhammer Emberiza citrinella L., as a model system to test whether higher territory densities result in lower fledging success, parental provisioning rates or nestling growth rates compared to lower densities. Organic landscapes held higher territory densities, but nests on organic farms fledged fewer nestlings, translating to a 5 times higher rate of population shrinkage on organic farms compared to conventional. In addition, when parental provisioning behaviour was not restricted by predation risk (i.e., at times of low corvid activity, nestling provisioning rates were higher at lower territory densities, resulting in a much greater increase in nestling mass in low density areas, suggesting that food limitation occurred at high densities. These findings in turn suggest an ecological trap, whereby preferred nesting habitat does not provide sufficient food for rearing nestlings at high population density, creating a population sink. Habitat management for farmland birds should focus not simply on creating a high nesting density, but also on ensuring heterogeneous habitats to provide food resources in close proximity to nesting birds, even if this occurs through potentially restricting overall nest density but increasing population-level breeding success.

  10. Density functional theory of polydisperse fluid interfaces

    International Nuclear Information System (INIS)

    Baus, M.; Bellier-Castella, L.; Xu, H.

    2002-01-01

    Most colloids usually exhibit one or several polydispersities. A natural framework for the theoretical description of polydisperse systems is provided by the extension of density functional theory to 'continuous' mixtures. This will be illustrated here by the study of both the bulk and interfacial properties of a simple van der Waals model for a polydisperse colloidal fluid. (author)

  11. Chemical hardness and density functional theory

    Indian Academy of Sciences (India)

    Unknown

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

  12. Density functional and neural network analysis

    DEFF Research Database (Denmark)

    Jalkanen, K. J.; Suhai, S.; Bohr, Henrik

    1997-01-01

    Density functional theory (DFT) calculations have been carried out for hydrated L-alanine, L-alanyl-L-alanine and N-acetyl L-alanine N'-methylamide and examined with respect to the effect of water on the structure, the vibrational frequencies, vibrational absorption (VA) and vibrational circular...

  13. Founder takes all: density-dependent processes structure biodiversity.

    Science.gov (United States)

    Waters, Jonathan M; Fraser, Ceridwen I; Hewitt, Godfrey M

    2013-02-01

    Density-dependent processes play a key role in the spatial structuring of biodiversity. Specifically, interrelated demographic processes, such as gene surfing, high-density blocking, and competitive exclusion, can generate striking geographic contrasts in the distributions of genes and species. Here, we propose that well-studied evolutionary and ecological biogeographic patterns of postglacial recolonization, progressive island colonization, microbial sectoring, and even the 'Out of Africa' pattern of human expansion, are fundamentally similar, underpinned by a 'founder takes all' density-dependent principle. Additionally, we hypothesize that older historic constraints of density-dependent processes are seen today in the dramatic biogeographic shifts that occur in response to human-mediated extinction events, whereby surviving lineages rapidly expand their ranges to replace extinct sister taxa. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. 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.

  15. Building a universal nuclear energy density functional

    International Nuclear Information System (INIS)

    Bertsch, G F

    2007-01-01

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

  16. The effect of oxide shell thickness on the structural, electronic, and optical properties of Si-SiO{sub 2} core-shell nano-crystals: A (time dependent)density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Nazemi, Sanaz, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir; Soleimani, Ebrahim Asl [School of Electrical and Computer Engineering, University of Tehran, Tehran 14395-515 (Iran, Islamic Republic of); Pourfath, Mahdi, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir [School of Electrical and Computer Engineering, University of Tehran, Tehran 14395-515 (Iran, Islamic Republic of); Institute for Microelectronics, Technische Universität Wien, Wien A-1040 (Austria); Kosina, Hans [Institute for Microelectronics, Technische Universität Wien, Wien A-1040 (Austria)

    2016-04-14

    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-SiO{sub 2} 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 (Si{sup n+}, 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-SiO{sub 2} 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 SiO{sub 2} 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.

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

    Science.gov (United States)

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

    2015-04-21

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

  18. The dependence of stellar properties on initial cloud density

    Science.gov (United States)

    Jones, Michael O.; Bate, Matthew R.

    2018-05-01

    We investigate the dependence of stellar properties on the initial mean density of the molecular cloud in which stellar clusters form using radiation hydrodynamical simulations that resolve the opacity limit for fragmentation. We have simulated the formation of three star clusters from the gravitational collapse of molecular clouds whose densities vary by a factor of a hundred. As with previous calculations including radiative feedback, we find that the dependence of the characteristic stellar mass, Mc, on the initial mean density of the cloud, ρ, is weaker than the dependence of the thermal Jeans mass. However, unlike previous calculations, which found no statistically significant variation in the median mass with density, we find a weak dependence approximately of the form Mc∝ρ-1/5. The distributions of properties of multiple systems do not vary significantly between the calculations. We compare our results to the result of observational surveys of star-forming regions, and suggest that the similarities between the properties of our lowest density calculation and the nearby Taurus-Auriga region indicate that the apparent excess of solar-type stars observed may be due to the region's low density.

  19. Temperature Dependence Viscosity and Density of Different Biodiesel Blends

    Directory of Open Access Journals (Sweden)

    Vojtěch Kumbár

    2015-01-01

    Full Text Available The main goal of this paper is to assess the effect of rapeseed oil methyl ester (RME concentration in diesel fuel on its viscosity and density behaviour. The density and dynamic viscosity were observed at various mixing ratios of RME and diesel fuel. All measurements were performed at constant temperature of 40 °C. Increasing ratio of RME in diesel fuel was reflected in increased density value and dynamic viscosity of the blend. In case of pure RME, pure diesel fuel, and a blend of both (B30, temperature dependence of dynamic viscosity and density was examined. Temperature range in the experiment was −10 °C to 80 °C. Considerable temperature dependence of dynamic viscosity and density was found and demonstrated for all three samples. This finding is in accordance with theoretical assumptions and reference data. Mathematical models were developed and tested. Temperature dependence of dynamic viscosity was modeled using a polynomial 3rd polynomial degree. Correlation coefficients R −0.796, −0.948, and −0.974 between measured and calculated values were found. Temperature dependence of density was modeled using a 2nd polynomial degree. Correlation coefficients R −0.994, −0.979, and −0.976 between measured and calculated values were acquired. The proposed models can be used for flow behaviour prediction of RME, diesel fuel, and their blends.

  20. Linear scaling of density functional algorithms

    International Nuclear Information System (INIS)

    Stechel, E.B.; Feibelman, P.J.; Williams, A.R.

    1993-01-01

    An efficient density functional algorithm (DFA) that scales linearly with system size will revolutionize electronic structure calculations. Density functional calculations are reliable and accurate in determining many condensed matter and molecular ground-state properties. However, because current DFA's, including methods related to that of Car and Parrinello, scale with the cube of the system size, density functional studies are not routinely applied to large systems. Linear scaling is achieved by constructing functions that are both localized and fully occupied, thereby eliminating the need to calculate global eigenfunctions. It is, however, widely believed that exponential localization requires the existence of an energy gap between the occupied and unoccupied states. Despite this, the authors demonstrate that linear scaling can still be achieved for metals. Using a linear scaling algorithm, they have explicitly constructed localized, almost fully occupied orbitals for the quintessential metallic system, jellium. The algorithm is readily generalizable to any system geometry and Hamiltonian. They will discuss the conceptual issues involved, convergence properties and scaling for their new algorithm

  1. Density-dependent expressions for photoionization cross-sections

    Energy Technology Data Exchange (ETDEWEB)

    Sun Weiguo; Ma Xiaoguang; Cheng Yansong

    2004-06-07

    Alternative expressions for photoionization cross-sections and dielectric influence functions are suggested to study the photoionization cross-sections of atoms in solid system. The basic picture is that the photoionization cross-section of atoms in a real system can be described as the coupling between quantum quantity (QQ) and classical quantity (CQ) parts. The QQ part represents the photoionization cross-sections of an isolated particle, while the CQ part may represent most of the important influence of the macroscopic effects (e.g., the interactions of all surrounding polarized particles, and the dielectric property, etc.) on the photoionization cross-sections. The applications to the barium system show that the number-density-dependent new photoionization formula not only obtains the same cross-sections as those from the first order approximation for ideal gas, but also can generate the cross-sections for solid barium by transforming those of ideal gas of the same species using the dielectric influence function.

  2. Density-dependent expressions for photoionization cross-sections

    International Nuclear Information System (INIS)

    Sun Weiguo; Ma Xiaoguang; Cheng Yansong

    2004-01-01

    Alternative expressions for photoionization cross-sections and dielectric influence functions are suggested to study the photoionization cross-sections of atoms in solid system. The basic picture is that the photoionization cross-section of atoms in a real system can be described as the coupling between quantum quantity (QQ) and classical quantity (CQ) parts. The QQ part represents the photoionization cross-sections of an isolated particle, while the CQ part may represent most of the important influence of the macroscopic effects (e.g., the interactions of all surrounding polarized particles, and the dielectric property, etc.) on the photoionization cross-sections. The applications to the barium system show that the number-density-dependent new photoionization formula not only obtains the same cross-sections as those from the first order approximation for ideal gas, but also can generate the cross-sections for solid barium by transforming those of ideal gas of the same species using the dielectric influence function

  3. Teaching Density Functional Theory Through Experiential Learning

    International Nuclear Information System (INIS)

    Narasimhan, Shobhana

    2015-01-01

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

  4. 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...

  5. Density-dependent squeezing of excitons in highly excited semiconductors

    International Nuclear Information System (INIS)

    Nguyen Hong Quang.

    1995-07-01

    The time evolution from coherent states to squeezed states of high density excitons is studied theoretically based on the boson formalism and within the Random Phase Approximation. Both the mutual interaction between excitons and the anharmonic exciton-photon interaction due to phase-space filling of excitons are taken into account. It is shown that the exciton squeezing depends strongly on the exciton density in semiconductors and becomes smaller with increasing the latter. (author). 16 refs, 2 figs

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

    International Nuclear Information System (INIS)

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

    2013-01-01

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

  7. Nuclear matter studies with density-dependent meson-nucleon coupling constants

    International Nuclear Information System (INIS)

    Banerjee, M.K.; Tjon, J.A.; Banerjee, M.K.; Tjon, J.A.

    1997-01-01

    Due to the internal structure of the nucleon, we should expect, in general, that the effective meson nucleon parameters may change in nuclear medium. We study such changes by using a chiral confining model of the nucleon. We use density-dependent masses for all mesons except the pion. Within a Dirac-Brueckner analysis, based on the relativistic covariant structure of the NN amplitude, we show that the effect of such a density dependence in the NN interaction on the saturation properties of nuclear matter, while not large, is quite significant. Due to the density dependence of the g σNN , as predicted by the chiral confining model, we find, in particular, a looping behavior of the binding energy at saturation as a function of the saturation density. A simple model is described, which exhibits looping and which is shown to be mainly caused by the presence of a peak in the density dependence of the medium modified σN coupling constant at low density. The effect of density dependence of the coupling constants and the meson masses tends to improve the results for E/A and density of nuclear matter at saturation. From the present study we see that the relationship between binding energy and saturation density may not be as universal as found in nonrelativistic studies and that more model dependence is exhibited once medium modifications of the basic nuclear interactions are considered. copyright 1997 The American Physical Society

  8. A density functional approach to ferrogels

    Science.gov (United States)

    Cremer, P.; Heinen, M.; Menzel, A. M.; Löwen, H.

    2017-07-01

    Ferrogels consist of magnetic colloidal particles embedded in an elastic polymer matrix. As a consequence, their structural and rheological properties are governed by a competition between magnetic particle-particle interactions and mechanical matrix elasticity. Typically, the particles are permanently fixed within the matrix, which makes them distinguishable by their positions. Over time, particle neighbors do not change due to the fixation by the matrix. Here we present a classical density functional approach for such ferrogels. We map the elastic matrix-induced interactions between neighboring colloidal particles distinguishable by their positions onto effective pairwise interactions between indistinguishable particles similar to a ‘pairwise pseudopotential’. Using Monte-Carlo computer simulations, we demonstrate for one-dimensional dipole-spring models of ferrogels that this mapping is justified. We then use the pseudopotential as an input into classical density functional theory of inhomogeneous fluids and predict the bulk elastic modulus of the ferrogel under various conditions. In addition, we propose the use of an ‘external pseudopotential’ when one switches from the viewpoint of a one-dimensional dipole-spring object to a one-dimensional chain embedded in an infinitely extended bulk matrix. Our mapping approach paves the way to describe various inhomogeneous situations of ferrogels using classical density functional concepts of inhomogeneous fluids.

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

    Science.gov (United States)

    Rickayzen, G; Heyes, D M

    2013-02-28

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

  10. Global asymptotic stability of density dependent integral population projection models.

    Science.gov (United States)

    Rebarber, Richard; Tenhumberg, Brigitte; Townley, Stuart

    2012-02-01

    Many stage-structured density dependent populations with a continuum of stages can be naturally modeled using nonlinear integral projection models. In this paper, we study a trichotomy of global stability result for a class of density dependent systems which include a Platte thistle model. Specifically, we identify those systems parameters for which zero is globally asymptotically stable, parameters for which there is a positive asymptotically stable equilibrium, and parameters for which there is no asymptotically stable equilibrium. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    International Nuclear Information System (INIS)

    Capelle, K.; Gross, E.

    1997-01-01

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

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

    Science.gov (United States)

    Umezawa, Naoto

    2017-09-14

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

  13. Stationary solution of a time dependent density matrix formalism

    International Nuclear Information System (INIS)

    Tohyama, Mitsuru

    1994-01-01

    A stationary solution of a time-dependent density-matrix formalism, which is an extension of the time-dependent Hartree-Fock theory to include the effects of two-body correlations, is obtained for the Lipkin model hamiltonian, using an adiabatic treatment of the two-body interaction. It is found that the obtained result is a reasonable approximation for the exact solution of the model. (author)

  14. 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.

  15. Functional derivative of noninteracting kinetic energy density functional

    International Nuclear Information System (INIS)

    Liu Shubin; Ayers, Paul W.

    2004-01-01

    Proofs from different theoretical frameworks, namely, the Hohenbergh-Kohn theorems, the Kohn-Sham scheme, and the first-order density matrix representation, have been presented in this paper to show that the functional derivative of the noninteracting kinetic energy density functional can uniquely be expressed as the negative of the Kohn-Sham effective potential, arbitrary only to an additive orbital-independent constant. Key points leading to the current result as well as confusion about the quantity in the literature are briefly discussed

  16. Density-dependent phonoriton states in highly excited semiconductors

    International Nuclear Information System (INIS)

    Nguyen Hong Quang; Nguyen Minh Khue; Nguyen Que Huong

    1995-09-01

    The dynamical aspects of the phonoriton state in highly-photoexcited semiconductors is studied theoretically. The effect of the exciton-exciton interaction and nonbosonic character of high-density excitons are taken into account. Using Green's function method and within the Random Phase Approximation it is shown that the phonoriton dispersion and damping are very sensitive to the exciton density, characterizing the excitation degree of semiconductors. (author). 18 refs, 3 figs

  17. Cuticular antifungals in spiders: density- and condition dependence.

    Directory of Open Access Journals (Sweden)

    Daniel González-Tokman

    Full Text Available Animals living in groups face a high risk of disease contagion. In many arthropod species, cuticular antimicrobials constitute the first protective barrier that prevents infections. Here we report that group-living spiders produce cuticular chemicals which inhibit fungal growth. Given that cuticular antifungals may be costly to produce, we explored whether they can be modulated according to the risk of contagion (i.e. under high densities. For this purpose, we quantified cuticular antifungal activity in the subsocial crab spider Diaea ergandros in both natural nests and experimentally manipulated nests of varying density. We quantified the body-condition of spiders to test whether antifungal activity is condition dependent, as well as the effect of spider density on body-condition. We predicted cuticular antifungal activity to increase and body-condition to decrease with high spider densities, and that antifungal activity would be inversely related to body-condition. Contrary to our predictions, antifungal activity was neither density- nor condition-dependent. However, body-condition decreased with density in natural nests, but increased in experimental nests. We suggest that pathogen pressure is so important in nature that it maintains high levels of cuticular antifungal activity in spiders, impacting negatively on individual energetic condition. Future studies should identify the chemical structure of the isolated antifungal compounds in order to understand the physiological basis of a trade-off between disease prevention and energetic condition caused by group living, and its consequences in the evolution of sociality in spiders.

  18. Cuticular antifungals in spiders: density- and condition dependence.

    Science.gov (United States)

    González-Tokman, Daniel; Ruch, Jasmin; Pulpitel, Tamara; Ponton, Fleur

    2014-01-01

    Animals living in groups face a high risk of disease contagion. In many arthropod species, cuticular antimicrobials constitute the first protective barrier that prevents infections. Here we report that group-living spiders produce cuticular chemicals which inhibit fungal growth. Given that cuticular antifungals may be costly to produce, we explored whether they can be modulated according to the risk of contagion (i.e. under high densities). For this purpose, we quantified cuticular antifungal activity in the subsocial crab spider Diaea ergandros in both natural nests and experimentally manipulated nests of varying density. We quantified the body-condition of spiders to test whether antifungal activity is condition dependent, as well as the effect of spider density on body-condition. We predicted cuticular antifungal activity to increase and body-condition to decrease with high spider densities, and that antifungal activity would be inversely related to body-condition. Contrary to our predictions, antifungal activity was neither density- nor condition-dependent. However, body-condition decreased with density in natural nests, but increased in experimental nests. We suggest that pathogen pressure is so important in nature that it maintains high levels of cuticular antifungal activity in spiders, impacting negatively on individual energetic condition. Future studies should identify the chemical structure of the isolated antifungal compounds in order to understand the physiological basis of a trade-off between disease prevention and energetic condition caused by group living, and its consequences in the evolution of sociality in spiders.

  19. Detection of density dependence requires density manipulations and calculation of lambda.

    Science.gov (United States)

    Fowler, N L; Overath, R Deborah; Pease, Craig M

    2006-03-01

    To investigate density-dependent population regulation in the perennial bunchgrass Bouteloua rigidiseta, we experimentally manipulated density by removing adults or adding seeds to replicate quadrats in a natural population for three annual intervals. We monitored the adjacent control quadrats for 14 annual intervals. We constructed a population projection matrix for each quadrat in each interval, calculated lambda, and did a life table response experiment (LTRE) analysis. We tested the effects of density upon lambda by comparing experimental and control quadrats, and by an analysis of the 15-year observational data set. As measured by effects on lambda and on N(t+1/Nt in the experimental treatments, negative density dependence was strong: the population was being effectively regulated. The relative contributions of different matrix elements to treatment effect on lambda differed among years and treatments; overall the pattern was one of small contributions by many different life cycle stages. In contrast, density dependence could not be detected using only the observational (control quadrats) data, even though this data set covered a much longer time span. Nor did experimental effects on separate matrix elements reach statistical significance. These results suggest that ecologists may fail to detect density dependence when it is present if they have only descriptive, not experimental, data, do not have data for the entire life cycle, or analyze life cycle components separately.

  20. Evolution of density-dependent movement during experimental range expansions.

    Science.gov (United States)

    Fronhofer, E A; Gut, S; Altermatt, F

    2017-12-01

    Range expansions and biological invasions are prime examples of transient processes that are likely impacted by rapid evolutionary changes. As a spatial process, range expansions are driven by dispersal and movement behaviour. Although it is widely accepted that dispersal and movement may be context-dependent, for instance density-dependent, and best represented by reaction norms, the evolution of density-dependent movement during range expansions has received little experimental attention. We therefore tested current theory predicting the evolution of increased movement at low densities at range margins using highly replicated and controlled range expansion experiments across multiple genotypes of the protist model system Tetrahymena thermophila. Although rare, we found evolutionary changes during range expansions even in the absence of initial standing genetic variation. Range expansions led to the evolution of negatively density-dependent movement at range margins. In addition, we report the evolution of increased intrastrain competitive ability and concurrently decreased population growth rates in range cores. Our findings highlight the importance of understanding movement and dispersal as evolving reaction norms and plastic life-history traits of central relevance for range expansions, biological invasions and the dynamics of spatially structured systems in general. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

  1. Rydberg energies using excited state density functional theory

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  2. Density of biogas digestate depending on temperature and composition.

    Science.gov (United States)

    Gerber, Mandy; Schneider, Nico

    2015-09-01

    Density is one of the most important physical properties of biogas digestate to ensure an optimal dimensioning and a precise design of biogas plant components like stirring devices, pumps and heat exchangers. In this study the density of biogas digestates with different compositions was measured using pycnometers at ambient pressure in a temperature range from 293.15 to 313.15K. The biogas digestates were taken from semi-continuous experiments, in which the marine microalga Nannochloropsis salina, corn silage and a mixture of both were used as feedstocks. The results show an increase of density with increasing total solid content and a decrease with increasing temperature. Three equations to calculate the density of biogas digestate were set up depending on temperature as well as on the total solid content, organic composition and elemental composition, respectively. All correlations show a relative deviation below 1% compared to experimental data. Copyright © 2015. Published by Elsevier Ltd.

  3. Functional methods for arbitrary densities in curved spacetime

    International Nuclear Information System (INIS)

    Basler, M.

    1993-01-01

    This paper gives an introduction to the technique of functional differentiation and integration in curved spacetime, applied to examples from quantum field theory. Special attention is drawn on the choice of functional integral measure. Referring to a suggestion by Toms, fields are choosen as arbitrary scalar, spinorial or vectorial densities. The technique developed by Toms for a pure quadratic Lagrangian are extended to the calculation of the generating functional with external sources. Included are two examples of interacting theories, a self-interacting scalar field and a Yang-Mills theory. For these theories the complete set of Feynman graphs depending on the weight of variables is derived. (orig.)

  4. Functional development in density functional theory for superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Sanna, Antonio; Gross, E.K.U.; Essenberger, Frank [Max Planck Institute of Microstructure Physics, Halle (Saale) (Germany)

    2015-07-01

    Density functional theory for superconductors (SCDFT) is a fully parameter-free approach to superconductivity that allows for accurate predictions of critical temperature and properties of superconductors. We report on the most recent extensions of the method, in particular the development of new functionals to: (1) incorporate in a correct fashion Migdal's theorem; (2) compute the excitation spectrum; (3) include spin-fluctuation mediated pairing Applications and predictions are shown for a set of materials, including conventional and unconventional superconductors.

  5. Modulation Based on Probability Density Functions

    Science.gov (United States)

    Williams, Glenn L.

    2009-01-01

    A proposed method of modulating a sinusoidal carrier signal to convey digital information involves the use of histograms representing probability density functions (PDFs) that characterize samples of the signal waveform. The method is based partly on the observation that when a waveform is sampled (whether by analog or digital means) over a time interval at least as long as one half cycle of the waveform, the samples can be sorted by frequency of occurrence, thereby constructing a histogram representing a PDF of the waveform during that time interval.

  6. Density Functional Simulation of a Breaking Nanowire

    DEFF Research Database (Denmark)

    Nakamura, A.; Brandbyge, Mads; Hansen, Lars Bruno

    1999-01-01

    to a specific number of eigenchannels. The transitions between plateaus can be abrupt in connection with structural rearrangements or extend over a few a of elongation. The interplay between conductance modes and structural deformation is discussed by means of the eigenchannel transmission probabilities.......We study the deformation and breaking of an atomic-sized sodium wire using density functional simulations. The wire deforms through sudden atomic rearrangements and smoother atomic displacements. The conductance of the wire exhibits plateaus at integer values in units of 2e(2)/h corresponding...

  7. Model dependence of isospin sensitive observables at high densities

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Wen-Mei [Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); School of Science, Huzhou Teachers College, Huzhou 313000 (China); Yong, Gao-Chan, E-mail: yonggaochan@impcas.ac.cn [Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Beijing 100190 (China); Wang, Yongjia [School of Science, Huzhou Teachers College, Huzhou 313000 (China); School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); Li, Qingfeng [School of Science, Huzhou Teachers College, Huzhou 313000 (China); Zhang, Hongfei [School of Nuclear Science and Technology, Lanzhou University, Lanzhou 730000 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Beijing 100190 (China); Zuo, Wei [Institute of Modern Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); State Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of Sciences, Beijing 100190 (China)

    2013-10-07

    Within two different frameworks of isospin-dependent transport model, i.e., Boltzmann–Uehling–Uhlenbeck (IBUU04) and Ultrarelativistic Quantum Molecular Dynamics (UrQMD) transport models, sensitive probes of nuclear symmetry energy are simulated and compared. It is shown that neutron to proton ratio of free nucleons, π{sup −}/π{sup +} ratio as well as isospin-sensitive transverse and elliptic flows given by the two transport models with their “best settings”, all have obvious differences. Discrepancy of numerical value of isospin-sensitive n/p ratio of free nucleon from the two models mainly originates from different symmetry potentials used and discrepancies of numerical value of charged π{sup −}/π{sup +} ratio and isospin-sensitive flows mainly originate from different isospin-dependent nucleon–nucleon cross sections. These demonstrations call for more detailed studies on the model inputs (i.e., the density- and momentum-dependent symmetry potential and the isospin-dependent nucleon–nucleon cross section in medium) of isospin-dependent transport model used. The studies of model dependence of isospin sensitive observables can help nuclear physicists to pin down the density dependence of nuclear symmetry energy through comparison between experiments and theoretical simulations scientifically.

  8. Stochastic density functional theory at finite temperatures

    Science.gov (United States)

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

    2018-03-01

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

  9. Time-dependent density functional theory/discrete reaction field spectra of open shell systems: The visual spectrum of [FeIII(PyPepS)2]- in aqueous solution.

    Science.gov (United States)

    van Duijnen, Piet Th; Greene, Shannon N; Richards, Nigel G J

    2007-07-28

    We report the calculated visible spectrum of [FeIII(PyPepS)2]- in aqueous solution. From all-classical molecular dynamics simulations on the solute and 200 water molecules with a polarizable force field, 25 solute/solvent configurations were chosen at random from a 50 ps production run and subjected the systems to calculations using time-dependent density functional theory (TD-DFT) for the solute, combined with a solvation model in which the water molecules carry charges and polarizabilities. In each calculation the first 60 excited states were collected in order to span the experimental spectrum. Since the solute has a doublet ground state several excitations to states are of type "three electrons in three orbitals," each of which gives rise to a manifold of a quartet and two doublet states which cannot properly be represented by single Slater determinants. We applied a tentative scheme to analyze this type of spin contamination in terms of Delta and Delta transitions between the same orbital pairs. Assuming the associated states as pure single determinants obtained from restricted calculations, we construct conformation state functions (CFSs), i.e., eigenfunctions of the Hamiltonian Sz and S2, for the two doublets and the quartet for each Delta,Delta pair, the necessary parameters coming from regular and spin-flip calculations. It appears that the lower final states remain where they were originally calculated, while the higher states move up by some tenths of an eV. In this case filtering out these higher states gives a spectrum that compares very well with experiment, but nevertheless we suggest investigating a possible (re)formulation of TD-DFT in terms of CFSs rather than determinants.

  10. Microhartree precision in density functional theory calculations

    Science.gov (United States)

    Gulans, Andris; Kozhevnikov, Anton; Draxl, Claudia

    2018-04-01

    To address ultimate precision in density functional theory calculations we employ the full-potential linearized augmented plane-wave + local-orbital (LAPW + lo) method and justify its usage as a benchmark method. LAPW + lo and two completely unrelated numerical approaches, the multiresolution analysis (MRA) and the linear combination of atomic orbitals, yield total energies of atoms with mean deviations of 0.9 and 0.2 μ Ha , respectively. Spectacular agreement with the MRA is reached also for total and atomization energies of the G2-1 set consisting of 55 molecules. With the example of α iron we demonstrate the capability of LAPW + lo to reach μ Ha /atom precision also for periodic systems, which allows also for the distinction between the numerical precision and the accuracy of a given functional.

  11. A density functional for sparse matter

    DEFF Research Database (Denmark)

    Langreth, D.C.; Lundqvist, Bengt; Chakarova-Kack, S.D.

    2009-01-01

    forces in molecules, to adsorbed molecules, like benzene, naphthalene, phenol and adenine on graphite, alumina and metals, to polymer and carbon nanotube (CNT) crystals, and hydrogen storage in graphite and metal-organic frameworks (MOFs), and to the structure of DNA and of DNA with intercalators......Sparse matter is abundant and has both strong local bonds and weak nonbonding forces, in particular nonlocal van der Waals (vdW) forces between atoms separated by empty space. It encompasses a broad spectrum of systems, like soft matter, adsorption systems and biostructures. Density-functional...... theory (DFT), long since proven successful for dense matter, seems now to have come to a point, where useful extensions to sparse matter are available. In particular, a functional form, vdW-DF (Dion et al 2004 Phys. Rev. Lett. 92 246401; Thonhauser et al 2007 Phys. Rev. B 76 125112), has been proposed...

  12. Angular momentum dependence of the nuclear level density parameter

    International Nuclear Information System (INIS)

    Aggarwal, Mamta; Kailas, S.

    2010-01-01

    Dependence of nuclear level density parameter on the angular momentum and temperature is investigated in a theoretical framework using the statistical theory of hot rotating nuclei. The structural effects are incorporated by including shell correction, shape, and deformation. The nuclei around Z≅50 with an excitation energy range of 30 to 40 MeV are considered. The calculations are in good agreement with the experimentally deduced inverse level density parameter values especially for 109 In, 113 Sb, 122 Te, 123 I, and 127 Cs nuclei.

  13. Self-contained filtered density function

    International Nuclear Information System (INIS)

    Nouri, Arash G.; Pope, Stephen B.

    2017-01-01

    The filtered density function (FDF) closure is extended to a “self-contained” format to include the subgrid-scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large-eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF). In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via a set of stochastic differential equation for each of the transport variables. This yields a self-contained SGS closure. We demonstrated how LES is conducted of a turbulent shear flow with transport of a passive scalar. Finally, the consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.

  14. Self-contained filtered density function

    Science.gov (United States)

    Nouri, A. G.; Nik, M. B.; Givi, P.; Livescu, D.; Pope, S. B.

    2017-09-01

    The filtered density function (FDF) closure is extended to a "self-contained" format to include the subgrid-scale (SGS) statistics of all of the hydro-thermo-chemical variables in turbulent flows. These are the thermodynamic pressure, the specific internal energy, the velocity vector, and the composition field. In this format, the model is comprehensive and facilitates large-eddy simulation (LES) of flows at both low and high compressibility levels. A transport equation is developed for the joint pressure-energy-velocity-composition filtered mass density function (PEVC-FMDF). In this equation, the effect of convection appears in closed form. The coupling of the hydrodynamics and thermochemistry is modeled via a set of stochastic differential equation for each of the transport variables. This yields a self-contained SGS closure. For demonstration, LES is conducted of a turbulent shear flow with transport of a passive scalar. The consistency of the PEVC-FMDF formulation is established, and its overall predictive capability is appraised via comparison with direct numerical simulation (DNS) data.

  15. Does density-dependent diversification mirror ecological competitive exclusion?

    Directory of Open Access Journals (Sweden)

    Melanie J Monroe

    Full Text Available Density-dependence is a term used in ecology to describe processes such as birth and death rates that are regulated by the number of individuals in a population. Evolutionary biologists have borrowed the term to describe decreasing rates of species accumulation, suggesting that speciation and extinction rates depend on the total number of species in a clade. If this analogy with ecological density-dependence holds, diversification of clades is restricted because species compete for limited resources. We hypothesize that such competition should not only affect numbers of species, but also prevent species from being phenotypically similar. Here, we present a method to detect whether competitive interactions between species have ordered phenotypic traits on a phylogeny, assuming that competition prevents related species from having identical trait values. We use the method to analyze clades of birds and mammals, with body size as the phenotypic trait. We find no sign that competition has prevented species from having the same body size. Thus, since body size is a key ecological trait and competition does not seem to be responsible for differences in body size between species, we conclude that the diversification slowdown that is prevalent in these clades is unlikely due to the ecological interference implied by the term density dependence.

  16. Modelling the effect of autotoxicity on density-dependent phytotoxicity.

    Science.gov (United States)

    Sinkkonen, A

    2007-01-21

    An established method to separate resource competition from chemical interference is cultivation of monospecific, even-aged stands. The stands grow at several densities and they are exposed to homogenously spread toxins. Hence, the dose received by individual plants is inversely related to stand density. This results in distinguishable alterations in dose-response slopes. The method is often recommended in ecological studies of allelopathy. However, many plant species are known to release autotoxic compounds. Often, the probability of autotoxicity increases as sowing density increases. Despite this, the possibility of autotoxicity is ignored when experiments including monospecific stands are designed and when their results are evaluated. In this paper, I model mathematically how autotoxicity changes the outcome of dose-response slopes as different densities of monospecific stands are grown on homogenously phytotoxic substrata. Several ecologically reasonable relations between plant density and autotoxin exposure are considered over a range of parameter values, and similarities between different relations are searched for. The models indicate that autotoxicity affects the outcome of density-dependent dose-response experiments. Autotoxicity seems to abolish the effects of other phytochemicals in certain cases, while it may augment them in other cases. Autotoxicity may alter the outcome of tests using the method of monospecific stands even if the dose of autotoxic compounds per plant is a fraction of the dose of non-autotoxic phytochemicals with similar allelopathic potential. Data from the literature support these conclusions. A faulty null hypothesis may be accepted if the autotoxic potential of a test species is overlooked in density-response experiments. On the contrary, if test species are known to be non-autotoxic, the method of monospecific stands does not need fine-tuning. The results also suggest that the possibility of autotoxicity should be investigated in

  17. Comparison of density estimators. [Estimation of probability density functions

    Energy Technology Data Exchange (ETDEWEB)

    Kao, S.; Monahan, J.F.

    1977-09-01

    Recent work in the field of probability density estimation has included the introduction of some new methods, such as the polynomial and spline methods and the nearest neighbor method, and the study of asymptotic properties in depth. This earlier work is summarized here. In addition, the computational complexity of the various algorithms is analyzed, as are some simulations. The object is to compare the performance of the various methods in small samples and their sensitivity to change in their parameters, and to attempt to discover at what point a sample is so small that density estimation can no longer be worthwhile. (RWR)

  18. Density-Dependent Phase Polyphenism in Nonmodel Locusts: A Minireview

    Directory of Open Access Journals (Sweden)

    Hojun Song

    2011-01-01

    Full Text Available Although the specific mechanisms of locust phase transformation are wellunderstood for model locust species such as the desert locust Schistocerca gregaria and the migratory locust Locusta migratoria, the expressions of density-dependent phase polyphenism in other nonmodel locust species are not wellknown. The present paper is an attempt to review and synthesize what we know about these nonmodel locusts. Based on all available data, I find that locust phase polyphenism is expressed in many different ways in different locust species and identify a pattern that locust species often belong to large taxonomic groups which contain mostly nonswarming grasshopper species. Although locust phase polyphenism has evolved multiple times within Acrididae, I argue that its evolution should be studied from a phylogenetic perspective because I find similar density-dependent phenotypic plasticity among closely related species. Finally, I emphasize the importance of comparative analyses in understanding the evolution of locust phase and propose a phylogeny-based research framework.

  19. Time dependent density matrix theory and effective interaction

    Energy Technology Data Exchange (ETDEWEB)

    Tohyama, Mitsuru [Kyorin Univ., Mitaka, Tokyo (Japan). School of Medicine

    1998-07-01

    A correlated ground state of {sup 16}O and an E2 giant resonance built on it are calculated using an extended version of the time-dependent Hartree-Fock theory called the time-dependent density-matrix theory (TDDM). The Skyrme force is used in the calculation of both a mean field and two-body correlations. It is found that TDDM gives reasonable ground-state correlations and a large spreading width of the E2 giant resonance when single-particle states in the continuum are treated appropriately. (author)

  20. Density dependent atomic motion in a liquid alkali metal

    International Nuclear Information System (INIS)

    Pilgrim, W.-C.; Hosokawa, S.; Morkel, C.

    2001-01-01

    Inelastic X-ray and neutron scattering results obtained from liquid sodium and rubidium are presented. They cover the entire liquid range between melting and liquid vapour critical point. At high densities the dynamics of the liquid metal is characterized by collective excitations. The corresponding dispersion relations indicate the existence of surprisingly stable next neighbouring shells leading to an increase of the propagation speed for the collective modes. Below 2ρ crit. the dynamics changes from collective to localized indicating the existence of molecular aggregates. This interpretation is in accord with a simple model where the properties of a Rb- and a Rb 2 - lattice are calculated using density functional theory. (orig.)

  1. Nuclear level density parameter 's dependence on angular momentum

    International Nuclear Information System (INIS)

    Aggarwal, Mamta; Kailas, S.

    2009-01-01

    Nuclear level densities represent a very important ingredient in the statistical Model calculations of nuclear reaction cross sections and help to understand the microscopic features of the excited nuclei. Most of the earlier experimental nuclear level density measurements are confined to low excitation energy and low spin region. A recent experimental investigation of nuclear level densities in high excitation energy and angular momentum domain with some interesting results on inverse level density parameter's dependence on angular momentum in the region around Z=50 has motivated us to study and analyse these experimental results in a microscopic theoretical framework. In the experiment, heavy ion fusion reactions are used to populate the excited and rotating nuclei and measured the α particle evaporation spectra in coincidence with ray multiplicity. Residual nuclei are in the range of Z R 48-55 with excitation energy range 30 to 40 MeV and angular momentum in 10 to 25. The inverse level density parameter K is found to be in the range of 9.0 - 10.5 with some exceptions

  2. Qualitative assessment of ultra-fast non-Grotthuss proton dynamics in S1 excited state of liquid H2O from ab initio time-dependent density functional theory★

    Science.gov (United States)

    Ziaei, Vafa; Bredow, Thomas

    2017-11-01

    We study qualitatively ultra-fast proton transfer (PT) in the first singlet (S1) state of liquid water (absorption onset) through excited-state dynamics by means of time-dependent density functional theory and ab initio Born-Oppenheimer molecular dynamics. We find that after the initial excitation, a PT occurs in S1 in form of a rapid jump to a neighboring water molecule, on which the proton either may rest for a relatively long period of time (as a consequence of possible defect in the hydrogen bond network) followed by back and forth hops to its neighboring water molecule or from which it further moves to the next water molecule accompanied by back and forth movements. In this way, the proton may become delocalized over a long water wire branch, followed again by back and forth jumps or short localization on a water molecule for some femtoseconds. As a result, the mechanism of PT in S1 is in most cases highly non-Grotthuss-like, delayed and discrete. Furthermore, upon PT an excess charge is ejected to the solvent trap, the so-called solvated electron. The spatial extent of the ejected solvated electron is mainly localized within one solvent shell with overlappings on the nearest neighbor water molecules and delocalizing (diffuse) tails extending beyond the first solvent sphere. During the entire ultra-short excited-state dynamics the remaining OH radical from the initially excited water molecule exhibits an extremely low mobility and is non-reactive. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80329-7.

  3. When Density Functional Approximations Meet Iron Oxides.

    Science.gov (United States)

    Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-Dong

    2016-10-11

    Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe 2 O 3 , Fe 3 O 4 , and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

  4. Density and starting-energy dependent effective interaction

    International Nuclear Information System (INIS)

    Yamaguchi, Norio; Nagata, Sinobu; Kasuga, Teruo

    1979-01-01

    A new effective potential constructed from the reaction matrix calculation of nuclear matters is proposed, taking three-body effects into account. Starting from the two-body scattering equation for nuclear matters, an equation with averaged momentum is introduced as the definition of effective interaction. The parameters in the equation are the Fermi momentum and the starting energy. The nuclear density dependence and the starting energy dependence are independently treated in the potential. The effective interactions including three-body effects were calculated. The dependence on the starting energy is large. The effective interaction is more attractive in the triplet E state, and assures overall saturation without any artificial renormalization. The reaction matrix calculation can be well reproduced by the calculation with this effective potential. The results of calculation for the binding energy of He-4 and O-16 and the shell model matrix elements of O-16 are represented. (Kato, T.)

  5. Specifying Functional Requirements Dependency in the REWiki

    OpenAIRE

    ZHANG, ZHANG

    2013-01-01

    Most of the individual requirements cannot be treated in isolation. Requirements may affect each other in various ways. The dependency between requirements impacts a number of software development aspects and activities. How to classify and specify requirements dependency remains a classic research topic. This research aims at providing an approach of specifying functional requirements dependency. In this thesis we generalize a classification of functional requirements dependency. We also pro...

  6. Density regulation in Northeast Atlantic fish populations: Density dependence is stronger in recruitment than in somatic growth.

    Science.gov (United States)

    Zimmermann, Fabian; Ricard, Daniel; Heino, Mikko

    2018-05-01

    Population regulation is a central concept in ecology, yet in many cases its presence and the underlying mechanisms are difficult to demonstrate. The current paradigm maintains that marine fish populations are predominantly regulated by density-dependent recruitment. While it is known that density-dependent somatic growth can be present too, its general importance remains unknown and most practical applications neglect it. This study aimed to close this gap by for the first time quantifying and comparing density dependence in growth and recruitment over a large set of fish populations. We fitted density-dependent models to time-series data on population size, recruitment and age-specific weight from commercially exploited fish populations in the Northeast Atlantic Ocean and the Baltic Sea. Data were standardized to enable a direct comparison within and among populations, and estimated parameters were used to quantify the impact of density regulation on population biomass. Statistically significant density dependence in recruitment was detected in a large proportion of populations (70%), whereas for density dependence in somatic growth the prevalence of density dependence depended heavily on the method (26% and 69%). Despite age-dependent variability, the density dependence in recruitment was consistently stronger among age groups and between alternative approaches that use weight-at-age or weight increments to assess growth. Estimates of density-dependent reduction in biomass underlined these results: 97% of populations with statistically significant parameters for growth and recruitment showed a larger impact of density-dependent recruitment on population biomass. The results reaffirm the importance of density-dependent recruitment in marine fishes, yet they also show that density dependence in somatic growth is not uncommon. Furthermore, the results are important from an applied perspective because density dependence in somatic growth affects productivity and

  7. Building a Universal Nuclear Energy Density Functional

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-12-30

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

  8. Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self- consistent field wave functions

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Jensen, Hans Jørgen Aagaard; Knecht, Stefan

    2013-01-01

    -MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the CAM-B3LYP functional. The SOPPA-srDFT scheme is tested for a subset of molecules used for benchmarking...

  9. Landau parameters for finite range density dependent nuclear interactions

    International Nuclear Information System (INIS)

    Farine, M.

    1997-01-01

    The Landau parameters represent the effective particle-hole interaction at Fermi level. Since between the physical observables and the Landau parameters there is a direct relation their derivation from an effective interaction is of great interest. The parameter F 0 determines the incompressibility K of the system. The parameter F 1 determines the effective mass (which controls the level density at the Fermi level). In addition, F 0 ' determines the symmetry energy, G 0 the magnetic susceptibility, and G 0 ' the pion condensation threshold in nuclear matter. This paper is devoted to a general derivation of Landau parameters for an interaction with density dependent finite range terms. Particular carefulness is devoted to the inclusion of rearrangement terms. This report is part of a larger project which aims at defining a new nuclear interaction improving the well-known D1 force of Gogny et al. for describing the average nuclear properties and exotic nuclei and satisfying, in addition, the sum rules

  10. The time-dependent density matrix renormalisation group method

    Science.gov (United States)

    Ma, Haibo; Luo, Zhen; Yao, Yao

    2018-04-01

    Substantial progress of the time-dependent density matrix renormalisation group (t-DMRG) method in the recent 15 years is reviewed in this paper. By integrating the time evolution with the sweep procedures in density matrix renormalisation group (DMRG), t-DMRG provides an efficient tool for real-time simulations of the quantum dynamics for one-dimensional (1D) or quasi-1D strongly correlated systems with a large number of degrees of freedom. In the illustrative applications, the t-DMRG approach is applied to investigate the nonadiabatic processes in realistic chemical systems, including exciton dissociation and triplet fission in polymers and molecular aggregates as well as internal conversion in pyrazine molecule.

  11. Nuclear ``pasta'' phase within density dependent hadronic models

    Science.gov (United States)

    Avancini, S. S.; Brito, L.; Marinelli, J. R.; Menezes, D. P.; de Moraes, M. M. W.; Providência, C.; Santos, A. M.

    2009-03-01

    In the present paper, we investigate the onset of the “pasta” phase with different parametrizations of the density dependent hadronic model and compare the results with one of the usual parametrizations of the nonlinear Walecka model. The influence of the scalar-isovector virtual δ meson is shown. At zero temperature, two different methods are used, one based on coexistent phases and the other on the Thomas-Fermi approximation. At finite temperature, only the coexistence phases method is used. npe matter with fixed proton fractions and in β equilibrium are studied. We compare our results with restrictions imposed on the values of the density and pressure at the inner edge of the crust, obtained from observations of the Vela pulsar and recent isospin diffusion data from heavy-ion reactions, and with predictions from spinodal calculations.

  12. Nuclear 'pasta' phase within density dependent hadronic models

    International Nuclear Information System (INIS)

    Avancini, S. S.; Marinelli, J. R.; Menezes, D. P.; Moraes, M. M. W. de; Brito, L.; Providencia, C.; Santos, A. M.

    2009-01-01

    In the present paper, we investigate the onset of the 'pasta' phase with different parametrizations of the density dependent hadronic model and compare the results with one of the usual parametrizations of the nonlinear Walecka model. The influence of the scalar-isovector virtual δ meson is shown. At zero temperature, two different methods are used, one based on coexistent phases and the other on the Thomas-Fermi approximation. At finite temperature, only the coexistence phases method is used. npe matter with fixed proton fractions and in β equilibrium are studied. We compare our results with restrictions imposed on the values of the density and pressure at the inner edge of the crust, obtained from observations of the Vela pulsar and recent isospin diffusion data from heavy-ion reactions, and with predictions from spinodal calculations

  13. A pair density functional theory utilizing the correlated wave function

    International Nuclear Information System (INIS)

    Higuchi, M; Higuchi, K

    2009-01-01

    We propose a practical scheme for calculating the ground-state pair density (PD) by utilizing the correlated wave function. As the correlated wave function, we adopt a linear combination of the single Slater determinants that are constructed from the solutions of the initial scheme [Higuchi M and Higuchi K 2007 Physica B 387, 117]. The single-particle equation is derived by performing the variational principle within the set of PDs that are constructed from such correlated wave functions. Since the search region of the PD is substantially extended as compared with the initial scheme, it is expected that the present scheme can cover more correlation effects. The single-particle equation is practical, and may be easily applied to actual calculations.

  14. SURFACE SYMMETRY ENERGY OF NUCLEAR ENERGY DENSITY FUNCTIONALS

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-12-20

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

  15. Local-scaling density-functional method: Intraorbit and interorbit density optimizations

    International Nuclear Information System (INIS)

    Koga, T.; Yamamoto, Y.; Ludena, E.V.

    1991-01-01

    The recently proposed local-scaling density-functional theory provides us with a practical method for the direct variational determination of the electron density function ρ(r). The structure of ''orbits,'' which ensures the one-to-one correspondence between the electron density ρ(r) and the N-electron wave function Ψ({r k }), is studied in detail. For the realization of the local-scaling density-functional calculations, procedures for intraorbit and interorbit optimizations of the electron density function are proposed. These procedures are numerically illustrated for the helium atom in its ground state at the beyond-Hartree-Fock level

  16. Relativistic Random-Phase Approximation with Density-dependent Meson-nucleon Couplings at Finite Temperature

    International Nuclear Information System (INIS)

    Niu, Y.; Paar, N.; Vretenar, D.; Meng, J.

    2009-01-01

    The fully self-consistent relativistic random-phase approximation (RRPA) framework based on effective interactions with a phenomenological density dependence is extended to finite temperatures. The RRPA configuration space is built from the spectrum of single-nucleon states at finite temperature obtained by the temperature dependent relativistic mean field (RMF-T) theory based on effective Lagrangian with density dependent meson-nucleon vertex functions. As an illustration, the dependence of binding energy, radius, entropy and single particle levels on temperature for spherical nucleus 2 08P b is investigated in RMF-T theory. The finite temperature RRPA has been employed in studies of giant monopole and dipole resonances, and the evolution of resonance properties has been studied as a function of temperature. In addition, exotic modes of excitation have been systematically explored at finite temperatures, with an emphasis on the case of pygmy dipole resonances.(author)

  17. Bone mineral density, adiposity and cognitive functions

    Directory of Open Access Journals (Sweden)

    Hamid R Sohrabi

    2015-02-01

    Full Text Available Cognitive decline and dementia due to Alzheimer’s disease have been associated with genetic, lifestyle, and environmental factors. A number of potentially modifiable risk factors should be taken into account when preventive or ameliorative interventions targeting dementia and its preclinical stages are investigated. Bone mineral density (BMD and body composition are two such potentially modifiable risk factors, and their association with cognitive decline was investigated in this study. 164 participants, aged 34 to 87 years old (62.78±9.27, were recruited for this longitudinal study and underwent cognitive and clinical examinations at baseline and after three years. Blood samples were collected for apolipoprotein E (APOE genotyping and dual energy x-ray absorptiometry (DXA was conducted at the same day as cognitive assessment. Using hierarchical regression analysis, we found that BMD and lean body mass, as measured using DXA were significant predictors of episodic memory. Age, gender, APOE status and premorbid IQ were controlled for. Specifically, the List A learning from California Verbal Learning Test was significantly associated with BMD and lean mass both at baseline and at follow up assessment. Our findings indicate that there is a significant association between BMD and lean body mass and episodic verbal learning. While the involvement of modifiable lifestyle factors in human cognitive function has been examined in different studies, there is a need for further research to understand the potential underlying mechanisms.

  18. 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

  19. Rationale for switching to nonlocal functionals in density functional theory.

    Science.gov (United States)

    Lazić, P; Atodiresei, N; Caciuc, V; Brako, R; Gumhalter, B; Blügel, S

    2012-10-24

    Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

  20. Rationale for switching to nonlocal functionals in density functional theory

    International Nuclear Information System (INIS)

    Lazić, P; Atodiresei, N; Caciuc, V; Blügel, S; Brako, R; Gumhalter, B

    2012-01-01

    Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

  1. Self-consistent embedding of density-matrix renormalization group wavefunctions in a density functional environment.

    Science.gov (United States)

    Dresselhaus, Thomas; Neugebauer, Johannes; Knecht, Stefan; Keller, Sebastian; Ma, Yingjin; Reiher, Markus

    2015-01-28

    We present the first implementation of a density matrix renormalization group algorithm embedded in an environment described by density functional theory. The frozen density embedding scheme is used with a freeze-and-thaw strategy for a self-consistent polarization of the orbital-optimized wavefunction and the environmental densities with respect to each other.

  2. Reduced density matrix functional theory at finite temperature

    Energy Technology Data Exchange (ETDEWEB)

    Baldsiefen, Tim

    2012-10-15

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

  3. Reduced density matrix functional theory at finite temperature

    International Nuclear Information System (INIS)

    Baldsiefen, Tim

    2012-10-01

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

  4. Development and application of a density dependent matrix ...

    Science.gov (United States)

    Ranging along the Atlantic coast from US Florida to the Maritime Provinces of Canada, the Atlantic killifish (Fundulus heteroclitus) is an important and well-studied model organism for understanding the effects of pollutants and other stressors in estuarine and marine ecosystems. Matrix population models are useful tools for ecological risk assessment because they integrate effects across the life cycle, provide a linkage between endpoints observed in the individual and ecological risk to the population as a whole, and project outcomes for many generations in the future. We developed a density dependent matrix population model for Atlantic killifish by modifying a model developed for fathead minnow (Pimephales promelas) that has proved to be extremely useful, e.g. to incorporate data from laboratory studies and project effects of endocrine disrupting chemicals. We developed a size-structured model (as opposed to one that is based upon developmental stages or age class structure) so that we could readily incorporate output from a Dynamic Energy Budget (DEB) model, currently under development. Due to a lack of sufficient data to accurately define killifish responses to density dependence, we tested a number of scenarios realistic for other fish species in order to demonstrate the outcome of including this ecologically important factor. We applied the model using published data for killifish exposed to dioxin-like compounds, and compared our results to those using

  5. Density functional theory and multiscale materials modeling

    Indian Academy of Sciences (India)

    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.

  6. Graphene on metals: A van der Waals density functional study

    DEFF Research Database (Denmark)

    Vanin, Marco; Mortensen, Jens Jørgen; Kelkkanen, Kari André

    2010-01-01

    We use density functional theory (DFT) with a recently developed van der Waals density functional (vdW-DF) to study the adsorption of graphene on Co, Ni, Pd, Ag, Au, Cu, Pt, and Al(111) surfaces. In contrast to the local-density approximation (LDA) which predicts relatively strong binding for Ni...

  7. Correlation functional in screened-exchange density functional theory procedures.

    Science.gov (United States)

    Chan, Bun; Kawashima, Yukio; Hirao, Kimihiko

    2017-10-15

    In the present study, we have explored several prospects for the further development of screened-exchange density functional theory (SX-DFT) procedures. Using the performance of HSE06 as our measure, we find that the use of alternative correlation functionals (as oppose to PBEc in HSE06) also yields adequate results for a diverse set of thermochemical properties. We have further examined the performance of new SX-DFT procedures (termed HSEB-type methods) that comprise the HSEx exchange and a (near-optimal) reparametrized B97c (c OS,0  = c SS,0  = 1, c OS,1  = -1.5, c OS,2  = -0.644, c SS,1  = -0.5, and c SS,2  = 1.10) correlation functionals. The different variants of HSEB all perform comparably to or slightly better than the original HSE-type procedures. These results, together with our fundamental analysis of correlation functionals, point toward various directions for advancing SX-DFT methods. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  8. Symmetry Energy as a Function of Density and Mass

    International Nuclear Information System (INIS)

    Danielewicz, Pawel; Lee, Jenny

    2007-01-01

    Energy in nuclear matter is, in practice, completely characterized at different densities and asymmetries, when the density dependencies of symmetry energy and of energy of symmetric matter are specified. The density dependence of the symmetry energy at subnormal densities produces mass dependence of nuclear symmetry coefficient and, thus, can be constrained by that latter dependence. We deduce values of the mass dependent symmetry coefficients, by using excitation energies to isobaric analog states. The coefficient systematic, for intermediate and high masses, is well described in terms of the symmetry coefficient values of a a V = (31.5-33.5) MeV for the volume coefficient and a a S = (9-12) MeV for the surface coefficient. These two further correspond to the parameter values describing density dependence of symmetry energy, of L∼95 MeV and K sym ∼25 MeV

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

    Science.gov (United States)

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

    2018-03-01

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

  10. Time-dependent potential-functional embedding theory

    International Nuclear Information System (INIS)

    Huang, Chen; Libisch, Florian; Peng, Qing; Carter, Emily A.

    2014-01-01

    We introduce a time-dependent potential-functional embedding theory (TD-PFET), in which atoms are grouped into subsystems. In TD-PFET, subsystems can be propagated by different suitable time-dependent quantum mechanical methods and their interactions can be treated in a seamless, first-principles manner. TD-PFET is formulated based on the time-dependent quantum mechanics variational principle. The action of the total quantum system is written as a functional of the time-dependent embedding potential, i.e., a potential-functional formulation. By exploiting the Runge-Gross theorem, we prove the uniqueness of the time-dependent embedding potential under the constraint that all subsystems share a common embedding potential. We derive the integral equation that such an embedding potential needs to satisfy. As proof-of-principle, we demonstrate TD-PFET for a Na 4 cluster, in which each Na atom is treated as one subsystem and propagated by time-dependent Kohn-Sham density functional theory (TDDFT) using the adiabatic local density approximation (ALDA). Our results agree well with a direct TDDFT calculation on the whole Na 4 cluster using ALDA. We envision that TD-PFET will ultimately be useful for studying ultrafast quantum dynamics in condensed matter, where key regions are solved by highly accurate time-dependent quantum mechanics methods, and unimportant regions are solved by faster, less accurate methods

  11. Density dependence triggers runaway selection of reduced senescence.

    Directory of Open Access Journals (Sweden)

    Robert M Seymour

    2007-12-01

    Full Text Available In the presence of exogenous mortality risks, future reproduction by an individual is worth less than present reproduction to its fitness. Senescent aging thus results inevitably from transferring net fertility into younger ages. Some long-lived organisms appear to defy theory, however, presenting negligible senescence (e.g., hydra and extended lifespans (e.g., Bristlecone Pine. Here, we investigate the possibility that the onset of vitality loss can be delayed indefinitely, even accepting the abundant evidence that reproduction is intrinsically costly to survival. For an environment with constant hazard, we establish that natural selection itself contributes to increasing density-dependent recruitment losses. We then develop a generalized model of accelerating vitality loss for analyzing fitness optima as a tradeoff between compression and spread in the age profile of net fertility. Across a realistic spectrum of senescent age profiles, density regulation of recruitment can trigger runaway selection for ever-reducing senescence. This novel prediction applies without requirement for special life-history characteristics such as indeterminate somatic growth or increasing fecundity with age. The evolution of nonsenescence from senescence is robust to the presence of exogenous adult mortality, which tends instead to increase the age-independent component of vitality loss. We simulate examples of runaway selection leading to negligible senescence and even intrinsic immortality.

  12. Parton densities in quantum chromodynamics. Gauge invariance, path-dependence, and Wilson lines

    International Nuclear Information System (INIS)

    Cherednikov, Igor O.

    2017-01-01

    The purpose of this book is to give a systematic pedagogical exposition of the quantitative analysis of Wilson lines and gauge-invariant correlation functions in quantum chromodynamics. Using techniques from the previous volume (Wilson Lines in Quantum Field Theory, 2014), an ab initio methodology is developed and practical tools for its implementation are presented. Emphasis is put on the implications of gauge invariance and path-dependence properties of transverse-momentum dependent parton density functions. The latter are associated with the QCD factorization approach to semi-inclusive hadronic processes, studied at currently operating and planned experimental facilities.

  13. Parton densities in quantum chromodynamics. Gauge invariance, path-dependence, and Wilson lines

    Energy Technology Data Exchange (ETDEWEB)

    Cherednikov, Igor O. [Antwerpen Univ. (Belgium). Dept. Fysica; Veken, Frederik F. van der [CERN, Geneva (Switzerland)

    2017-05-01

    The purpose of this book is to give a systematic pedagogical exposition of the quantitative analysis of Wilson lines and gauge-invariant correlation functions in quantum chromodynamics. Using techniques from the previous volume (Wilson Lines in Quantum Field Theory, 2014), an ab initio methodology is developed and practical tools for its implementation are presented. Emphasis is put on the implications of gauge invariance and path-dependence properties of transverse-momentum dependent parton density functions. The latter are associated with the QCD factorization approach to semi-inclusive hadronic processes, studied at currently operating and planned experimental facilities.

  14. Orthogonal bases of radial functions for charge density refinements

    International Nuclear Information System (INIS)

    Restori, R.

    1990-01-01

    Charge density determination from X-ray measurements necessitates the evaluation of the Fourier-Bessel transforms of the radial functions used to expand the charge density. Analytical expressions are given here for four sets of orthogonal functions which can substitute for the 'traditional exponential functions' set in least-squares refinements. (orig.)

  15. Strong Correlation in Kohn-Sham Density Functional Theory

    NARCIS (Netherlands)

    Malet, F.; Gori Giorgi, P.

    2012-01-01

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

  16. Improved Density Functional Tight Binding Potentials for Metalloid Aluminum Clusters

    Science.gov (United States)

    2016-06-01

    unlimited IMPROVED DENSITY-FUNCTIONAL TIGHT BINDING POTENTIALS FOR METALLOID ALUMINUM CLUSTERS by Joon H. Kim June 2016 Thesis Advisor...DATES COVERED Master’s thesis 4. TITLE AND SUBTITLE IMPROVED DENSITY-FUNCTIONAL TIGHT BINDING POTENTIALS FOR METALLOID ALUMINUM CLUSTERS 5. FUNDING...repulsive potentials for use in density-functional tight binding (DFTB) simulations of low-valence aluminum metalloid clusters . These systems are under

  17. Discovery of functional and approximate functional dependencies in relational databases

    Directory of Open Access Journals (Sweden)

    Ronald S. King

    2003-01-01

    Full Text Available This study develops the foundation for a simple, yet efficient method for uncovering functional and approximate functional dependencies in relational databases. The technique is based upon the mathematical theory of partitions defined over a relation's row identifiers. Using a levelwise algorithm the minimal non-trivial functional dependencies can be found using computations conducted on integers. Therefore, the required operations on partitions are both simple and fast. Additionally, the row identifiers provide the added advantage of nominally identifying the exceptions to approximate functional dependencies, which can be used effectively in practical data mining applications.

  18. Error estimation and parameter dependence of the calculation of the fast ion distribution function, temperature, and density using data from the KF1 high energy neutral particle analyzer on Joint European Torus

    International Nuclear Information System (INIS)

    Schlatter, Christian; Testa, Duccio; Cecconello, Marco; Murari, Andrea; Santala, Marko

    2004-01-01

    Joint European Torus high energy neutral particle analyzer measures the flux of fast neutrals originating from the plasma core. From this data, the fast ion distribution function f i fast , temperature T i,perpendicular fast , and density n i fast are derived using knowledge of various plasma parameters and of the cross section for the required atomic processes. In this article, a systematic sensitivity study of the effect of uncertainties in these quantities on the evaluation of the neutral particle analyzer f i fast , T i,perpendicular fast , and n i fast is reported. The dominant parameter affecting n i fast is the impurity confinement time and therefore a reasonable estimate of this quantity is necessary to reduce the uncertainties in n i fast below 50%. On the other hand, T i,perpendicular fast is much less sensitive and can certainly be provided with an accuracy of better than 10%

  19. A comparative study of density functional and density functional tight binding calculations of defects in graphene

    Energy Technology Data Exchange (ETDEWEB)

    Zobelli, Alberto [Laboratoire de Physique des Solides, Univ. Paris Sud, CNRS UMR, Orsay (France); Ivanovskaya, Viktoria; Wagner, Philipp; Yaya, Abu; Ewels, Chris P. [Institut des Materiaux Jean Rouxel (IMN), CNRS UMR, University of Nantes (France); Suarez-Martinez, Irene [Nanochemistry Research Institute, Curtin University of Technology, Perth, Western Australia (Australia)

    2012-02-15

    The density functional tight binding approach (DFTB) is well adapted for the study of point and line defects in graphene based systems. After briefly reviewing the use of DFTB in this area, we present a comparative study of defect structures, energies, and dynamics between DFTB results obtained using the dftb+ code, and density functional results using the localized Gaussian orbital code, AIMPRO. DFTB accurately reproduces structures and energies for a range of point defect structures such as vacancies and Stone-Wales defects in graphene, as well as various unfunctionalized and hydroxylated graphene sheet edges. Migration barriers for the vacancy and Stone-Wales defect formation barriers are accurately reproduced using a nudged elastic band approach. Finally we explore the potential for dynamic defect simulations using DFTB, taking as an example electron irradiation damage in graphene. DFTB-MD derived sputtering energy threshold map for a carbon atom in a graphene plane. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Postnatal development of depth-dependent collagen density in ovine articular cartilage

    Directory of Open Access Journals (Sweden)

    Kranenbarg Sander

    2010-10-01

    Full Text Available Abstract Background Articular cartilage (AC is the layer of tissue that covers the articulating ends of the bones in diarthrodial joints. Adult AC is characterised by a depth-dependent composition and structure of the extracellular matrix that results in depth-dependent mechanical properties, important for the functions of adult AC. Collagen is the most abundant solid component and it affects the mechanical behaviour of AC. The current objective is to quantify the postnatal development of depth-dependent collagen density in sheep (Ovis aries AC between birth and maturity. We use Fourier transform infra-red micro-spectroscopy to investigate collagen density in 48 sheep divided over ten sample points between birth (stillborn and maturity (72 weeks. In each animal, we investigate six anatomical sites (caudal, distal and rostral locations at the medial and lateral side of the joint in the distal metacarpus of a fore leg and a hind leg. Results Collagen density increases from birth to maturity up to our last sample point (72 weeks. Collagen density increases at the articular surface from 0.23 g/ml ± 0.06 g/ml (mean ± s.d., n = 48 at 0 weeks to 0.51 g/ml ± 0.10 g/ml (n = 46 at 72 weeks. Maximum collagen density in the deeper cartilage increases from 0.39 g/ml ± 0.08 g/ml (n = 48 at 0 weeks to 0.91 g/ml ± 0.13 g/ml (n = 46 at 72 weeks. Most collagen density profiles at 0 weeks (85% show a valley, indicating a minimum, in collagen density near the articular surface. At 72 weeks, only 17% of the collagen density profiles show a valley in collagen density near the articular surface. The fraction of profiles with this valley stabilises at 36 weeks. Conclusions Collagen density in articular cartilage increases in postnatal life with depth-dependent variation, and does not stabilize up to 72 weeks, the last sample point in our study. We find strong evidence for a valley in collagen densities near the articular surface that is present in the youngest

  1. Modelling the dependability in Network Function Virtualisation

    OpenAIRE

    Lin, Wenqi

    2017-01-01

    Network Function Virtualization has been brought up to allow the TSPs to have more possibilities and flexibilities to provision services with better load optimizing, energy utilizing and dynamic scaling. Network functions will be decoupled from the underlying dedicated hardware into software instances that run on commercial off-the-shelf servers. However, the development is still at an early stage and the dependability concerns raise by the virtualization of the network functions are touched ...

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

    Science.gov (United States)

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

    2015-09-08

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

  3. Experimental evidence for density-dependent reproduction in a cooperatively breeding passerine

    NARCIS (Netherlands)

    Brouwer, Lyanne; Tinbergen, Joost M.; Both, Christiaan; Bristol, Rachel; Richardson, David S.; Komdeur, Jan; Sauer, J.R.

    Temporal variation in survival, fecundity, and dispersal rates is associated with density-dependent and density-independent processes. Stable natural populations are expected to be regulated by density-dependent factors. However, detecting this by investigating natural variation in density is

  4. Density of the Breit--Wigner functions

    International Nuclear Information System (INIS)

    Perry, W.L.; Luning, C.D.

    1975-01-01

    It is shown, for certain sequences [lambda/sub i/] in the complex plane, that linear combinations of the Breit-Wigner functions [B/sub i/] approximate, in the mean square, any function in L 2 (0,infinity). Implications and numerical use of this result are discussed

  5. Bone mineral density and menstrual function in adolescent female ...

    African Journals Online (AJOL)

    Bone mineral density and menstrual function in adolescent female long-distance runners - A prospective comparative study of bone structure and menstrual function in adolescent female endurance athletes from five secondary schools in Pretoria.

  6. Density-density functionals and effective potentials in many-body electronic structure calculations

    International Nuclear Information System (INIS)

    Reboredo, Fernando A.; Kent, Paul R.

    2008-01-01

    We demonstrate the existence of different density-density functionals designed to retain selected properties of the many-body ground state in a non-interacting solution starting from the standard density functional theory ground state. We focus on diffusion quantum Monte Carlo applications that require trial wave functions with optimal Fermion nodes. The theory is extensible and can be used to understand current practices in several electronic structure methods within a generalized density functional framework. The theory justifies and stimulates the search of optimal empirical density functionals and effective potentials for accurate calculations of the properties of real materials, but also cautions on the limits of their applicability. The concepts are tested and validated with a near-analytic model.

  7. Characterizing the Spatial Density Functions of Neural Arbors

    Science.gov (United States)

    Teeter, Corinne Michelle

    Recently, it has been proposed that a universal function describes the way in which all arbors (axons and dendrites) spread their branches over space. Data from fish retinal ganglion cells as well as cortical and hippocampal arbors from mouse, rat, cat, monkey and human provide evidence that all arbor density functions (adf) can be described by a Gaussian function truncated at approximately two standard deviations. A Gaussian density function implies that there is a minimal set of parameters needed to describe an adf: two or three standard deviations (depending on the dimensionality of the arbor) and an amplitude. However, the parameters needed to completely describe an adf could be further constrained by a scaling law found between the product of the standard deviations and the amplitude of the function. In the following document, I examine the scaling law relationship in order to determine the minimal set of parameters needed to describe an adf. First, I find that the at, two-dimensional arbors of fish retinal ganglion cells require only two out of the three fundamental parameters to completely describe their density functions. Second, the three-dimensional, volume filling, cortical arbors require four fundamental parameters: three standard deviations and the total length of an arbor (which corresponds to the amplitude of the function). Next, I characterize the shape of arbors in the context of the fundamental parameters. I show that the parameter distributions of the fish retinal ganglion cells are largely homogenous. In general, axons are bigger and less dense than dendrites; however, they are similarly shaped. The parameter distributions of these two arbor types overlap and, therefore, can only be differentiated from one another probabilistically based on their adfs. Despite artifacts in the cortical arbor data, different types of arbors (apical dendrites, non-apical dendrites, and axons) can generally be differentiated based on their adfs. In addition, within

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

    Science.gov (United States)

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

    2018-05-03

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

  9. Density-functional theory for internal magnetic fields

    Science.gov (United States)

    Tellgren, Erik I.

    2018-01-01

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

  10. Changes in seasonal climate outpace compensatory density-dependence in eastern brook trout

    Science.gov (United States)

    Bassar, Ronald D.; Letcher, Benjamin H.; Nislow, Keith H.; Whiteley, Andrew R.

    2016-01-01

    Understanding how multiple extrinsic (density-independent) factors and intrinsic (density-dependent) mechanisms influence population dynamics has become increasingly urgent in the face of rapidly changing climates. It is particularly unclear how multiple extrinsic factors with contrasting effects among seasons are related to declines in population numbers and changes in mean body size and whether there is a strong role for density-dependence. The primary goal of this study was to identify the roles of seasonal variation in climate driven environmental direct effects (mean stream flow and temperature) versus density-dependence on population size and mean body size in eastern brook trout (Salvelinus fontinalis). We use data from a 10-year capture-mark-recapture study of eastern brook trout in four streams in Western Massachusetts, USA to parameterize a discrete-time population projection model. The model integrates matrix modeling techniques used to characterize discrete population structures (age, habitat type and season) with integral projection models (IPMs) that characterize demographic rates as continuous functions of organismal traits (in this case body size). Using both stochastic and deterministic analyses we show that decreases in population size are due to changes in stream flow and temperature and that these changes are larger than what can be compensated for through density-dependent responses. We also show that the declines are due mostly to increasing mean stream temperatures decreasing the survival of the youngest age class. In contrast, increases in mean body size over the same period are the result of indirect changes in density with a lesser direct role of climate-driven environmental change.

  11. Measure and dimension functions: measurability and densities

    Science.gov (United States)

    Mattila, Pertti; Mauldin, R. Daniel

    1997-01-01

    During the past several years, new types of geometric measure and dimension have been introduced; the packing measure and dimension, see [Su], [Tr] and [TT1]. These notions are playing an increasingly prevalent role in various aspects of dynamics and measure theory. Packing measure is a sort of dual of Hausdorff measure in that it is defined in terms of packings rather than coverings. However, in contrast to Hausdorff measure, the usual definition of packing measure requires two limiting procedures, first the construction of a premeasure and then a second standard limiting process to obtain the measure. This makes packing measure somewhat delicate to deal with. The question arises as to whether there is some simpler method for defining packing measure and dimension. In this paper, we find a basic limitation on this possibility. We do this by determining the descriptive set-theoretic complexity of the packing functions. Whereas the Hausdorff dimension function on the space of compact sets is Borel measurable, the packing dimension function is not. On the other hand, we show that the packing dimension functions are measurable with respect to the [sigma]-algebra generated by the analytic sets. Thus, the usual sorts of measurability properties used in connection with Hausdorff measure, for example measures of sections and projections, remain true for packing measure.

  12. A consumer-resource approach to the density-dependent population dynamics of mutualism.

    Science.gov (United States)

    Holland, J Nathaniel; DeAngelis, Donald L

    2010-05-01

    Like predation and competition, mutualism is now recognized as a consumer-resource (C-R) interaction, including, in particular, bi-directional (e.g., coral, plant-mycorrhizae) and uni-directional (e.g., ant-plant defense, plant-pollinator) C-R mutualisms. Here, we develop general theory for the density-dependent population dynamics of mutualism based on the C-R mechanism of interspecific interaction. To test the influence of C-R interactions on the dynamics and stability of bi- and uni-directional C-R mutualisms, we developed simple models that link consumer functional response of one mutualistic species with the resources supplied by another. Phase-plane analyses show that the ecological dynamics of C-R mutualisms are stable in general. Most transient behavior leads to an equilibrium of mutualistic coexistence, at which both species densities are greater than in the absence of interactions. However, due to the basic nature of C-R interactions, certain density-dependent conditions can lead to C-R dynamics characteristic of predator-prey interactions, in which one species overexploits and causes the other to go extinct. Consistent with empirical phenomena, these results suggest that the C-R interaction can provide a broad mechanism for understanding density-dependent population dynamics of mutualism. By unifying predation, competition, and mutualism under the common ecological framework of consumer-resource theory, we may also gain a better understanding of the universal features of interspecific interactions in general.

  13. A consumer-resource approach to the density-dependent population dynamics of mutualism

    Science.gov (United States)

    Holland, J. Nathaniel; DeAngelis, Donald L.

    2010-01-01

    Like predation and competition, mutualism is now recognized as a consumer resource (C-R) interaction, including, in particular, bi-directional (e.g., coral, plant- mycorrhizae) and uni-directional (e.g., ant-plant defense, plant-pollinator) C-R mutualisms. Here, we develop general theory for the density-dependent population dynamics of mutualism based on the C-R mechanism of interspecific interaction. To test the influence of C-R interactions on the dynamics and stability of bi- and uni-directional C-R mutualisms, we developed simple models that link consumer functional response of one mutualistic species with the resources supplied by another. Phase-plane analyses show that the ecological dynamics of C-R mutualisms are stable in general. Most transient behavior leads to an equilibrium of mutualistic coexistence, at which both species densities are greater than in the absence of interactions. However, due to the basic nature of C-R interactions, certain density-dependent conditions can lead to C-R dynamics characteristic of predator-prey interactions, in which one species overexploits and causes the other to go extinct. Consistent with empirical phenomena, these results suggest that the C-R interaction can provide a broad mechanism for understanding density-dependent population dynamics of mutualism. By unifying predation, competition, and mutualism under the common ecological framework of consumer-resource theory, we may also gain a better understanding of the universal features of interspecific interactions in general.

  14. Chewing Maintains Hippocampus-Dependent Cognitive Function.

    Science.gov (United States)

    Chen, Huayue; Iinuma, Mitsuo; Onozuka, Minoru; Kubo, Kin-Ya

    2015-01-01

    Mastication (chewing) is important not only for food intake, but also for preserving and promoting the general health. Recent studies have showed that mastication helps to maintain cognitive functions in the hippocampus, a central nervous system region vital for spatial memory and learning. The purpose of this paper is to review the recent progress of the association between mastication and the hippocampus-dependent cognitive function. There are multiple neural circuits connecting the masticatory organs and the hippocampus. Both animal and human studies indicated that cognitive functioning is influenced by mastication. Masticatory dysfunction is associated with the hippocampal morphological impairments and the hippocampus-dependent spatial memory deficits, especially in elderly. Mastication is an effective behavior for maintaining the hippocampus-dependent cognitive performance, which deteriorates with aging. Therefore, chewing may represent a useful approach in preserving and promoting the hippocampus-dependent cognitive function in older people. We also discussed several possible mechanisms involved in the interaction between mastication and the hippocampal neurogenesis and the future directions for this unique fascinating research.

  15. Density-dependent growth and metamorphosis in the larval bronze ...

    Indian Academy of Sciences (India)

    Effects of density and kinship on growth and metamorphosis in tadpoles of Rana temporalis were studied in a 2 × 4 factorial experiment. Fifteen egg masses were collected from streams in the Western Ghat region of south India. The tadpoles were raised as siblings or in groups of non-siblings at increasing density levels, viz ...

  16. Refitting density dependent relativistic model parameters including Center-of-Mass corrections

    International Nuclear Information System (INIS)

    Avancini, Sidney S.; Marinelli, Jose R.; Carlson, Brett Vern

    2011-01-01

    Full text: Relativistic mean field models have become a standard approach for precise nuclear structure calculations. After the seminal work of Serot and Walecka, which introduced a model Lagrangian density where the nucleons interact through the exchange of scalar and vector mesons, several models were obtained through its generalization, including other meson degrees of freedom, non-linear meson interactions, meson-meson interactions, etc. More recently density dependent coupling constants were incorporated into the Walecka-like models, which are then extensively used. In particular, for these models a connection with the density functional theory can be established. Due to the inherent difficulties presented by field theoretical models, only the mean field approximation is used for the solution of these models. In order to calculate finite nuclei properties in the mean field approximation, a reference set has to be fixed and therefore the translational symmetry is violated. It is well known that in such case spurious effects due to the center-of-mass (COM) motion are present, which are more pronounced for light nuclei. In a previous work we have proposed a technique based on the Pierls-Yoccoz projection operator applied to the mean-field relativistic solution, in order to project out spurious COM contributions. In this work we obtain a new fitting for the density dependent parameters of a density dependent hadronic model, taking into account the COM corrections. Our fitting is obtained taking into account the charge radii and binding energies for He 4 , O 16 , Ca 40 , Ca 48 , Ni 56 , Ni 68 , Sn 100 , Sn 132 and Pb 208 . We show that the nuclear observables calculated using our fit are of a quality comparable to others that can be found in the literature, with the advantage that now a translational invariant many-body wave function is at our disposal. (author)

  17. Diameter dependent failure current density of gold nanowires

    International Nuclear Information System (INIS)

    Karim, S; Maaz, K; Ali, G; Ensinger, W

    2009-01-01

    Failure current density of single gold nanowires is investigated in this paper. Single wires with diameters ranging from 80 to 720 nm and length 30 μm were electrochemically deposited in ion track-etched single-pore polycarbonate membranes. The maximum current density was investigated while keeping the wires embedded in the polymer matrix and ramping up the current until failure occurred. The current density is found to increase with diminishing diameter and the wires with a diameter of 80 nm withstand 1.2 x 10 12 A m -2 before undergoing failure. Possible reasons for these results are discussed in this paper.

  18. Density dependence of stopping cross sections measured in liquid ethane

    International Nuclear Information System (INIS)

    Both, G.; Krotz, R.; Lohmer, K.; Neuwirth, W.

    1983-01-01

    Electronic stopping cross sections for 7 Li projectiles (840--175 keV) have been measured with the inverted Doppler-shift attenuation method in liquid ethane (C 2 H 6 ) at two different densities. The density of the target has been varied by changing the temperature, and measurements have been performed at 0.525 g/cm 3 (199 K) and 0.362 g/cm 3 (287 K). At the higher density the stopping cross section is about 2% smaller. This result agrees with a calculation of the stopping cross section of liquid ethane, applying Lindhard's theory in the local-density approximation using a simple model of the liquid. It is also in agreement with various observations of the so-called physical-state effect, which show that the stopping cross section of the same substance is smaller in a condensed phase than in the gaseous one

  19. Dielectric Screening Meets Optimally Tuned Density Functionals.

    Science.gov (United States)

    Kronik, Leeor; Kümmel, Stephan

    2018-04-17

    A short overview of recent attempts at merging two independently developed methods is presented. These are the optimal tuning of a range-separated hybrid (OT-RSH) functional, developed to provide an accurate first-principles description of the electronic structure and optical properties of gas-phase molecules, and the polarizable continuum model (PCM), developed to provide an approximate but computationally tractable description of a solvent in terms of an effective dielectric medium. After a brief overview of the OT-RSH approach, its combination with the PCM as a potentially accurate yet low-cost approach to the study of molecular assemblies and solids, particularly in the context of photocatalysis and photovoltaics, is discussed. First, solvated molecules are considered, with an emphasis on the challenge of balancing eigenvalue and total energy trends. Then, it is shown that the same merging of methods can also be used to study the electronic and optical properties of molecular solids, with a similar discussion of the pros and cons. Tuning of the effective scalar dielectric constant as one recent approach that mitigates some of the difficulties in merging the two approaches is considered. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Bone mineral density in patients with noninsulin-dependent diabetes mellitus by dual photon absorptiometry

    International Nuclear Information System (INIS)

    Kao, C.H.; Tsou, C.T.; Chen, C.C.; Wang, S.J.

    1993-01-01

    Bone mineral density (BMD) in 38 male patients with noninsulin-dependent diabetes mellitus (NIDDM) was measured by dual photon absorptiometry (DPA) using a M and SE Osteo Tech 300 scanner. The BMD of the second to fourth lumbar vertebrae was measured and the mean density was presented as g cm -2 . The patients were distinguished according to the following three criteria: (1) blood sugar control was good or poor; (2) the duration of diabetes was long or short; (3) renal function was evaluated by effective renal plasma flow (ERPF) as good or poor. The results showed about half the cases of NIDDM had lower BMD. The patients with poor blood sugar control, longer disease duration and poor renal function had lower BMD. However, the difference between any two groups distinguished by the three criteria is not significant. We think that the causes of osteoporosis in patients with NIDDM may not be explained by only a single factor. (author)

  1. Density-dependent effects on physical condition and reproduction in North American elk: an experimental test.

    Science.gov (United States)

    Kelley M. Stewart; R. Terry Bowyer; Brian L. Dick; Bruce K. Johnson; John G. Kie

    2005-01-01

    Density dependence plays a key role in life-history characteristics and population ecology of large, herbivorous mammals. We designed a manipulative experiment to test hypotheses relating effects of density-dependent mechanisms on physical condition and fecundity of North American elk (Cervus elaphus) by creating populations at low and high density...

  2. 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...

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

    Indian Academy of Sciences (India)

    ZIRAN CHEN

    2017-08-04

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

  4. Continuation of probability density functions using a generalized Lyapunov approach

    NARCIS (Netherlands)

    Baars, S.; Viebahn, J. P.; Mulder, T. E.; Kuehn, C.; Wubs, F. W.; Dijkstra, H. A.

    2017-01-01

    Techniques from numerical bifurcation theory are very useful to study transitions between steady fluid flow patterns and the instabilities involved. Here, we provide computational methodology to use parameter continuation in determining probability density functions of systems of stochastic partial

  5. Density Functional Calculations of Solid State Heats of Formation

    National Research Council Canada - National Science Library

    Politzer, Peter

    1999-01-01

    It is now feasible to compute quite accurate gas phase heats of formation for relatively small molecules by means of ab initio or density functional techniques and one of several possible approaches...

  6. Dynamical density functional theory for dense atomic liquids

    International Nuclear Information System (INIS)

    Archer, A J

    2006-01-01

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

  7. Function of Maximal Microvessel Density in Breast Tumor Metastasis

    National Research Council Canada - National Science Library

    McLeskey, Sandra

    2000-01-01

    .... These data are gained by quantitating the number of microvessels in "hot spots" of high-density tumor vasculature, implying that such hot spots have functional significance in the process of metastasis...

  8. A classical density functional theory of ionic liquids.

    Science.gov (United States)

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

    2011-04-28

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

  9. Constraints on parton density functions from D0

    Energy Technology Data Exchange (ETDEWEB)

    Hays, Jonathan M.; /Imperial Coll., London

    2008-04-01

    Five recent results from D0 which either impact or have the potential to impact on uncertainties in parton density functions are presented. Many analyses at D0 are sensitive to the modeling of the partonic structure of the proton. When theoretical and experimental uncertainties are well controlled there exists the possibility for additional constraints on parton density functions (PDF). Five measurements are presented which either have already been included in global parton fits or have the potential to contribute in the future.

  10. Improved density functional calculations for atoms, molecules and surfaces

    International Nuclear Information System (INIS)

    Fricke, B.; Anton, J.; Fritzsche, S.; Sarpe-Tudoran, C.

    2005-01-01

    The non-collinear and collinear descriptions within relativistic density functional theory is described. We present results of both non-collinear and collinear calculations for atoms, diatomic molecules, and some surface simulations. We find that the accuracy of our density functional calculations for the smaller systems is comparable to good quantum chemical calculations, and thus this method provides a sound basis for larger systems where no such comparison is possible. (author)

  11. Density dependence of electron mobility in the accumulation mode for fully depleted SOI films

    Energy Technology Data Exchange (ETDEWEB)

    Naumova, O. V., E-mail: naumova@isp.nsc.ru; Zaitseva, E. G.; Fomin, B. I.; Ilnitsky, M. A.; Popov, V. P. [Russian Academy of Sciences, Rzhanov Institute of Semiconductor Physics, Siberian Branch (Russian Federation)

    2015-10-15

    The electron mobility µ{sub eff} in the accumulation mode is investigated for undepleted and fully depleted double-gate n{sup +}–n–n{sup +} silicon-on-insulator (SOI) metal–oxide–semiconductor field-effect transistors (MOSFET). To determine the range of possible values of the mobility and the dominant scattering mechanisms in thin-film structures, it is proposed that the field dependence of the mobility µ{sub eff} be replaced with the dependence on the density N{sub e} of induced charge carriers. It is shown that the dependences µ{sub eff}(N{sub e}) can be approximated by the power functions µ{sub eff}(N{sub e}) ∝ N{sub e}{sup -n}, where the exponent n is determined by the chargecarrier scattering mechanism as in the mobility field dependence. The values of the exponent n in the dependences µ{sub eff}(N{sub e}) are determined when the SOI-film mode near one of its surfaces varies from inversion to accumulation. The obtained results are explained from the viewpoint of the electron-density redistribution over the SOI-film thickness and changes in the scattering mechanisms.

  12. Response functions for infinite fermion systems with velocity dependent interactions

    International Nuclear Information System (INIS)

    Garcia-Recio, C.; Salcedo, L.L.; Navarro, J.; Nguyen Van Giai

    1991-01-01

    Response functions of infinite Fermi systems are studied in the framework of the self-consistent Random Phase Approximation. Starting from an effective interaction with velocity and density dependence, or equivalently from a local energy density functional, algebraic expressions for the RPA response function are derived. Simple formulae for the energy-weighted and polarizability sum rules are obtained. The method is illustrated by applications to nuclear matter and liquid 3 He. In nuclear matter, it is shown that existing Skyrme interactions give spin-isospin response functions close to those calculated with finite range interactions. The different renormalization of longitudinal and transverse Coulomb sum rules in nuclear matter is discussed. In 3 He, the low-lying collective spin oscillation can be well described in a wide range of momenta with a Skyrme-type interaction if the relevant Landau parameters are fitted. For the high-lying density oscillation, the introduction of a finite range term in the energy functional improves considerably the agreement with the data. (author) 54 refs., 19 figs., 4 tabs

  13. Long-term persistence, density dependence and effects of climate change on rosyside dace (Cyprinidae)

    Science.gov (United States)

    Gary D. Grossman; Gary Sundin; Robert E. Ratajczak

    2016-01-01

    SummaryWe used long-term population data for rosyside dace (Clinostomus funduloides), a numerically dominant member of a stochastically organised fish assemblage, to evaluate the relative importance of density-dependent and density-independent processes to population...

  14. Density dependence, whitebark pine, and vital rates of grizzly bears

    Science.gov (United States)

    van Manen, Frank T.; Haroldson, Mark A.; Bjornlie, Daniel D.; Ebinger, Michael R.; Thompson, Daniel J.; Costello, Cecily M.; White, Gary C.

    2016-01-01

    Understanding factors influencing changes in population trajectory is important for effective wildlife management, particularly for populations of conservation concern. Annual population growth of the grizzly bear (Ursus arctos) population in the Greater Yellowstone Ecosystem, USA has slowed from 4.2–7.6% during 1983–2001 to 0.3–2.2% during 2002–2011. Substantial changes in availability of a key food source and bear population density have occurred. Whitebark pine (Pinus albicaulis), the seeds of which are a valuable but variable fall food for grizzly bears, has experienced substantial mortality primarily due to a mountain pine beetle (Dendroctonus ponderosae) outbreak that started in the early 2000s. Positive growth rates of grizzly bears have resulted in populations reaching high densities in some areas and have contributed to continued range expansion. We tested research hypotheses to examine if changes in vital rates detected during the past decade were more associated with whitebark pine decline or, alternatively, increasing grizzly bear density. We focused our assessment on known-fate data to estimate survival of cubs-of-the-year (cubs), yearlings, and independent bears (≥2 yrs), and reproductive transition of females from having no offspring to having cubs. We used spatially and temporally explicit indices for grizzly bear density and whitebark pine mortality as individual covariates. Models indicated moderate support for an increase in survival of independent male bears over 1983–2012, whereas independent female survival did not change. Cub survival, yearling survival, and reproductive transition from no offspring to cubs all changed during the 30-year study period, with lower rates evident during the last 10–15 years. Cub survival and reproductive transition were negatively associated with an index of grizzly bear density, indicating greater declines where bear densities were higher. Our analyses did not support a similar relationship for the

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

    Science.gov (United States)

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

    2018-03-13

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

  16. Density functional theory for polymeric systems in 2D

    International Nuclear Information System (INIS)

    Słyk, Edyta; Bryk, Paweł; Roth, Roland

    2016-01-01

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

  17. Comments on the locality in density-functional theory

    International Nuclear Information System (INIS)

    Lindgren, Ingvar; Salomonson, Sten

    2003-01-01

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

  18. Modeling charged defects inside density functional theory band gaps

    International Nuclear Information System (INIS)

    Schultz, Peter A.; Edwards, Arthur H.

    2014-01-01

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

  19. Density-dependent vulnerability of forest ecosystems to drought

    Science.gov (United States)

    Alessandra Bottero; Anthony W. D' Amato; Brian J. Palik; John B. Bradford; Shawn Fraver; Mike A. Battaglia; Lance A. Asherin; Harald Bugmann

    2017-01-01

    Climate models predict increasing drought intensity and frequency for many regions, which may have negative consequences for tree recruitment, growth and mortality, as well as forest ecosystem services. Furthermore, practical strategies for minimizing vulnerability to drought are limited. Tree population density, a metric of tree abundance in a given area, is a primary...

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

    International Nuclear Information System (INIS)

    Holas, A.; March, N.H.

    2002-01-01

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

  1. 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.

  2. Density-functional, density-functional tight-binding, and wave-function calculations on biomolecular systems

    Czech Academy of Sciences Publication Activity Database

    Kubař, Tomáš; Jurečka, Petr; Černý, Jiří; Řezáč, Jan; Otyepka, M.; Valdes, Haydee; Hobza, Pavel

    2007-01-01

    Roč. 111, č. 26 (2007), s. 5642-5647 ISSN 1089-5639 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550510; GA ČR(CZ) GD203/05/H001; GA ČR GA203/05/0009 Institutional research plan: CEZ:AV0Z40550506 Keywords : density functional theory * empirical dispersion-energy term * non-covalent interactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.918, year: 2007

  3. Uniform magnetic fields in density-functional theory

    Science.gov (United States)

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

    2018-01-01

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

  4. Electron mobility in supercritical pentanes as a function of density and temperature

    International Nuclear Information System (INIS)

    Itoh, Kengo; Nakagawa, Kazumichi; Nishikawa, Masaru

    1988-01-01

    The excess electron mobility in supercritical n-, iso- and neopentane was measured isothermally as a function of density. The density-normalized mobility μN in all three isomers goes through a minimum at a density below the respective critical densities, and the mobility is quite temperature-dependent in this region, then goes through a minimum. The μN behavior around the minimum in n-pentane is well accounted for by the Cohen-Lekner model with the structure factor S(K) estimated from the speed of sound, while that in iso- and neopentane is not. (author)

  5. Density dependence of the diffusion coefficient of alkali metals

    International Nuclear Information System (INIS)

    Adebayo, G.A.; Anusionwu, B.C.; Njah, A.N.; Mathew, B.; Fabamise, O.A.T.

    2004-06-01

    The effect of density on transport coefficients of liquid Li, Na and K at high temperatures using the method of Molecular Dynamics simulation has been studied. Simulation of these liquid alkali metals were carried out with 800 particles in simulation boxes with periodic boundary conditions imposed. In order to test the reliability of the interatomic potential used in the calculations, experimental data on the structural properties were compared with calculated results. The calculations showed a linear relationship between the density and the diffusion coefficient in all the systems investigated except in lithium, where, due to the small size of the atom, standard molecular dynamics simulation method may not be appropriate for calculating the properties of interest. (author)

  6. A real-space stochastic density matrix approach for density functional electronic structure.

    Science.gov (United States)

    Beck, Thomas L

    2015-12-21

    The recent development of real-space grid methods has led to more efficient, accurate, and adaptable approaches for large-scale electrostatics and density functional electronic structure modeling. With the incorporation of multiscale techniques, linear-scaling real-space solvers are possible for density functional problems if localized orbitals are used to represent the Kohn-Sham energy functional. These methods still suffer from high computational and storage overheads, however, due to extensive matrix operations related to the underlying wave function grid representation. In this paper, an alternative stochastic method is outlined that aims to solve directly for the one-electron density matrix in real space. In order to illustrate aspects of the method, model calculations are performed for simple one-dimensional problems that display some features of the more general problem, such as spatial nodes in the density matrix. This orbital-free approach may prove helpful considering a future involving increasingly parallel computing architectures. Its primary advantage is the near-locality of the random walks, allowing for simultaneous updates of the density matrix in different regions of space partitioned across the processors. In addition, it allows for testing and enforcement of the particle number and idempotency constraints through stabilization of a Feynman-Kac functional integral as opposed to the extensive matrix operations in traditional approaches.

  7. Wigner Function of Density Operator for Negative Binomial Distribution

    International Nuclear Information System (INIS)

    Xu Xinglei; Li Hongqi

    2008-01-01

    By using the technique of integration within an ordered product (IWOP) of operator we derive Wigner function of density operator for negative binomial distribution of radiation field in the mixed state case, then we derive the Wigner function of squeezed number state, which yields negative binomial distribution by virtue of the entangled state representation and the entangled Wigner operator

  8. 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...

  9. Higher-accuracy van der Waals density functional

    DEFF Research Database (Denmark)

    Lee, Kyuho; Murray, Éamonn D.; Kong, Lingzhu

    2010-01-01

    We propose a second version of the van der Waals density functional of Dion et al. [Phys. Rev. Lett. 92, 246401 (2004)], employing a more accurate semilocal exchange functional and the use of a large-N asymptote gradient correction in determining the vdW kernel. The predicted binding energy...

  10. Level densities of iron isotopes and lower-energy enhancement of y-strength function

    International Nuclear Information System (INIS)

    Voinov, A V; Grimes, S M; Agvaanluvsan, U; Algin, E; Belgya, T; Brune, C R; Guttormsen, M; Hornish, M J; Massey, T N; Mitchell, G; Rekstad, J; Schiller, A; Siem, S

    2005-01-01

    The neutron spectrum from the 55 Mn(d,n) 56 Fe reaction has been measured at E d = 7 MeV. The level density of 56 Fe obtained from neutron evaporation spectrum has been compared to the level density from Oslo-type 57 Fe( 3 He, aγ) 56 Fe experiment [1]. The good agreement supports the recent results [1, 8] including an availability of a low-energy enhancement in the γ-strength function for iron isotopes. The new level density function allowed us to investigate an excitation energy dependence of this enhancement, which is shown to increase with increasing excitation energy

  11. Optimal Bandwidth Selection for Kernel Density Functionals Estimation

    Directory of Open Access Journals (Sweden)

    Su Chen

    2015-01-01

    Full Text Available The choice of bandwidth is crucial to the kernel density estimation (KDE and kernel based regression. Various bandwidth selection methods for KDE and local least square regression have been developed in the past decade. It has been known that scale and location parameters are proportional to density functionals ∫γ(xf2(xdx with appropriate choice of γ(x and furthermore equality of scale and location tests can be transformed to comparisons of the density functionals among populations. ∫γ(xf2(xdx can be estimated nonparametrically via kernel density functionals estimation (KDFE. However, the optimal bandwidth selection for KDFE of ∫γ(xf2(xdx has not been examined. We propose a method to select the optimal bandwidth for the KDFE. The idea underlying this method is to search for the optimal bandwidth by minimizing the mean square error (MSE of the KDFE. Two main practical bandwidth selection techniques for the KDFE of ∫γ(xf2(xdx are provided: Normal scale bandwidth selection (namely, “Rule of Thumb” and direct plug-in bandwidth selection. Simulation studies display that our proposed bandwidth selection methods are superior to existing density estimation bandwidth selection methods in estimating density functionals.

  12. Detecting positive quadrant dependence and positive function dependence

    NARCIS (Netherlands)

    Janic-Wróblewska, A.; Kallenberg, W.C.M.; Ledwina, T.

    2004-01-01

    There is a lot of interest in positive dependence going beyond linear correlation. In this paper three new rank tests for testing independence against positive dependence are introduced. The first one is directed on positive quadrant dependence, the second and third one concentrate on positive

  13. Detecting positive quadrant dependence and positive function dependence

    NARCIS (Netherlands)

    Janic-Wróblewska, A.; Kallenberg, W.C.M.; Ledwina, T.

    2003-01-01

    There is a lot of interest in positive dependence going beyond linear correlation. In this paper three new rank tests for testing independence against positive dependence are introduced. The first one is directed on positive quadrant dependence, the second and third one concentrate on positive

  14. Transport through correlated systems with density functional theory.

    Science.gov (United States)

    Kurth, S; Stefanucci, G

    2017-10-18

    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.

  15. Study of excitation energy dependence of nuclear level density parameter

    International Nuclear Information System (INIS)

    Mohanto, G.; Nayak, B.K.; Saxena, A.

    2016-01-01

    In the present study, we have populated CN by fusion reaction and excitation energy of the intermediate nuclei is determined after first chance α-emission to investigate excitation energy dependence of the NLD parameter. Evaporated neutron spectra were measured following alpha evaporation for obtaining NLD parameter for the reaction 11 B + 197 Au, populating CN 208 Po. This CN after evaporating an α-particle populates intermediate nucleus 204 Pb. The 204 Pb has magic number of Z=82. Our aim is to study the excitation energy dependence of NLD parameter for closed shell nuclei

  16. On Improving Density Estimators which are not Bona Fide Functions

    OpenAIRE

    Gajek, Leslaw

    1986-01-01

    In order to improve the rate of decrease of the IMSE for nonparametric kernel density estimators with nonrandom bandwidth beyond $O(n^{-4/5})$ all current methods must relax the constraint that the density estimate be a bona fide function, that is, be nonnegative and integrate to one. In this paper we show how to achieve similar improvement without relaxing any of these constraints. The method can also be applied for orthogonal series, adaptive orthogonal series, spline, jackknife, and other ...

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

    Science.gov (United States)

    Soirat, Arnaud J. A.

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

  18. Discovering context-aware conditional functional dependencies

    Institute of Scientific and Technical Information of China (English)

    Yuefeng DU; Derong SHEN; Tiezheng NIE; Yue KOU; Ge YU

    2017-01-01

    Conditional functional dependencies(CFDs) are important techniques for data consistency.However,CFDs are limited to 1) provide the reasonable values for consistency repairing and 2) detect potential errors.This paper presents context-aware conditional functional dependencies(CCFDs) which contribute to provide reasonable values and detect potential errors.Especially,we focus on automatically discovering minimal CCFDs.In this paper,we present context relativity to measure the relationship of CFDs.The overlap of the related CFDs can provide reasonable values which result in more accuracy consistency repairing,and some related CFDs are combined into CCFDs.Moreover,we prove that discovering minimal CCFDs is NP-complete and we design the precise method and the heuristic method.We also present the dominating value to facilitate the process in both the precise method and the heuristic method.Additionally,the context relativity of the CFDs affects the cleaning results.We will give an approximate threshold of context relativity according to data distribution for suggestion.The repairing results are approved more accuracy,even evidenced by our empirical evaluation.

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

    NARCIS (Netherlands)

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

    2013-01-01

    The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the

  20. The functional response to prey density in an acarine system

    NARCIS (Netherlands)

    Fransz, H.G.

    1974-01-01

    Predacious mites are considered to be important natural enemies of phytophagous mites. Their efficiency in the natural control of prey populations depends on the relationships of the number of prey killed per predator per time unit and the oviposition rate on the one hand and prey density on the

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

    Science.gov (United States)

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

    2017-08-01

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

  2. Vibrational Spectroscopic Studies of Tenofovir Using Density Functional Theory Method

    Directory of Open Access Journals (Sweden)

    G. R. Ramkumaar

    2013-01-01

    Full Text Available A systematic vibrational spectroscopic assignment and analysis of tenofovir has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis was aided by electronic structure calculations—hybrid density functional methods (B3LYP/6-311++G(d,p, B3LYP/6-31G(d,p, and B3PW91/6-31G(d,p. Molecular equilibrium geometries, electronic energies, IR intensities, and harmonic vibrational frequencies have been computed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties such as HOMO and LUMO energies and were determined by time-dependent DFT (TD-DFT method. The geometrical, thermodynamical parameters, and absorption wavelengths were compared with the experimental data. The B3LYP/6-311++G(d,p-, B3LYP/6-31G(d,p-, and B3PW91/6-31G(d,p-based NMR calculation procedure was also done. It was used to assign the 13C and 1H NMR chemical shift of tenofovir.

  3. Density functional approach to the many-body problem : Key concepts and exact functionals

    NARCIS (Netherlands)

    van Leeuwen, Robert

    2003-01-01

    We give an overview of the fundamental concepts of density functional theory. We give a careful discussion of the several density functionals and their differentiability properties. We show that for nondegenerate ground states we can calculate the necessary functional derivatives by means of linear

  4. Transverse momentum dependent (TMD) parton distribution functions. Status and prospects

    International Nuclear Information System (INIS)

    Angeles-Martinez, R.; Bacchetta, A.; Pavia Univ.; Balitsky, I.I.

    2015-07-01

    We provide a concise overview on transverse momentum dependent (TMD) parton distribution functions, their application to topical issues in high-energy physics phenomenology, and their theoretical connections with QCD resummation, evolution and factorization theorems. We illustrate the use of TMDs via examples of multi-scale problems in hadronic collisions. These include transverse momentum q T spectra of Higgs and vector bosons for low q T , and azimuthal correlations in the production of multiple jets associated with heavy bosons at large jet masses. We discuss computational tools for TMDs, and present an application of a new tool, TMDlib, to parton density fits and parameterizations.

  5. Performance of density functional theory methods to describe ...

    Indian Academy of Sciences (India)

    Fukui function shows a small dependence with both the exchange and correlation functional and the basis set. Evolution of the Fukui function along the reaction path describes important changes in the basic sites of the corresponding molecules. These results are in agreement with the chemical behavior of those species.

  6. Strong orientation dependence of surface mass density profiles of dark haloes at large scales

    Science.gov (United States)

    Osato, Ken; Nishimichi, Takahiro; Oguri, Masamune; Takada, Masahiro; Okumura, Teppei

    2018-06-01

    We study the dependence of surface mass density profiles, which can be directly measured by weak gravitational lensing, on the orientation of haloes with respect to the line-of-sight direction, using a suite of N-body simulations. We find that, when major axes of haloes are aligned with the line-of-sight direction, surface mass density profiles have higher amplitudes than those averaged over all halo orientations, over all scales from 0.1 to 100 Mpc h-1 we studied. While the orientation dependence at small scales is ascribed to the halo triaxiality, our results indicate even stronger orientation dependence in the so-called two-halo regime, up to 100 Mpc h-1. The orientation dependence for the two-halo term is well approximated by a multiplicative shift of the amplitude and therefore a shift in the halo bias parameter value. The halo bias from the two-halo term can be overestimated or underestimated by up to {˜ } 30 per cent depending on the viewing angle, which translates into the bias in estimated halo masses by up to a factor of 2 from halo bias measurements. The orientation dependence at large scales originates from the anisotropic halo-matter correlation function, which has an elliptical shape with the axis ratio of ˜0.55 up to 100 Mpc h-1. We discuss potential impacts of halo orientation bias on other observables such as optically selected cluster samples and a clustering analysis of large-scale structure tracers such as quasars.

  7. Probability density function method for variable-density pressure-gradient-driven turbulence and mixing

    International Nuclear Information System (INIS)

    Bakosi, Jozsef; Ristorcelli, Raymond J.

    2010-01-01

    Probability density function (PDF) methods are extended to variable-density pressure-gradient-driven turbulence. We apply the new method to compute the joint PDF of density and velocity in a non-premixed binary mixture of different-density molecularly mixing fluids under gravity. The full time-evolution of the joint PDF is captured in the highly non-equilibrium flow: starting from a quiescent state, transitioning to fully developed turbulence and finally dissipated by molecular diffusion. High-Atwood-number effects (as distinguished from the Boussinesq case) are accounted for: both hydrodynamic turbulence and material mixing are treated at arbitrary density ratios, with the specific volume, mass flux and all their correlations in closed form. An extension of the generalized Langevin model, originally developed for the Lagrangian fluid particle velocity in constant-density shear-driven turbulence, is constructed for variable-density pressure-gradient-driven flows. The persistent small-scale anisotropy, a fundamentally 'non-Kolmogorovian' feature of flows under external acceleration forces, is captured by a tensorial diffusion term based on the external body force. The material mixing model for the fluid density, an active scalar, is developed based on the beta distribution. The beta-PDF is shown to be capable of capturing the mixing asymmetry and that it can accurately represent the density through transition, in fully developed turbulence and in the decay process. The joint model for hydrodynamics and active material mixing yields a time-accurate evolution of the turbulent kinetic energy and Reynolds stress anisotropy without resorting to gradient diffusion hypotheses, and represents the mixing state by the density PDF itself, eliminating the need for dubious mixing measures. Direct numerical simulations of the homogeneous Rayleigh-Taylor instability are used for model validation.

  8. Linking density functional and mode coupling models for supercooled liquids

    Energy Technology Data Exchange (ETDEWEB)

    Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P. [School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067 (India)

    2016-03-28

    We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

  9. Linking density functional and mode coupling models for supercooled liquids.

    Science.gov (United States)

    Premkumar, Leishangthem; Bidhoodi, Neeta; Das, Shankar P

    2016-03-28

    We compare predictions from two familiar models of the metastable supercooled liquid, respectively, constructed with thermodynamic and dynamic approaches. In the so called density functional theory the free energy F[ρ] of the liquid is a functional of the inhomogeneous density ρ(r). The metastable state is identified as a local minimum of F[ρ]. The sharp density profile characterizing ρ(r) is identified as a single particle oscillator, whose frequency is obtained from the parameters of the optimum density function. On the other hand, a dynamic approach to supercooled liquids is taken in the mode coupling theory (MCT) which predict a sharp ergodicity-non-ergodicity transition at a critical density. The single particle dynamics in the non-ergodic state, treated approximately, represents a propagating mode whose characteristic frequency is computed from the corresponding memory function of the MCT. The mass localization parameters in the above two models (treated in their simplest forms) are obtained, respectively, in terms of the corresponding natural frequencies depicted and are shown to have comparable magnitudes.

  10. The maximal-density mass function for primordial black hole dark matter

    Science.gov (United States)

    Lehmann, Benjamin V.; Profumo, Stefano; Yant, Jackson

    2018-04-01

    The advent of gravitational wave astronomy has rekindled interest in primordial black holes (PBH) as a dark matter candidate. As there are many different observational probes of the PBH density across different masses, constraints on PBH models are dependent on the functional form of the PBH mass function. This complicates general statements about the mass functions allowed by current data, and, in particular, about the maximum total density of PBH. Numerical studies suggest that some forms of extended mass functions face tighter constraints than monochromatic mass functions, but they do not preclude the existence of a functional form for which constraints are relaxed. We use analytical arguments to show that the mass function which maximizes the fraction of the matter density in PBH subject to all constraints is a finite linear combination of monochromatic mass functions. We explicitly compute the maximum fraction of dark matter in PBH for different combinations of current constraints, allowing for total freedom of the mass function. Our framework elucidates the dependence of the maximum PBH density on the form of observational constraints, and we discuss the implications of current and future constraints for the viability of the PBH dark matter paradigm.

  11. Similarity of dependences of thermal conductivity and density of uranium and tungsten hexafluorides on desublimation conditions

    International Nuclear Information System (INIS)

    Barkov, V.A.

    1989-01-01

    Consideration is given to results of investigations of the dependence of thermal conductivity and density of UF 6 and WF 6 desublimates on volume content of hexafluoride in initial gaseous mixture. Similarity of these dependences, as well as the dependences of thermal conductivity of desublimates on their density was revealed. Generalized expressions, relating thermal conductivity and density of desublimates among each ofter and with volume content of hexafluoride in gaseous mixture were derived. Possibility of applying the generalized relations for calculation of thermal conductivity and density of other compounds of MeF 6 type under prescribed desublimation conclitions is shown. 15 refs.; 6 figs

  12. Kinetic-energy density functional: Atoms and shell structure

    International Nuclear Information System (INIS)

    Garcia-Gonzalez, P.; Alvarellos, J.E.; Chacon, E.

    1996-01-01

    We present a nonlocal kinetic-energy functional which includes an anisotropic average of the density through a symmetrization procedure. This functional allows a better description of the nonlocal effects of the electron system. The main consequence of the symmetrization is the appearance of a clear shell structure in the atomic density profiles, obtained after the minimization of the total energy. Although previous results with some of the nonlocal kinetic functionals have given incipient structures for heavy atoms, only our functional shows a clear shell structure for most of the atoms. The atomic total energies have a good agreement with the exact calculations. Discussion of the chemical potential and the first ionization potential in atoms is included. The functional is also extended to spin-polarized systems. copyright 1996 The American Physical Society

  13. Effects of Density-Dependent Bag Constant and Strange Star Rotation

    Institute of Scientific and Technical Information of China (English)

    ZHOU Qiao-Er; GUO Hua

    2003-01-01

    With the emphasis on the effects of the density-dependent bag constant and the rotation of strange star the limiting mass of strange star is calculated. The obtained results show that the limiting mass and the corresponding radius of strange star increase as the rotation frequency increases, and tend to be lowered when the density-dependent bag constant is considered.

  14. On the evolution of the density probability density function in strongly self-gravitating systems

    International Nuclear Information System (INIS)

    Girichidis, Philipp; Konstandin, Lukas; Klessen, Ralf S.; Whitworth, Anthony P.

    2014-01-01

    The time evolution of the probability density function (PDF) of the mass density is formulated and solved for systems in free-fall using a simple approximate function for the collapse of a sphere. We demonstrate that a pressure-free collapse results in a power-law tail on the high-density side of the PDF. The slope quickly asymptotes to the functional form P V (ρ)∝ρ –1.54 for the (volume-weighted) PDF and P M (ρ)∝ρ –0.54 for the corresponding mass-weighted distribution. From the simple approximation of the PDF we derive analytic descriptions for mass accretion, finding that dynamically quiet systems with narrow density PDFs lead to retarded star formation and low star formation rates (SFRs). Conversely, strong turbulent motions that broaden the PDF accelerate the collapse causing a bursting mode of star formation. Finally, we compare our theoretical work with observations. The measured SFRs are consistent with our model during the early phases of the collapse. Comparison of observed column density PDFs with those derived from our model suggests that observed star-forming cores are roughly in free-fall.

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

    International Nuclear Information System (INIS)

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

    1983-11-01

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

  16. On Farmer's line, probability density functions, and overall risk

    International Nuclear Information System (INIS)

    Munera, H.A.; Yadigaroglu, G.

    1986-01-01

    Limit lines used to define quantitative probabilistic safety goals can be categorized according to whether they are based on discrete pairs of event sequences and associated probabilities, on probability density functions (pdf's), or on complementary cumulative density functions (CCDFs). In particular, the concept of the well-known Farmer's line and its subsequent reinterpretations is clarified. It is shown that Farmer's lines are pdf's and, therefore, the overall risk (defined as the expected value of the pdf) that they represent can be easily calculated. It is also shown that the area under Farmer's line is proportional to probability, while the areas under CCDFs are generally proportional to expected value

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

    International Nuclear Information System (INIS)

    Goerling, A.

    1996-01-01

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

  18. Demographic models reveal the shape of density dependence for a specialist insect herbivore on variable host plants.

    Science.gov (United States)

    Miller, Tom E X

    2007-07-01

    1. It is widely accepted that density-dependent processes play an important role in most natural populations. However, persistent challenges in our understanding of density-dependent population dynamics include evaluating the shape of the relationship between density and demographic rates (linear, concave, convex), and identifying extrinsic factors that can mediate this relationship. 2. I studied the population dynamics of the cactus bug Narnia pallidicornis on host plants (Opuntia imbricata) that varied naturally in relative reproductive effort (RRE, the proportion of meristems allocated to reproduction), an important plant quality trait. I manipulated per-plant cactus bug densities, quantified subsequent dynamics, and fit stage-structured models to the experimental data to ask if and how density influences demographic parameters. 3. In the field experiment, I found that populations with variable starting densities quickly converged upon similar growth trajectories. In the model-fitting analyses, the data strongly supported a model that defined the juvenile cactus bug retention parameter (joint probability of surviving and not dispersing) as a nonlinear decreasing function of density. The estimated shape of this relationship shifted from concave to convex with increasing host-plant RRE. 4. The results demonstrate that host-plant traits are critical sources of variation in the strength and shape of density dependence in insects, and highlight the utility of integrated experimental-theoretical approaches for identifying processes underlying patterns of change in natural populations.

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

    Science.gov (United States)

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

    2005-05-13

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

  20. Effective size of density-dependent two-sex populations: the effect of mating systems.

    Science.gov (United States)

    Myhre, A M; Engen, S; SAEther, B-E

    2017-08-01

    Density dependence in vital rates is a key feature affecting temporal fluctuations of natural populations. This has important implications for the rate of random genetic drift. Mating systems also greatly affect effective population sizes, but knowledge of how mating system and density regulation interact to affect random genetic drift is poor. Using theoretical models and simulations, we compare N e in short-lived, density-dependent animal populations with different mating systems. We study the impact of a fluctuating, density-dependent sex ratio and consider both a stable and a fluctuating environment. We find a negative relationship between annual N e /N and adult population size N due to density dependence, suggesting that loss of genetic variation is reduced at small densities. The magnitude of this decrease was affected by mating system and life history. A male-biased, density-dependent sex ratio reduces the rate of genetic drift compared to an equal, density-independent sex ratio, but a stochastic change towards male bias reduces the N e /N ratio. Environmental stochasticity amplifies temporal fluctuations in population size and is thus vital to consider in estimation of effective population sizes over longer time periods. Our results on the reduced loss of genetic variation at small densities, particularly in polygamous populations, indicate that density regulation may facilitate adaptive evolution at small population sizes. © 2017 European Society For Evolutionary Biology. Journal of Evolutionary Biology © 2017 European Society For Evolutionary Biology.

  1. Influence of molecular geometry, exchange-correlation functional, and solvent effects in the modeling of vertical excitation energies in phthalocyanines using time-dependent density functional theory (TDDFT) and polarized continuum model TDDFT methods: can modern computational chemistry methods explain experimental controversies?

    Science.gov (United States)

    Nemykin, Victor N; Hadt, Ryan G; Belosludov, Rodion V; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

    2007-12-20

    A time-dependent density functional theory (TDDFT) approach coupled with 14 different exchange-correlation functionals was used for the prediction of vertical excitation energies in zinc phthalocyanine (PcZn). In general, the TDDFT approach provides a more accurate description of both visible and ultraviolet regions of the UV-vis and magnetic circular dichroism (MCD) spectra of PcZn in comparison to the more popular semiempirical ZINDO/S and PM3 methods. It was found that the calculated vertical excitation energies of PcZn correlate with the amount of Hartree-Fock exchange involved in the exchange-correlation functional. The correlation was explained on the basis of the calculated difference in energy between occupied and unoccupied molecular orbitals. The influence of PcZn geometry, optimized using different exchange-correlation functionals, on the calculated vertical excitation energies in PcZn was found to be relatively small. The influence of solvents on the calculated vertical excitation energies in PcZn was considered for the first time using a polarized continuum model TDDFT (PCM-TDDFT) method and was found to be relatively small in excellent agreement with the experimental data. For all tested TDDFT and PCM-TDDFT cases, an assignment of the Q-band as an almost pure a1u (HOMO)-->eg (LUMO) transition, initially suggested by Gouterman, was confirmed. Pure exchange-correlation functionals indicate the presence of six 1Eu states in the B-band region of the UV-vis spectrum of PcZn, while hybrid exchange-correlation functionals predict only five 1Eu states for the same energy envelope. The first two symmetry-forbidden n-->pi* transitions were predicted in the Q0-2 region and in the low-energy tail of the B-band, while the first two symmetry-allowed n-->pi* transitions were found within the B-band energy envelope when pure exchange-correlation functionals were used for TDDFT calculations. The presence of a symmetry-forbidden but vibronically allowed n

  2. Linear density response function in the projector augmented wave method

    DEFF Research Database (Denmark)

    Yan, Jun; Mortensen, Jens Jørgen; Jacobsen, Karsten Wedel

    2011-01-01

    We present an implementation of the linear density response function within the projector-augmented wave method with applications to the linear optical and dielectric properties of both solids, surfaces, and interfaces. The response function is represented in plane waves while the single...... functions of Si, C, SiC, AlP, and GaAs compare well with previous calculations. While optical properties of semiconductors, in particular excitonic effects, are generally not well described by ALDA, we obtain excellent agreement with experiments for the surface loss function of graphene and the Mg(0001...

  3. Redshift space correlations and scale-dependent stochastic biasing of density peaks

    Science.gov (United States)

    Desjacques, Vincent; Sheth, Ravi K.

    2010-01-01

    We calculate the redshift space correlation function and the power spectrum of density peaks of a Gaussian random field. Our derivation, which is valid on linear scales k≲0.1hMpc-1, is based on the peak biasing relation given by Desjacques [Phys. Rev. DPRVDAQ1550-7998, 78, 103503 (2008)10.1103/PhysRevD.78.103503]. In linear theory, the redshift space power spectrum is Ppks(k,μ)=exp⁡(-f2σvel2k2μ2)[bpk(k)+bvel(k)fμ2]2Pδ(k), where μ is the angle with respect to the line of sight, σvel is the one-dimensional velocity dispersion, f is the growth rate, and bpk(k) and bvel(k) are k-dependent linear spatial and velocity bias factors. For peaks, the value of σvel depends upon the functional form of bvel. When the k dependence is absent from the square brackets and bvel is set to unity, the resulting expression is assumed to describe models where the bias is linear and deterministic, but the velocities are unbiased. The peak model is remarkable because it has unbiased velocities in this same sense—peak motions are driven by dark matter flows—but, in order to achieve this, bvel must be k dependent. We speculate that this is true in general: k dependence of the spatial bias will lead to k dependence of bvel even if the biased tracers flow with the dark matter. Because of the k dependence of the linear bias parameters, standard manipulations applied to the peak model will lead to k-dependent estimates of the growth factor that could erroneously be interpreted as a signature of modified dark energy or gravity. We use the Fisher formalism to show that the constraint on the growth rate f is degraded by a factor of 2 if one allows for a k-dependent velocity bias of the peak type. Our analysis also demonstrates that the Gaussian smoothing term is part and parcel of linear theory. We discuss a simple estimate of nonlinear evolution and illustrate the effect of the peak bias on the redshift space multipoles. For k≲0.1hMpc-1, the peak bias is deterministic but k

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

    Science.gov (United States)

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

    2018-02-01

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

  5. KIDS Nuclear Energy Density Functional: 1st Application in Nuclei

    Science.gov (United States)

    Gil, Hana; Papakonstantinou, Panagiota; Hyun, Chang Ho; Oh, Yongseok

    We apply the KIDS (Korea: IBS-Daegu-Sungkyunkwan) nuclear energy density functional model, which is based on the Fermi momentum expansion, to the study of properties of lj-closed nuclei. The parameters of the model are determined by the nuclear properties at the saturation density and theoretical calculations on pure neutron matter. For applying the model to the study of nuclei, we rely on the Skyrme force model, where the Skyrme force parameters are determined through the KIDS energy density functional. Solving Hartree-Fock equations, we obtain the energies per particle and charge radii of closed magic nuclei, namely, 16O, 28O, 40Ca, 48Ca, 60Ca, 90Zr, 132Sn, and 208Pb. The results are compared with the observed data and further improvement of the model is shortly mentioned.

  6. Population-Level Density Dependence Influences the Origin and Maintenance of Parental Care.

    Directory of Open Access Journals (Sweden)

    Elijah Reyes

    Full Text Available Parental care is a defining feature of animal breeding systems. We now know that both basic life-history characteristics and ecological factors influence the evolution of care. However, relatively little is known about how these factors interact to influence the origin and maintenance of care. Here, we expand upon previous work and explore the relationship between basic life-history characteristics (stage-specific rates of mortality and maturation and the fitness benefits associated with the origin and the maintenance of parental care for two broad ecological scenarios: the scenario in which egg survival is density dependent and the case in which adult survival is density dependent. Our findings suggest that high offspring need is likely critical in driving the origin, but not the maintenance, of parental care regardless of whether density dependence acts on egg or adult survival. In general, parental care is more likely to result in greater fitness benefits when baseline adult mortality is low if 1 egg survival is density dependent or 2 adult mortality is density dependent and mutant density is relatively high. When density dependence acts on egg mortality, low rates of egg maturation and high egg densities are less likely to lead to strong fitness benefits of care. However, when density dependence acts on adult mortality, high levels of egg maturation and increasing adult densities are less likely to maintain care. Juvenile survival has relatively little, if any, effect on the origin and maintenance of egg-only care. More generally, our results suggest that the evolution of parental care will be influenced by an organism's entire life history characteristics, the stage at which density dependence acts, and whether care is originating or being maintained.

  7. Population-Level Density Dependence Influences the Origin and Maintenance of Parental Care.

    Science.gov (United States)

    Reyes, Elijah; Thrasher, Patsy; Bonsall, Michael B; Klug, Hope

    2016-01-01

    Parental care is a defining feature of animal breeding systems. We now know that both basic life-history characteristics and ecological factors influence the evolution of care. However, relatively little is known about how these factors interact to influence the origin and maintenance of care. Here, we expand upon previous work and explore the relationship between basic life-history characteristics (stage-specific rates of mortality and maturation) and the fitness benefits associated with the origin and the maintenance of parental care for two broad ecological scenarios: the scenario in which egg survival is density dependent and the case in which adult survival is density dependent. Our findings suggest that high offspring need is likely critical in driving the origin, but not the maintenance, of parental care regardless of whether density dependence acts on egg or adult survival. In general, parental care is more likely to result in greater fitness benefits when baseline adult mortality is low if 1) egg survival is density dependent or 2) adult mortality is density dependent and mutant density is relatively high. When density dependence acts on egg mortality, low rates of egg maturation and high egg densities are less likely to lead to strong fitness benefits of care. However, when density dependence acts on adult mortality, high levels of egg maturation and increasing adult densities are less likely to maintain care. Juvenile survival has relatively little, if any, effect on the origin and maintenance of egg-only care. More generally, our results suggest that the evolution of parental care will be influenced by an organism's entire life history characteristics, the stage at which density dependence acts, and whether care is originating or being maintained.

  8. Density functional theory in surface science and heterogeneous catalysis

    DEFF Research Database (Denmark)

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

    2006-01-01

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

  9. Probability-density-function characterization of multipartite entanglement

    International Nuclear Information System (INIS)

    Facchi, P.; Florio, G.; Pascazio, S.

    2006-01-01

    We propose a method to characterize and quantify multipartite entanglement for pure states. The method hinges upon the study of the probability density function of bipartite entanglement and is tested on an ensemble of qubits in a variety of situations. This characterization is also compared to several measures of multipartite entanglement

  10. Graph approach to the gradient expansion of density functionals

    International Nuclear Information System (INIS)

    Kozlowski, P.M.; Nalewajski, R.F.

    1986-01-01

    A graph representation of terms in the gradient expansion of the kinetic energy density functional is presented. They briefly discuss the implications of the virial theorem for the graph structure and relations between possible graphs at a given order of expansion

  11. Applications of Density Functional Theory in Soft Condensed Matter

    Science.gov (United States)

    Löwen, Hartmut

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

  12. A density functional study on the adsorption of hydrogen molecule

    Indian Academy of Sciences (India)

    An all-electron scalar relativistic calculation on the adsorption of hydrogen molecule onto small copper clusters has been performed by using density functional theory with the generalized gradient approximation (GGA) at PW91 level. Our results reveal that after adsorption of H2 molecule, the Cu-Cu interaction is ...

  13. A density functional theory-based chemical potential equalisation

    Indian Academy of Sciences (India)

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

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

    Indian Academy of Sciences (India)

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

  15. Energy density functional analysis of shape coexistence in 44S

    International Nuclear Information System (INIS)

    Li, Z. P.; Yao, J. M.; Vretenar, D.; Nikšić, T.; Meng, J.

    2012-01-01

    The structure of low-energy collective states in the neutron-rich nucleus 44 S is analyzed using a microscopic collective Hamiltonian model based on energy density functionals (EDFs). The calculated triaxial energy map, low-energy spectrum and corresponding probability distributions indicate a coexistence of prolate and oblate shapes in this nucleus.

  16. Benchmarking Density Functionals for Chemical Bonds of Gold

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Gold plays a major role in nanochemistry, catalysis, and electrochemistry. Accordingly, hundreds of studies apply density functionals to study chemical bonding with gold, yet there is no systematic attempt to assess the accuracy of these methods applied to gold. This paper reports a benchmark aga...

  17. Density-correlation functions in Calogero-Sutherland models

    International Nuclear Information System (INIS)

    Minahan, J.A.; Polychronakos, A.P.

    1994-01-01

    Using arguments from two-dimensional Yang-Mills theory and the collective coordinate formulation of the Calogero-Sutherland model, we conjecture the dynamical density-correlation function for coupling l and 1/l, where l is an integer. We present overwhelming evidence that the conjecture is indeed correct

  18. Density correlation functions in Calogero-Sutherland models

    CERN Document Server

    Minahan, Joseph A.; Joseph A Minahan; Alexios P Polychronakos

    1994-01-01

    Using arguments from two dimensional Yang-Mills theory and the collective coordinate formulation of the Calogero-Sutherland model, we conjecture the dynamical density correlation function for coupling l and 1/l, where l is an integer. We present overwhelming evidence that the conjecture is indeed correct.

  19. Basic concepts of Density Functional Theory: Electronic structure calculation

    International Nuclear Information System (INIS)

    Sharma, B. Indrajit

    2016-01-01

    We are looking for a material which possesses the required properties as demanded for technological applications. For this we have to repeat the preparation of the appropriate materials and its characterizations. So, before proceeding to experiments, one can study on computer generated structure and predict the properties of the desired material. To do this, a concept of Density Functional Theory comes out. (paper)

  20. Density-functional theory of atoms and molecules

    CERN Document Server

    Parr, Robert G

    1995-01-01

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

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

    Science.gov (United States)

    Kvaal, Simen; Helgaker, Trygve

    2015-11-14

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

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

    Science.gov (United States)

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

    2009-11-01

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

  3. Local thermodynamic mapping for effective liquid density-functional theory

    Science.gov (United States)

    Kyrlidis, Agathagelos; Brown, Robert A.

    1992-01-01

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

  4. How important is self-consistency for the dDsC density dependent dispersion correction?

    Energy Technology Data Exchange (ETDEWEB)

    Brémond, Éric; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch [Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Golubev, Nikolay [Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Steinmann, Stephan N., E-mail: sns25@duke.edu [Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States)

    2014-05-14

    The treatment of dispersion interactions is ubiquitous but computationally demanding for seamless ab initio approaches. A highly popular and simple remedy consists in correcting for the missing interactions a posteriori by adding an attractive energy term summed over all atom pairs to standard density functional approximations. These corrections were originally based on atom pairwise parameters and, hence, had a strong touch of empiricism. To overcome such limitations, we recently proposed a robust system-dependent dispersion correction, dDsC, that is computed from the electron density and that provides a balanced description of both weak inter- and intramolecular interactions. From the theoretical point of view and for the sake of increasing reliability, we here verify if the self-consistent implementation of dDsC impacts ground-state properties such as interaction energies, electron density, dipole moments, geometries, and harmonic frequencies. In addition, we investigate the suitability of the a posteriori scheme for molecular dynamics simulations, for which the analysis of the energy conservation constitutes a challenging tests. Our study demonstrates that the post-SCF approach in an excellent approximation.

  5. Density functional study of condensation in capped capillaries.

    Science.gov (United States)

    Yatsyshin, P; Savva, N; Kalliadasis, S

    2015-07-15

    We study liquid adsorption in narrow rectangular capped capillaries formed by capping two parallel planar walls (a slit pore) with a third wall orthogonal to the two planar walls. The most important transition in confined fluids is arguably condensation, where the pore becomes filled with the liquid phase which is metastable in the bulk. Depending on the temperature T, the condensation in capped capillaries can be first-order (at T≤Tcw) or continuous (at T>Tcw), where Tcw is the capillary wetting temperature. At T>Tcw, the capping wall can adsorb mesoscopic amounts of metastable under-condensed liquid. The onset of condensation is then manifested by the continuous unbinding of the interface between the liquid adsorbed on the capping wall and the gas filling the rest of the capillary volume. In wide capped capillaries there may be a remnant of wedge filling transition, which is manifested by the adsorption of liquid drops in the corners. Our classical statistical mechanical treatment predicts a possibility of three-phase coexistence between gas, corner drops and liquid slabs adsorbed on the capping wall. In sufficiently wide capillaries we find that thick prewetting films of finite length may be nucleated at the capping wall below the boundary of the prewetting transition. Prewetting then proceeds in a continuous manner manifested by the unbinding interface between the thick and thin films adsorbed on the side walls. Our analysis is based on a detailed numerical investigation of the density functional theory for the fluid equilibria for a number of illustrative case studies.

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

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2010-01-01

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

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

    Science.gov (United States)

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

    2017-07-06

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

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

    DEFF Research Database (Denmark)

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

    2007-01-01

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

  9. 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.

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

    Science.gov (United States)

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

    2017-09-07

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

  11. Stochastic chaos induced by diffusion processes with identical spectral density but different probability density functions.

    Science.gov (United States)

    Lei, Youming; Zheng, Fan

    2016-12-01

    Stochastic chaos induced by diffusion processes, with identical spectral density but different probability density functions (PDFs), is investigated in selected lightly damped Hamiltonian systems. The threshold amplitude of diffusion processes for the onset of chaos is derived by using the stochastic Melnikov method together with a mean-square criterion. Two quasi-Hamiltonian systems, namely, a damped single pendulum and damped Duffing oscillator perturbed by stochastic excitations, are used as illustrative examples. Four different cases of stochastic processes are taking as the driving excitations. It is shown that in such two systems the spectral density of diffusion processes completely determines the threshold amplitude for chaos, regardless of the shape of their PDFs, Gaussian or otherwise. Furthermore, the mean top Lyapunov exponent is employed to verify analytical results. The results obtained by numerical simulations are in accordance with the analytical results. This demonstrates that the stochastic Melnikov method is effective in predicting the onset of chaos in the quasi-Hamiltonian systems.

  12. An exponential scaling law for the strain dependence of the Nb3Sn critical current density

    International Nuclear Information System (INIS)

    Bordini, B; Alknes, P; Bottura, L; Rossi, L; Valentinis, D

    2013-01-01

    The critical current density of the Nb 3 Sn superconductor is strongly dependent on the strain applied to the material. In order to investigate this dependence, it is a common practice to measure the critical current of Nb 3 Sn strands for different values of applied axial strain. In the literature, several models have been proposed to describe these experimental data in the reversible strain region. All these models are capable of fitting the measurement results in the strain region where data are collected, but tend to predict unphysical trends outside the range of data, and especially for large strain values. In this paper we present a model of a new strain function, together with the results obtained by applying the new scaling law on relevant datasets. The data analyzed consisted of the critical current measurements at 4.2 K that were carried out under applied axial strain at Durham University and the University of Geneva on different strand types. With respect to the previous models proposed, the new scaling function does not present problems at large strain values, has a lower number of fitting parameters (only two instead of three or four), and is very stable, so that, starting from few experimental points, it can estimate quite accurately the strand behavior in a strain region where there are no data. A relationship is shown between the proposed strain function and the elastic strain energy, and an analogy is drawn with the exponential form of the McMillan equation for the critical temperature. (paper)

  13. Recent advances in density functional methods, pt. 1-2

    CERN Document Server

    Chong, Delano P

    1995-01-01

    Of all the different areas in computational chemistry, density functional theory (DFT) enjoys the most rapid development. Even at the level of the local density approximation (LDA), which is computationally less demanding, DFT can usually provide better answers than Hartree-Fock formalism for large systems such as clusters and solids. For atoms and molecules, the results from DFT often rival those obtained by ab initio quantum chemistry, partly because larger basis sets can be used. Such encouraging results have in turn stimulated workers to further investigate the formal theory as well as the

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

    Science.gov (United States)

    Hsu, J Y

    2003-09-26

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

  15. Ab initio derivation of model energy density functionals

    International Nuclear Information System (INIS)

    Dobaczewski, Jacek

    2016-01-01

    I propose a simple and manageable method that allows for deriving coupling constants of model energy density functionals (EDFs) directly from ab initio calculations performed for finite fermion systems. A proof-of-principle application allows for linking properties of finite nuclei, determined by using the nuclear nonlocal Gogny functional, to the coupling constants of the quasilocal Skyrme functional. The method does not rely on properties of infinite fermion systems but on the ab initio calculations in finite systems. It also allows for quantifying merits of different model EDFs in describing the ab initio results. (letter)

  16. Time-dependent quantum many-body systems. Linear response, electronic transport, and reduced density matrices

    International Nuclear Information System (INIS)

    Appel, H.

    2007-05-01

    In part I of this work we present a double-pole approximation (DPA) to the response equations of time-dependent density functional theory (TDDFT). The double-pole approximation provides an exact description of systems with two strongly coupled excitations which are isolated from the rest of the spectrum. In contrast to the traditional single-pole approximation of TDDFT the DPA also yields corrections to the Kohn-Sham oscillator strengths. We also demonstrate how to invert the double-pole solution which allows us to predict matrix elements of the exchange-correlation kernel f xc from experimental input. We attempt some first steps towards a time-dependent generalization of reduced density matrix functional theory (RDMFT). In part II we derive equations of motion for natural orbitals and occupation numbers. Using the equation of motion for the occupation numbers we show that an adiabatic extension of presently known ground-state functionals of static RDMFT always leads to occupation numbers which are constant in time. From the stationary conditions of the equations of motion for the N-body correlations (correlated parts of the N-body matrices) we derive a new class of ground-state functionals which can be used in static RDMFT. Applications are presented for a one-dimensional model system where the time-dependent many-body Schroedinger equation can be propagated numerically. We use optimal control theory to find optimized laser pulses for transitions in a model for atomic Helium. From the numerically exact correlated wavefunction we extract the exact time evolution of natural orbitals and occupation numbers for (i) laser-driven Helium and (ii) electron-ion scattering. Part III of this work considers time-dependent quantum transport within TDDFT. We present an algorithm for the calculation of extended eigenstates of single-particle Hamiltonians which is especially tailored to a finite-difference discretization of the Schroedinger equation. We consider the propagation

  17. Time-dependent quantum many-body systems. Linear response, electronic transport, and reduced density matrices

    Energy Technology Data Exchange (ETDEWEB)

    Appel, H.

    2007-05-15

    In part I of this work we present a double-pole approximation (DPA) to the response equations of time-dependent density functional theory (TDDFT). The double-pole approximation provides an exact description of systems with two strongly coupled excitations which are isolated from the rest of the spectrum. In contrast to the traditional single-pole approximation of TDDFT the DPA also yields corrections to the Kohn-Sham oscillator strengths. We also demonstrate how to invert the double-pole solution which allows us to predict matrix elements of the exchange-correlation kernel f{sub xc} from experimental input. We attempt some first steps towards a time-dependent generalization of reduced density matrix functional theory (RDMFT). In part II we derive equations of motion for natural orbitals and occupation numbers. Using the equation of motion for the occupation numbers we show that an adiabatic extension of presently known ground-state functionals of static RDMFT always leads to occupation numbers which are constant in time. From the stationary conditions of the equations of motion for the N-body correlations (correlated parts of the N-body matrices) we derive a new class of ground-state functionals which can be used in static RDMFT. Applications are presented for a one-dimensional model system where the time-dependent many-body Schroedinger equation can be propagated numerically. We use optimal control theory to find optimized laser pulses for transitions in a model for atomic Helium. From the numerically exact correlated wavefunction we extract the exact time evolution of natural orbitals and occupation numbers for (i) laser-driven Helium and (ii) electron-ion scattering. Part III of this work considers time-dependent quantum transport within TDDFT. We present an algorithm for the calculation of extended eigenstates of single-particle Hamiltonians which is especially tailored to a finite-difference discretization of the Schroedinger equation. We consider the

  18. Covariant Density Functionals: time-odd channel investigated

    International Nuclear Information System (INIS)

    Afanasjev, A. V.; Abusara, H.

    2009-01-01

    The description of exotic nuclear systems and phenomena requires a detailed understanding of all channels of density functional theories. The role of time-odd mean fields, their evidence in experiment, and an accurate description of these fields are subject of current interest. Recent studies advanced the understanding of these fields in energy density functional theories based on the Skyrme force [1,2]. Time-odd mean fields are related to nuclear magnetism in covariant density functional (CDF) theories [3]. They arise from space-like components of vector mesons and Lorentz invariance requires that their coupling strengths are identical to that of time-like components. There were only few limited efforts to understand the role of time-odd mean fields in covariant density functional theory [4,5]. For example, the microscopic role of nuclear magnetism and its impact on rotational properties of nuclei has been studied in Ref. [5]. It is known that time-odd mean fields modify the angular momentum content of the single-particle orbitals and thus the moments of inertia, effective alignments, alignment gains at the band crossings and other physical observables. We aim on more detailed and systematic understanding of the role of time-odd mean fields in covariant density functional theory. This investigation covers both rotating and non-rotating systems. It is shown that contrary to the Skyrme energy density functionals time-odd mean fields of CDF theory always provide additional binding in the systems with broken time-reversal symmetry (rotating nuclei, odd mass nuclei). This additional binding increases with spin and has its maximum exactly at the terminating state [6], where it can reach several MeV. The impact of time-odd mean fields on the properties of rotating systems has been studied in a systematic way (as a function of particle number and deformation) across the nuclear chart [7]. In addition, this contribution extends these studies to non-rotating systems such as

  19. Density-dependent electron scattering in photoexcited GaAs in strongly diffusive regime

    DEFF Research Database (Denmark)

    Mics, Zoltán; D’Angio, Andrea; Jensen, Søren A.

    2013-01-01

    In a series of systematic optical pump–terahertz probe experiments, we study the density-dependent electron scattering rate in photoexcited GaAs in the regime of strong carrier diffusion. The terahertz frequency-resolved transient sheet conductivity spectra are perfectly described by the Drude...... model, directly yielding the electron scattering rates. A diffusion model is applied to determine the spatial extent of the photoexcited electron-hole gas at each moment after photoexcitation, yielding the time-dependent electron density, and hence the density-dependent electron scattering time. We find...

  20. General framework for fluctuating dynamic density functional theory

    Science.gov (United States)

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

    2017-12-01

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

  1. Experimental evidence that density dependence strongly influences plant invasions through fragmented landscapes.

    Science.gov (United States)

    Williams, Jennifer L; Levine, Jonathan M

    2018-04-01

    Populations of range expanding species encounter patches of both favorable and unfavorable habitat as they spread across landscapes. Theory shows that increasing patchiness slows the spread of populations modeled with continuously varying population density when dispersal is not influence by the environment or individual behavior. However, as is found in uniformly favorable landscapes, spread remains driven by fecundity and dispersal from low density individuals at the invasion front. In contrast, when modeled populations are composed of discrete individuals, patchiness causes populations to build up to high density before dispersing past unsuitable habitat, introducing an important influence of density dependence on spread velocity. To test the hypothesized interaction between habitat patchiness and density dependence, we simultaneously manipulated these factors in a greenhouse system of annual plants spreading through replicated experimental landscapes. We found that increasing the size of gaps and amplifying the strength of density dependence both slowed spread velocity, but contrary to predictions, the effect of amplified density dependence was similar across all landscape types. Our results demonstrate that the discrete nature of individuals in spreading populations has a strong influence on how both landscape patchiness and density dependence influence spread through demographic and dispersal stochasticity. Both finiteness and landscape structure should be critical components to theoretical predictions of future spread for range expanding native species or invasive species colonizing new habitat. © 2018 by the Ecological Society of America.

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

    Science.gov (United States)

    Husowitz, B; Talanquer, V

    2007-02-07

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

  3. Functional approach for pairing in finite systems: How to define restoration of broken symmetries in Energy Density Functional theory?

    International Nuclear Information System (INIS)

    Hupin, G; Lacroix, D; Bender, M

    2011-01-01

    The Multi-Reference Energy Density Functional (MR-EDF) approach (also called configuration mixing or Generator Coordinate Method), that is commonly used to treat pairing in finite nuclei and project onto particle number, is re-analyzed. It is shown that, under certain conditions, the MR-EDF energy can be interpreted as a functional of the one-body density matrix of the projected state with good particle number. Based on this observation, we propose a new approach, called Symmetry-Conserving EDF (SC-EDF), where the breaking and restoration of symmetry are accounted for simultaneously. We show, that such an approach is free from pathologies recently observed in MR-EDF and can be used with a large flexibility on the density dependence of the functional.

  4. THE TURBULENCE SPECTRUM OF MOLECULAR CLOUDS IN THE GALACTIC RING SURVEY: A DENSITY-DEPENDENT PRINCIPAL COMPONENT ANALYSIS CALIBRATION

    International Nuclear Information System (INIS)

    Roman-Duval, Julia; Jackson, James; Federrath, Christoph; Klessen, Ralf S.; Brunt, Christopher; Heyer, Mark

    2011-01-01

    Turbulence plays a major role in the formation and evolution of molecular clouds. Observationally, turbulent velocities are convolved with the density of an observed region. To correct for this convolution, we investigate the relation between the turbulence spectrum of model clouds, and the statistics of their synthetic observations obtained from principal component analysis (PCA). We apply PCA to spectral maps generated from simulated density and velocity fields, obtained from hydrodynamic simulations of supersonic turbulence, and from fractional Brownian motion (fBm) fields with varying velocity, density spectra, and density dispersion. We examine the dependence of the slope of the PCA pseudo-structure function, α PCA , on intermittency, on the turbulence velocity (β v ) and density (β n ) spectral indexes, and on density dispersion. We find that PCA is insensitive to β n and to the log-density dispersion σ s , provided σ s ≤ 2. For σ s > 2, α PCA increases with σ s due to the intermittent sampling of the velocity field by the density field. The PCA calibration also depends on intermittency. We derive a PCA calibration based on fBm structures with σ s ≤ 2 and apply it to 367 13 CO spectral maps of molecular clouds in the Galactic Ring Survey. The average slope of the PCA structure function, (α PCA ) = 0.62 ± 0.2, is consistent with the hydrodynamic simulations and leads to a turbulence velocity exponent of (β v ) = 2.06 ± 0.6 for a non-intermittent, low density dispersion flow. Accounting for intermittency and density dispersion, the coincidence between the PCA slope of the GRS clouds and the hydrodynamic simulations suggests β v ≅ 1.9, consistent with both Burgers and compressible intermittent turbulence.

  5. Computational Benchmarking for Ultrafast Electron Dynamics: Wave Function Methods vs Density Functional Theory.

    Science.gov (United States)

    Oliveira, Micael J T; Mignolet, Benoit; Kus, Tomasz; Papadopoulos, Theodoros A; Remacle, F; Verstraete, Matthieu J

    2015-05-12

    Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrödinger equation based on the correlated field-free stationary electronic states computed with the equationof-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TDDFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.

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

    Science.gov (United States)

    Kaiser, N.; Weise, W.

    2010-05-01

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

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

    Science.gov (United States)

    Yu, Kuang; Carter, Emily A

    2017-12-19

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

  8. Density functional approach for pairing in finite size systems

    International Nuclear Information System (INIS)

    Hupin, G.

    2011-09-01

    The combination of functional theory where the energy is written as a functional of the density, and the configuration mixing method, provides an efficient description of nuclear ground and excited state properties. The specific pathologies that have been recently observed, show the lack of a clear underlying justification associated to the breaking and the restoration of symmetries within density functional theory. This thesis focuses on alternative treatments of pairing correlations in finite many body systems that consider the breaking and the restoration of the particle number conservation. The energy is written as a functional of a projected quasi-particle vacuum and can be linked to the one obtained within the configuration mixing framework. This approach has been applied to make the projection either before or after the application of the variational principle. It is more flexible than the usual configuration mixing method since it can handle more general effective interactions than the latter. The application to the Krypton isotopes shows the feasibility and the efficiency of the method to describe pairing near closed shell nuclei. Following a parallel path, a theory where the energy is written as a functional of the occupation number and natural orbitals is proposed. The new functional is benchmarked in an exactly solvable model, the pairing Hamiltonian. The efficiency and the applicability of the new theory have been tested for various pairing strengths, single particle energy spectra and numbers of particles. (author)

  9. Performance of exchange-correlation functionals in density functional theory calculations for liquid metal: A benchmark test for sodium

    Science.gov (United States)

    Han, Jeong-Hwan; Oda, Takuji

    2018-04-01

    The performance of exchange-correlation functionals in density-functional theory (DFT) calculations for liquid metal has not been sufficiently examined. In the present study, benchmark tests of Perdew-Burke-Ernzerhof (PBE), Armiento-Mattsson 2005 (AM05), PBE re-parameterized for solids, and local density approximation (LDA) functionals are conducted for liquid sodium. The pair correlation function, equilibrium atomic volume, bulk modulus, and relative enthalpy are evaluated at 600 K and 1000 K. Compared with the available experimental data, the errors range from -11.2% to 0.0% for the atomic volume, from -5.2% to 22.0% for the bulk modulus, and from -3.5% to 2.5% for the relative enthalpy depending on the DFT functional. The generalized gradient approximation functionals are superior to the LDA functional, and the PBE and AM05 functionals exhibit the best performance. In addition, we assess whether the error tendency in liquid simulations is comparable to that in solid simulations, which would suggest that the atomic volume and relative enthalpy performances are comparable between solid and liquid states but that the bulk modulus performance is not. These benchmark test results indicate that the results of liquid simulations are significantly dependent on the exchange-correlation functional and that the DFT functional performance in solid simulations can be used to roughly estimate the performance in liquid simulations.

  10. Intraspecific density dependence and a guild of consumers coexisting on one resource.

    Science.gov (United States)

    McPeek, Mark A

    2012-12-01

    The importance of negative intraspecific density dependence to promoting species coexistence in a community is well accepted. However, such mechanisms are typically omitted from more explicit models of community dynamics. Here I analyze a variation of the Rosenzweig-MacArthur consumer-resource model that includes negative intraspecific density dependence for consumers to explore its effect on the coexistence of multiple consumers feeding on a single resource. This analysis demonstrates that a guild of multiple consumers can easily coexist on a single resource if each limits its own abundance to some degree, and stronger intraspecific density dependence permits a wider variety of consumers to coexist. The mechanism permitting multiple consumers to coexist works in a fashion similar to apparent competition or to each consumer having its own specialized predator. These results argue for a more explicit emphasis on how negative intraspecific density dependence is generated and how these mechanisms combine with species interactions to shape overall community structure.

  11. 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.

  12. Analyzing the financial crisis using the entropy density function

    Science.gov (United States)

    Oh, Gabjin; Kim, Ho-yong; Ahn, Seok-Won; Kwak, Wooseop

    2015-02-01

    The risk that is created by nonlinear interactions among subjects in economic systems is assumed to increase during an abnormal state of a financial market. Nevertheless, investigating the systemic risk in financial markets following the global financial crisis is not sufficient. In this paper, we analyze the entropy density function in the return time series for several financial markets, such as the S&P500, KOSPI, and DAX indices, from October 2002 to December 2011 and analyze the variability in the entropy value over time. We find that the entropy density function of the S&P500 index during the subprime crisis exhibits a significant decrease compared to that in other periods, whereas the other markets, such as those in Germany and Korea, exhibit no significant decrease during the market crisis. These findings demonstrate that the S&P500 index generated a regular pattern in the return time series during the financial crisis.

  13. Modeling of nanoscale liquid mixture transport by density functional hydrodynamics

    Science.gov (United States)

    Dinariev, Oleg Yu.; Evseev, Nikolay V.

    2017-06-01

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

  14. A J matrix engine for density functional theory calculations

    International Nuclear Information System (INIS)

    White, C.A.; Head-Gordon, M.

    1996-01-01

    We introduce a new method for the formation of the J matrix (Coulomb interaction matrix) within a basis of Cartesian Gaussian functions, as needed in density functional theory and Hartree endash Fock calculations. By summing the density matrix into the underlying Gaussian integral formulas, we have developed a J matrix open-quote open-quote engine close-quote close-quote which forms the exact J matrix without explicitly forming the full set of two electron integral intermediates. Several precomputable quantities have been identified, substantially reducing the number of floating point operations and memory accesses needed in a J matrix calculation. Initial timings indicate a speedup of greater than four times for the (pp parallel pp) class of integrals with speedups increasing to over ten times for (ff parallel ff) integrals. copyright 1996 American Institute of Physics

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  16. Density functional application to strongly correlated electron systems

    International Nuclear Information System (INIS)

    Eschrig, H.; Koepernik, K.; Chaplygin, I.

    2003-01-01

    The local spin density approximation plus onsite Coulomb repulsion approach (LSDA+U) to density functional theory is carefully reanalyzed. Its possible link to single-particle Green's function theory is occasionally discussed. A simple and elegant derivation of the important sum rules for the on-site interaction matrix elements linking them to the values of U and J is presented. All necessary expressions for an implementation of LSDA+U into a non-orthogonal basis solver for the Kohn-Sham equations are given, and implementation into the full-potential local-orbital solver (Phys. Rev. B 59 (1999) 1743) is made. Results of application to several planar cuprate structures are reported in detail and conclusions on the interpretation of the physics of the electronic structure of the cuprates are drawn

  17. Self-consistent RPA and the time-dependent density matrix approach

    Energy Technology Data Exchange (ETDEWEB)

    Schuck, P. [Institut de Physique Nucleaire, Orsay (France); CNRS et Universite Joseph Fourier, Laboratoire de Physique et Modelisation des Milieux Condenses, Grenoble (France); Tohyama, M. [Kyorin University School of Medicine, Mitaka, Tokyo (Japan)

    2016-10-15

    The time-dependent density matrix (TDDM) or BBGKY (Bogoliubov, Born, Green, Kirkwood, Yvon) approach is decoupled and closed at the three-body level in finding a natural representation of the latter in terms of a quadratic form of two-body correlation functions. In the small amplitude limit an extended RPA coupled to an also extended second RPA is obtained. Since including two-body correlations means that the ground state cannot be a Hartree-Fock state, naturally the corresponding RPA is upgraded to Self-Consistent RPA (SCRPA) which was introduced independently earlier and which is built on a correlated ground state. SCRPA conserves all the properties of standard RPA. Applications to the exactly solvable Lipkin and the 1D Hubbard models show good performances of SCRPA and TDDM. (orig.)

  18. Explaining density-dependent regulation in earthworm populations using life-history analysis

    NARCIS (Netherlands)

    Kammenga, J.E.; Spurgeon, D.J.; Svendsen, C.; Weeks, J.M.

    2003-01-01

    At present there is little knowledge about how density regulates population growth rate and to what extent this is determined by life-history patterns. We compared density dependent population consequences in the Nicholsonian sense based oil experimental observations and life-history modeling for

  19. Magnetic field dependence of the critical current density in YBa2Cu3Ox ceramics

    International Nuclear Information System (INIS)

    Zhukov, A.A.; Moshchalkov, V.V.; Komarkov, D.A.; Shabatin, V.P.; Gordeev, S.N.; Shelomov, D.V.

    1989-01-01

    Three magnetic field ranges corresponding to different critical current density j c behavior have been found out. They correlate with grain magnetization changes. The inverse critical current density is shown to depend linearly on the sample cross-section due to the magnetic field induced by the flowing current

  20. Experimental investigation of statistical density function of decaying radioactive sources

    International Nuclear Information System (INIS)

    Salma, I.; Zemplen-Papp, E.

    1991-01-01

    The validity of the Poisson and the λ P(k) modified Poisson statistical density functions of observing k events in a short time interval is investigated experimentally in radioactive decay detection for various measuring times. The experiments to measure radioactive decay were performed with 89m Y, using a multichannel analyzer. According to the results, Poisson statistics adequately describes the counting experiment for short measuring times. (author) 13 refs.; 4 figs