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

International Nuclear Information System (INIS)

Magyar, R.J.; Burke, K.

2004-01-01

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

Nonperturbative perturbation theory

International Nuclear Information System (INIS)

Bender, C.M.

1989-01-01

In this talk we describe a recently proposed graphical perturbative calculational scheme for quantum field theory. The basic idea is to expand in the power of the interaction term. For example, to solve a λφ 4 theory in d-dimensional space-time, we introduce a small parameter δ and consider a λ(φ 2 ) 1+δ field theory. We show how to expand such a theory as a series in powers of δ. The resulting perturbation series appears to have a finite radius of convergence and numerical results for low-dimensional models are good. We have computed the two-point and four-point Green's functions to second order in powers of δ and the 2n-point Green's functions (n>2) to order δ. We explain how to renormalize the theory and show that, to first order in powers of δ, when δ>0 and d≥4 the theory is free. This conclusion remains valid to second order in powers of δ, and we believe that it remains valid to all orders in powers of δ. The new perturbative scheme is consistent with global supersymmetry invariance. We examine a two-dimensional supersymmetric quantum field theory in which we do not know of any other means for doing analytical calculations. We illustrate the power of this new technique by computing the ground-state energy density E to second order in this new perturbation theory. We show that there is a beautiful and delicate cancellation between infinite classes of graphs which leads to the result that E=0. (orig.)

Current Density and Plasma Displacement Near Perturbed Rational Surface

International Nuclear Information System (INIS)

Boozer, A.H.; Pomphrey, N.

2010-01-01

The current density in the vicinity of a rational surface of a force-free magnetic field subjected to an ideal perturbation is shown to be the sum of both a smooth and a delta-function distribution, which give comparable currents. The maximum perturbation to the smooth current density is comparable to a typical equilibrium current density and the width of the layer in which the current flows is shown to be proportional to the perturbation amplitude. In the standard linearized theory, the plasma displacement has an unphysical jump across the rational surface, but the full theory gives a continuous displacement.

Divergence of perturbation theory in large scale structures

Science.gov (United States)

Pajer, Enrico; van der Woude, Drian

2018-05-01

We make progress towards an analytical understanding of the regime of validity of perturbation theory for large scale structures and the nature of some non-perturbative corrections. We restrict ourselves to 1D gravitational collapse, for which exact solutions before shell crossing are known. We review the convergence of perturbation theory for the power spectrum, recently proven by McQuinn and White [1], and extend it to non-Gaussian initial conditions and the bispectrum. In contrast, we prove that perturbation theory diverges for the real space two-point correlation function and for the probability density function (PDF) of the density averaged in cells and all the cumulants derived from it. We attribute these divergences to the statistical averaging intrinsic to cosmological observables, which, even on very large and "perturbative" scales, gives non-vanishing weight to all extreme fluctuations. Finally, we discuss some general properties of non-perturbative effects in real space and Fourier space.

Second-order perturbation theory with a density matrix renormalization group self-consistent field reference function: theory and application to the study of chromium dimer.

Science.gov (United States)

Kurashige, Yuki; Yanai, Takeshi

2011-09-07

We present a second-order perturbation theory based on a density matrix renormalization group self-consistent field (DMRG-SCF) reference function. The method reproduces the solution of the complete active space with second-order perturbation theory (CASPT2) when the DMRG reference function is represented by a sufficiently large number of renormalized many-body basis, thereby being named DMRG-CASPT2 method. The DMRG-SCF is able to describe non-dynamical correlation with large active space that is insurmountable to the conventional CASSCF method, while the second-order perturbation theory provides an efficient description of dynamical correlation effects. The capability of our implementation is demonstrated for an application to the potential energy curve of the chromium dimer, which is one of the most demanding multireference systems that require best electronic structure treatment for non-dynamical and dynamical correlation as well as large basis sets. The DMRG-CASPT2/cc-pwCV5Z calculations were performed with a large (3d double-shell) active space consisting of 28 orbitals. Our approach using large-size DMRG reference addressed the problems of why the dissociation energy is largely overestimated by CASPT2 with the small active space consisting of 12 orbitals (3d4s), and also is oversensitive to the choice of the zeroth-order Hamiltonian. © 2011 American Institute of Physics

Effect of Interface Structure on Thermal Boundary Conductance by using First-principles Density Functional Perturbation Theory

Institute of Scientific and Technical Information of China (English)

GAO Xue; ZHANG Yue; SHANG Jia-Xiang

2011-01-01

We choose a Si/Ge interface as a research object to investigate the infiuence of interface disorder on thermal boundary conductance. In the calculations, the diffuse mismatch model is used to study thermal boundary conductance between two non-metallic materials, while the phonon dispersion relationship is calculated by the first-principles density functional perturbation theory. The results show that interface disorder limits thermal transport. The increase of atomic spacing at the interface results in weakly coupled interfaces and a decrease in the thermal boundary conductance. This approach shows a simplistic method to investigate the relationship between microstructure and thermal conductivity.%We choose a Si/Ge interface as a research object to investigate the influence of interface disorder on thermal boundary conductance.In the calculations,the diffuse mismatch model is used to study thermal boundary conductance between two non-metallic materials,while the phonon dispersion relationship is calculated by the first-principles density functional perturbation theory.The results show that interface disorder limits thermal transport.The increase of atomic spacing at the interface results in weakly coupled interfaces and a decrease in the thermal boundary conductance.This approach shows a simplistic method to investigate the relationship between microstructure and thermal conductivity.It is well known that interfaces can play a dominant role in the overall thermal transport characteristics of structures whose length scale is less than the phonon mean free path.When heat flows across an interface between two different materials,there exists a temperature jump at the interface.Thermal boundary conductance (TBC),which describes the efficiency of heat flow at material interfaces,plays an importance role in the transport of thermal energy in nanometerscale devices,semiconductor superlattices,thin film multilayers and nanocrystalline materials.[1

Statistics of Smoothed Cosmic Fields in Perturbation Theory. I. Formulation and Useful Formulae in Second-Order Perturbation Theory

Science.gov (United States)

Matsubara, Takahiko

2003-02-01

We formulate a general method for perturbative evaluations of statistics of smoothed cosmic fields and provide useful formulae for application of the perturbation theory to various statistics. This formalism is an extensive generalization of the method used by Matsubara, who derived a weakly nonlinear formula of the genus statistic in a three-dimensional density field. After describing the general method, we apply the formalism to a series of statistics, including genus statistics, level-crossing statistics, Minkowski functionals, and a density extrema statistic, regardless of the dimensions in which each statistic is defined. The relation between the Minkowski functionals and other geometrical statistics is clarified. These statistics can be applied to several cosmic fields, including three-dimensional density field, three-dimensional velocity field, two-dimensional projected density field, and so forth. The results are detailed for second-order theory of the formalism. The effect of the bias is discussed. The statistics of smoothed cosmic fields as functions of rescaled threshold by volume fraction are discussed in the framework of second-order perturbation theory. In CDM-like models, their functional deviations from linear predictions plotted against the rescaled threshold are generally much smaller than that plotted against the direct threshold. There is still a slight meatball shift against rescaled threshold, which is characterized by asymmetry in depths of troughs in the genus curve. A theory-motivated asymmetry factor in the genus curve is proposed.

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

International Nuclear Information System (INIS)

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

2003-01-01

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

Numerical stochastic perturbation theory in the Schroedinger functional

International Nuclear Information System (INIS)

Brambilla, Michele; Di Renzo, Francesco; Hesse, Dirk; Dalla Brida, Mattia; Sint, Stefan; Deutsches Elektronen-Synchrotron

2013-11-01

The Schroedinger functional (SF) is a powerful and widely used tool for the treatment of a variety of problems in renormalization and related areas. Albeit offering many conceptual advantages, one major downside of the SF scheme is the fact that perturbative calculations quickly become cumbersome with the inclusion of higher orders in the gauge coupling and hence the use of an automated perturbation theory framework is desirable. We present the implementation of the SF in numerical stochastic perturbation theory (NSPT) and compare first results for the running coupling at two loops in pure SU(3) Yang-Mills theory with the literature.

Numerical stochastic perturbation theory in the Schroedinger functional

Energy Technology Data Exchange (ETDEWEB)

Brambilla, Michele; Di Renzo, Francesco; Hesse, Dirk [Parma Univ. (Italy); INFN, Parma (Italy); Dalla Brida, Mattia [Trinity College Dublin (Ireland). School of Mathematics; Sint, Stefan [Trinity College Dublin (Ireland). School of Mathematics; Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC

2013-11-15

The Schroedinger functional (SF) is a powerful and widely used tool for the treatment of a variety of problems in renormalization and related areas. Albeit offering many conceptual advantages, one major downside of the SF scheme is the fact that perturbative calculations quickly become cumbersome with the inclusion of higher orders in the gauge coupling and hence the use of an automated perturbation theory framework is desirable. We present the implementation of the SF in numerical stochastic perturbation theory (NSPT) and compare first results for the running coupling at two loops in pure SU(3) Yang-Mills theory with the literature.

Assessing exchange-correlation functionals for elasticity and thermodynamics of α -ZrW2O8 : A density functional perturbation theory study

Science.gov (United States)

Weck, Philippe F.; Kim, Eunja; Greathouse, Jeffery A.; Gordon, Margaret E.; Bryan, Charles R.

2018-04-01

Elastic and thermodynamic properties of negative thermal expansion (NTE) α -ZrW2O8 have been calculated using PBEsol and PBE exchange-correlation functionals within the framework of density functional perturbation theory (DFPT). Measured elastic constants are reproduced within ∼ 2 % with PBEsol and ∼ 6 % with PBE. The thermal evolution of the Grüneisen parameter computed within the quasi-harmonic approximation exhibits negative values below the Debye temperature, consistent with observation. The standard molar heat capacity is predicted to be CP0 = 192.2 and 193.8 J mol-1K-1 with PBEsol and PBE, respectively. These results suggest superior accuracy of DFPT/PBEsol for studying the lattice dynamics, elasticity and thermodynamics of NTE materials.

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

International Nuclear Information System (INIS)

Anon.

1984-01-01

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

van der Waals forces in density functional theory: Perturbational long-range electron-interaction corrections

International Nuclear Information System (INIS)

Angyan, Janos G.; Gerber, Iann C.; Savin, Andreas; Toulouse, Julien

2005-01-01

Long-range exchange and correlation effects, responsible for the failure of currently used approximate density functionals in describing van der Waals forces, are taken into account explicitly after a separation of the electron-electron interaction in the Hamiltonian into short- and long-range components. We propose a 'range-separated hybrid' functional based on a local density approximation for the short-range exchange-correlation energy, combined with a long-range exact exchange energy. Long-range correlation effects are added by a second-order perturbational treatment. The resulting scheme is general and is particularly well adapted to describe van der Waals complexes, such as rare gas dimers

Perturbation Theory of the Cosmological Log-Density Field

DEFF Research Database (Denmark)

Wang, Xin; Neyrinck, Mark; Szapudi, István

2011-01-01

, motivating an analytic study of it. In this paper, we develop cosmological perturbation theory for the power spectrum of this field. Our formalism is developed in the context of renormalized perturbation theory, which helps to regulate the convergence behavior of the perturbation series, and of the Taylor...

Use of density functional theory orbitals in the GVVPT2 variant of second-order multistate multireference perturbation theory.

Science.gov (United States)

Hoffmann, Mark R; Helgaker, Trygve

2015-03-05

A new variation of the second-order generalized van Vleck perturbation theory (GVVPT2) for molecular electronic structure is suggested. In contrast to the established procedure, in which CASSCF or MCSCF orbitals are first obtained and subsequently used to define a many-electron model (or reference) space, the use of an orbital space obtained from the local density approximation (LDA) variant of density functional theory is considered. Through a final, noniterative diagonalization of an average Fock matrix within orbital subspaces, quasicanonical orbitals that are otherwise indistinguishable from quasicanonical orbitals obtained from a CASSCF or MCSCF calculation are obtained. Consequently, all advantages of the GVVPT2 method are retained, including use of macroconfigurations to define incomplete active spaces and rigorous avoidance of intruder states. The suggested variant is vetted on three well-known model problems: the symmetric stretching of the O-H bonds in water, the dissociation of N2, and the stretching of ground and excited states C2 to more than twice the equilibrium bond length of the ground state. It is observed that the LDA-based GVVPT2 calculations yield good results, of comparable quality to conventional CASSCF-based calculations. This is true even for the C2 model problem, in which the orbital space for each state was defined by the LDA orbitals. These results suggest that GVVPT2 can be applied to much larger problems than previously accessible.

Gauge-invariant cosmological density perturbations

International Nuclear Information System (INIS)

Sasaki, Misao.

1986-06-01

Gauge-invariant formulation of cosmological density perturbation theory is reviewed with special emphasis on its geometrical aspects. Then the gauge-invariant measure of the magnitude of a given perturbation is presented. (author)

Efficient perturbation theory to improve the density matrix renormalization group

Science.gov (United States)

Tirrito, Emanuele; Ran, Shi-Ju; Ferris, Andrew J.; McCulloch, Ian P.; Lewenstein, Maciej

2017-02-01

The density matrix renormalization group (DMRG) is one of the most powerful numerical methods available for many-body systems. It has been applied to solve many physical problems, including the calculation of ground states and dynamical properties. In this work, we develop a perturbation theory of the DMRG (PT-DMRG) to greatly increase its accuracy in an extremely simple and efficient way. Using the canonical matrix product state (MPS) representation for the ground state of the considered system, a set of orthogonal basis functions {| ψi> } is introduced to describe the perturbations to the ground state obtained by the conventional DMRG. The Schmidt numbers of the MPS that are beyond the bond dimension cutoff are used to define these perturbation terms. The perturbed Hamiltonian is then defined as H˜i j= ; its ground state permits us to calculate physical observables with a considerably improved accuracy compared to the original DMRG results. We benchmark the second-order perturbation theory with the help of a one-dimensional Ising chain in a transverse field and the Heisenberg chain, where the precision of the DMRG is shown to be improved O (10 ) times. Furthermore, for moderate L the errors of the DMRG and PT-DMRG both scale linearly with L-1 (with L being the length of the chain). The linear relation between the dimension cutoff of the DMRG and that of the PT-DMRG at the same precision shows a considerable improvement in efficiency, especially for large dimension cutoffs. In the thermodynamic limit we show that the errors of the PT-DMRG scale with √{L-1}. Our work suggests an effective way to define the tangent space of the ground-state MPS, which may shed light on the properties beyond the ground state. This second-order PT-DMRG can be readily generalized to higher orders, as well as applied to models in higher dimensions.

Density functional theory of the electrical double layer: the RFD functional

International Nuclear Information System (INIS)

Gillespie, Dirk; Valisko, Monika; Boda, Dezso

2005-01-01

Density functional theory (DFT) of electrolytes is applied to the electrical double layer under a wide range of conditions. The ions are charged, hard spheres of different size and valence, and the wall creating the double layer is uncharged, weakly charged, and strongly charged. Under all conditions, the density and electrostatic potential profiles calculated using the recently proposed RFD electrostatic functional (Gillespie et al 2002 J. Phys.: Condens. Matter 14 12129; 2003 Phys. Rev. E 68 031503) compare well to Monte Carlo simulations. When the wall is strongly charged, the RFD functional results agree with the results of a simpler perturbative electrostatic DFT, but the two functionals' results qualitatively disagree when the wall is uncharged or weakly charged. The RFD functional reproduces these phenomena of weakly charged double layers. It also reproduces bulk thermodynamic quantities calculated from pair correlation functions

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

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

Using projector augmented-wave (PAW) formalism inside the density-functional perturbation theory; L'utilisation du formalisme PAW en theorie de la fonctionnelle de la densite perturbee

Energy Technology Data Exchange (ETDEWEB)

Audouze, Ch

2006-07-01

In condensed matter physics, ab-initio simulation allows to get macroscopic quantities (for example equations of state) from microscopic ones, as phonon frequencies which characterize the vibration Eigenmodes of the system. Therefore, one can theoretically predict the behavior of the material at very high pressure conditions, which can be out of reach by experiences. Computations of phonon spectrum are obtained thanks to the linear response theory, where the equations of Density Functional Theory (as the Kohn-Sham model) are perturbed around their fundamental state. The linear response functionality is one of the options included in the ABINIT code, which is an open source package developed in particular by a team of the CEA-DAM (DPTA) and the Catholic University of Louvain-la-Neuve (Belgium). Nevertheless, in spite of using pseudopotentials, computations of phonon spectrum are not tractable for heavy chemical elements, even on massively parallel computers. In order to overcome this difficulty, the linear response theory had to be extended to the PAW (Projector Augmented-Waves) formalism. In this CEA report, we first detail the PAW model, giving to it a more mathematical framework. Then we establish the linear response equations within the PAW formalism, up to the third order derivative of the total energy, for an isolated molecular system and for generic perturbations. Lastly, all these results are specified to the particular case of atom displacements and for perturbations associated to the change of an external potential in which the molecule is set. (author)

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

Science.gov (United States)

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

2018-06-01

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

The calculation of isotopic partition function ratios by a perturbation theory technique

International Nuclear Information System (INIS)

Singh, G.; Wolfsberg, M.

1975-01-01

The vibrational Hamiltonian of a molecule in the harmonic approximation, H = (1/2) Σ (g/subi/jp/subi/p/subj/ + f/subi/jq/subi/q/subj/), has been divided into a diagonal part (terms with i=j) and an off-diagonal part (inot-equalj), which is regarded as the perturbation. The vibrational partition function of the molecule is then calculated by Schwinger perturbation theory as the partition function of the unperturbed problem, corresponding to a collection of oscillators with frequencies 2πν/subi/' = (f/subi/ig/subi/i)/sup 1 / 2 /, plus perturbation correction terms which are calculated to second order. With the usual assumptions of isotope effect calculations that the molecular translations and rotations are classical and separable from the vibrations, the perturbation formulation of the vibrational partition function is easily transformed into a perturbation theory formulation of (reduced) isotopic partition function ratios. If, for example, the molecular potential function is expressed in terms of the displacements of bond stretches and bond angle bends from their respective equilibrium values, the unperturbed partition function ratio corresponds to the isotope effect expected for noninteracting bond-stretch and bond-angle-bend oscillators. Detailed comparison is made for a number of molecular systems of perturbation theory calculations of partition functions and isotopic partition function ratios with exact calculations carried out by actually obtaining the normal mode vibrational frequencies of the vibrational Hamiltonian. Good agreement is found. The utility of the perturbation theory formulation resides in the fact that it permits one to look at isotope effects in a very simple manner; some demonstrations are given

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

A density functional perturbative approach for simple fluids: the structure of a nonuniform Lennard-Jones fluid at interfaces

International Nuclear Information System (INIS)

Kim, Soon-Chul; Lee, Song Hi

2004-01-01

A density functional perturbation approximation (DFPT), which is based both on the fundamental-measure theory (FMT) to the hard-sphere repulsion and on the weighted-density approximations (WDAs) to the attractive contribution, has been proposed for studying the structural properties of model fluids with an attractive part of the potential. The advantage of the present theory is the simplicity of the calculation of the weight function due to the attractive contribution. It has been applied to predict the equilibrium particle density distributions and adsorption isotherms of Lennard-Jones fluids at interfaces. The theoretical results show that the present theory describes quite well the adsorption isotherms of a Lennard-Jones ethane in a graphite slit pore as well as the equilibrium particle density distributions of a Lennard-Jones fluid near a planar slit pore

Developments in perturbation theory

International Nuclear Information System (INIS)

Greenspan, E.

1976-01-01

Included are sections dealing with perturbation expressions for reactivity, methods for the calculation of perturbed fluxes, integral transport theory formulations for reactivity, generalized perturbation theory, sensitivity and optimization studies, multigroup calculations of bilinear functionals, and solution of inhomogeneous Boltzmann equations with singular operators

Self-consistent many-body perturbation theory in range-separated density-functional theory

DEFF Research Database (Denmark)

Fromager, Emmanuel; Jensen, Hans Jørgen Aagaard

2008-01-01

effects adequately which, on the other hand, can be described by many-body perturbation theory MBPT. It is therefore of interest to develop a hybrid model which combines the best of both the MBPT and DFT approaches. This can be achieved by splitting the two-electron interaction into long-range and short...

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.

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...

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.

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.

Magnetic exchange couplings from noncollinear perturbation theory: dinuclear CuII complexes.

Science.gov (United States)

Phillips, Jordan J; Peralta, Juan E

2014-08-07

To benchmark the performance of a new method based on noncollinear coupled-perturbed density functional theory [J. Chem. Phys. 138, 174115 (2013)], we calculate the magnetic exchange couplings in a series of triply bridged ferromagnetic dinuclear Cu(II) complexes that have been recently synthesized [Phys. Chem. Chem. Phys. 15, 1966 (2013)]. We find that for any basis-set the couplings from our noncollinear coupled-perturbed methodology are practically identical to those of spin-projected energy-differences when a hybrid density functional approximation is employed. This demonstrates that our methodology properly recovers a Heisenberg description for these systems, and is robust in its predictive power of magnetic couplings. Furthermore, this indicates that the failure of density functional theory to capture the subtle variation of the exchange couplings in these complexes is not simply an artifact of broken-symmetry methods, but rather a fundamental weakness of current approximate density functionals for the description of magnetic couplings.

Assessment of Kohn-Sham density functional theory and Møller-Plesset perturbation theory for ionic liquids.

Science.gov (United States)

Zahn, Stefan; MacFarlane, Douglas R; Izgorodina, Ekaterina I

2013-08-28

We present high-level benchmark calculations of interaction energies of 236 ion pair structures of ionic liquids constituting a new IL-2013 set. 33 different approaches using various basis sets are validated against these benchmark data. Overall, traditional functionals like B3LYP, without an explicit dispersion correction, should be avoided when investigating ionic liquids. We can recommend the third version of Grimme's empirical dispersion correction (DFT-D3) and the LC-BOP functional, as well as most functionals of the Minnesota family of the M0X type. Our results highlight the importance of diffuse basis set functions for the accurate prediction of the IL energetics using any DFT functional. The best combination of reasonable accuracy and reasonable cost was found to be the M06-L functional in combination with the 6-31++G** basis set, producing a remarkable mean absolute deviation of only 4.2 kJ mol(-1) and a maximum deviation of -12.5 kJ mol(-1). Second-order Møller-Plesset perturbation theory (MP2) in combination with counterpoise-corrected triple-ζ basis sets can also be recommended for reliable calculations of energetics of ionic liquids.

Solitonic Integrable Perturbations of Parafermionic Theories

CERN Document Server

Fernández-Pousa, C R; Hollowood, Timothy J; Miramontes, J L

1997-01-01

The quantum integrability of a class of massive perturbations of the parafermionic conformal field theories associated to compact Lie groups is established by showing that they have quantum conserved densities of scale dimension 2 and 3. These theories are integrable for any value of a continuous vector coupling constant, and they generalize the perturbation of the minimal parafermionic models by their first thermal operator. The classical equations-of-motion of these perturbed theories are the non-abelian affine Toda equations which admit (charged) soliton solutions whose semi-classical quantization is expected to permit the identification of the exact S-matrix of the theory.

Relativistic many-body perturbation-theory calculations based on Dirac-Fock-Breit wave functions

International Nuclear Information System (INIS)

Ishikawa, Y.; Quiney, H.M.

1993-01-01

A relativistic many-body perturbation theory based on the Dirac-Fock-Breit wave functions has been developed and implemented by employing analytic basis sets of Gaussian-type functions. The instantaneous Coulomb and low-frequency Breit interactions are treated using a unified formalism in both the construction of the Dirac-Fock-Breit self-consistent-field atomic potential and in the evaluation of many-body perturbation-theory diagrams. The relativistic many-body perturbation-theory calculations have been performed on the helium atom and ions of the helium isoelectronic sequence up to Z=50. The contribution of the low-frequency Breit interaction to the relativistic correlation energy is examined for the helium isoelectronic sequence

Non-perturbative Green functions in quantum gauge theories

International Nuclear Information System (INIS)

Shabanov, S.V.

1991-01-01

Non-perturbative Green functions for gauge invariant variables are considered. The Green functions are found to be modified as compared with the usual ones in a definite gauge because of a physical configuration space (PCS) reduction. In the Yang-Mills theory with fermions this phenomenon follows from the Singer theorem about the absence of a global gauge condition for the fields tensing to zero at spatial infinity. 20 refs

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.

The correlation function for density perturbations in an expanding universe. IV - The evolution of the correlation function. [galaxy distribution

Science.gov (United States)

Mcclelland, J.; Silk, J.

1979-01-01

The evolution of the two-point correlation function for the large-scale distribution of galaxies in an expanding universe is studied on the assumption that the perturbation densities lie in a Gaussian distribution centered on any given mass scale. The perturbations are evolved according to the Friedmann equation, and the correlation function for the resulting distribution of perturbations at the present epoch is calculated. It is found that: (1) the computed correlation function gives a satisfactory fit to the observed function in cosmological models with a density parameter (Omega) of approximately unity, provided that a certain free parameter is suitably adjusted; (2) the power-law slope in the nonlinear regime reflects the initial fluctuation spectrum, provided that the density profile of individual perturbations declines more rapidly than the -2.4 power of distance; and (3) both positive and negative contributions to the correlation function are predicted for cosmological models with Omega less than unity.

The SU(3) beta function from numerical stochastic perturbation theory

Energy Technology Data Exchange (ETDEWEB)

Horsley, R. [Edinburgh Univ. (United Kingdom). School of Physics and Astronomy; Perlt, H. [Leipzig Univ. (Germany). Inst. fuer Theoretische Physik; Bonn Univ. (Germany). Helmholtz Inst. fuer Strahlen- und Kernphysik; Rakow, P.E.L. [Liverpool Univ. (United Kingdom). Theoretical Physics Div.; Schierholz, G.; Schiller, A. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

2013-09-15

The SU(3) beta function is derived from Wilson loops computed to 20th order in numerical stochastic perturbation theory. An attempt is made to include massless fermions, whose contribution is known analytically to 4th order. The question whether the theory admits an infrared stable fixed point is addressed.

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

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.

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

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

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)

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

Finite density two color chiral perturbation theory revisited

Science.gov (United States)

Adhikari, Prabal; Beleznay, Soma B.; Mannarelli, Massimo

2018-06-01

We revisit two-color, two-flavor chiral perturbation theory at finite isospin and baryon density. We investigate the phase diagram obtained varying the isospin and the baryon chemical potentials, focusing on the phase transition occurring when the two chemical potentials are equal and exceed the pion mass (which is degenerate with the diquark mass). In this case, there is a change in the order parameter of the theory that does not lend itself to the standard picture of first order transitions. We explore this phase transition both within a Ginzburg-Landau framework valid in a limited parameter space and then by inspecting the full chiral Lagrangian in all the accessible parameter space. Across the phase transition between the two broken phases the order parameter becomes an SU(2) doublet, with the ground state fixing the expectation value of the sum of the magnitude squared of the pion and the diquark fields. Furthermore, we find that the Lagrangian at equal chemical potentials is invariant under global SU(2) transformations and construct the effective Lagrangian of the three Goldstone degrees of freedom by integrating out the radial fluctuations.

Two-body perturbation theory versus first order perturbation theory: A comparison based on the square-well fluid.

Science.gov (United States)

Mercier Franco, Luís Fernando; Castier, Marcelo; Economou, Ioannis G

2017-12-07

We show that the Zwanzig first-order perturbation theory can be obtained directly from a truncated Taylor series expansion of a two-body perturbation theory and that such truncation provides a more accurate prediction of thermodynamic properties than the full two-body perturbation theory. This unexpected result is explained by the quality of the resulting approximation for the fluid radial distribution function. We prove that the first-order and the two-body perturbation theories are based on different approximations for the fluid radial distribution function. To illustrate the calculations, the square-well fluid is adopted. We develop an analytical expression for the two-body perturbed Helmholtz free energy for the square-well fluid. The equation of state obtained using such an expression is compared to the equation of state obtained from the first-order approximation. The vapor-liquid coexistence curve and the supercritical compressibility factor of a square-well fluid are calculated using both equations of state and compared to Monte Carlo simulation data. Finally, we show that the approximation for the fluid radial distribution function given by the first-order perturbation theory provides closer values to the ones calculated via Monte Carlo simulations. This explains why such theory gives a better description of the fluid thermodynamic behavior.

UV-Vis optoelectronic properties of α-SnWO4: A comparative experimental and density functional theory based study

KAUST Repository

Ziani, Ahmed

2015-09-03

We report a combined experimental and theoretical study on the optoelectronic properties of α-SnWO4 for UV-Vis excitation. The experimentally measured values for thin films were systematically compared with high-accuracy density functional theory and density functional perturbation theory using the HSE06 functional. The α-SnWO4 material shows an indirect bandgap of 1.52 eV with high absorption coefficient in the visible-light range (>2 × 105 cm−1). The results show relatively high dielectric constant (>30) and weak diffusion properties (large effective masses) of excited carriers.

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

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

Science.gov (United States)

Phillips, Jordan J; Peralta, Juan E

2011-11-14

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

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 ...

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.

UV-Vis optoelectronic properties of α-SnWO4: A comparative experimental and density functional theory based study

KAUST Repository

Ziani, Ahmed; Harb, Moussab; Noureldine, Dalal; Takanabe, Kazuhiro

2015-01-01

and density functional perturbation theory using the HSE06 functional. The α-SnWO4 material shows an indirect bandgap of 1.52 eV with high absorption coefficient in the visible-light range (>2 × 105 cm−1). The results show relatively high dielectric constant

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.

Density Functional Theory Simulations of Semiconductors for Photovoltaic Applications: Hybrid Organic-Inorganic Perovskites and III/V Heterostructures

Directory of Open Access Journals (Sweden)

Jacky Even

2014-01-01

Full Text Available Potentialities of density functional theory (DFT based methodologies are explored for photovoltaic materials through the modeling of the structural and optoelectronic properties of semiconductor hybrid organic-inorganic perovskites and GaAs/GaP heterostructures. They show how the properties of these bulk materials, as well as atomistic relaxations, interfaces, and electronic band-lineups in small heterostructures, can be thoroughly investigated. Some limitations of available standard DFT codes are discussed. Recent improvements able to treat many-body effects or based on density-functional perturbation theory are also reviewed in the context of issues relevant to photovoltaic technologies.

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.

Generalized perturbation theory using two-dimensional, discrete ordinates transport theory

International Nuclear Information System (INIS)

Childs, R.L.

1979-01-01

Perturbation theory for changes in linear and bilinear functionals of the forward and adjoint fluxes in a critical reactor has been implemented using two-dimensional discrete ordinates transport theory. The computer program DOT IV was modified to calculate the generalized functions Λ and Λ*. Demonstration calculations were performed for changes in a reaction-rate ratio and a reactivity worth caused by system perturbations. The perturbation theory predictions agreed with direct calculations to within about 2%. A method has been developed for calculating higher lambda eigenvalues and eigenfunctions using techniques similar to those developed for generalized functions. Demonstration calculations have been performed to obtain these eigenfunctions

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.

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...

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

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

Phase transitions of titanite CaTiSiO5 from density functional perturbation theory

Science.gov (United States)

Malcherek, Thomas; Fischer, Michael

2018-02-01

Phonon dispersion of titanite CaTiSiO5 has been calculated using the variational density functional perturbation theory. The experimentally known out-of-center distortion of the Ti atom is confirmed. The distortion is associated with a Bu mode that is unstable for wave vectors normal to the octahedral chain direction of the C 2 /c aristotype structure. The layer of wave vectors with imaginary mode frequencies also comprises the Brillouin zone boundary point Y (0 ,1 ,0 ) , which is critical for the transition to the P 21/c ground-state structure. The phonon branch equivalent to the imaginary branch of the titanite aristotype is found to be stable in malayaite CaSnSiO5. The unstable phonon mode in titanite leads to the formation of transoriented short and long Ti-O1 bonds. The Ti as well as the connecting O1 atom exhibit strongly anomalous Born effective charges along the octahedral chain direction [001], indicative of the strong covalency in this direction. Accordingly and in contrast to malayaite, LO-TO splitting is very large in titanite. In the C 2 /c phase of titanite, the Ti-O1-Ti distortion chain is disordered with respect to neighboring distortion chains, as all chain configurations are equally unstable along the phonon branch. This result is in agreement with diffuse x-ray scattering in layers normal to the chain direction that is observed at temperatures close to the P 21/c to C 2 /c transition temperature and above. The resulting dynamic chains of correlated Ti displacements are expected to order in two dimensions to yield the P 21/c ground-state structure of titanite.

Radiation perturbation theory in gravity and quantum universe as a hydrogen atom

International Nuclear Information System (INIS)

Pervushin, V.N.

1992-01-01

In quantum theory of gravity of the (n+1)-dimensional space-time the Faddeev-Popov functional integral is constructed for radiation perturbation theory. In this version the Universe expansion looks as the collective superfluid motion of quantum space, and the vacuum energy density plays the role of the hidden mass. 6 refs

Range-separated density-functional theory for molecular excitation energies

International Nuclear Information System (INIS)

Rebolini, E.

2014-01-01

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

Coupling-parameter expansion in thermodynamic perturbation theory.

Science.gov (United States)

Ramana, A Sai Venkata; Menon, S V G

2013-02-01

An approach to the coupling-parameter expansion in the liquid state theory of simple fluids is presented by combining the ideas of thermodynamic perturbation theory and integral equation theories. This hybrid scheme avoids the problems of the latter in the two phase region. A method to compute the perturbation series to any arbitrary order is developed and applied to square well fluids. Apart from the Helmholtz free energy, the method also gives the radial distribution function and the direct correlation function of the perturbed system. The theory is applied for square well fluids of variable ranges and compared with simulation data. While the convergence of perturbation series and the overall performance of the theory is good, improvements are needed for potentials with shorter ranges. Possible directions for further developments in the coupling-parameter expansion are indicated.

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.

The sine-Gordon model and the small κ+ region of light- cone perturbation theory

International Nuclear Information System (INIS)

Griffin, P.A.

1992-01-01

The non-perturbative ultraviolet divergence of the sine-Gordon model is used to study the k + = 0 region of light-cone perturbation theory. The light-cone vacuum is shown to be unstable at the non- perturbative β 2 = 8π critical point by a light-cone version of Coleman's variational method. Vacuum bubbles, which are k + = 0 diagram in light-cone field theory and are individually finite and non-vanishing for all β, conspire to generate ultraviolet divergences of the light-cone energy density. The k + = 0 region of momentum also contributed to connected Green's functions: the connected two point function will not diverge, as it should, at the critical point unless diagrams which contribute only at k + = 0 are properly included. This analysis shows in a simple way how the k + = 0 region cannot be ignored even for connected diagrams. This phenomenon is expected to occur in higher dimensional gauge theories starting at two loop order in light-cone perturbation theory

Perturbation theory for BAO reconstructed fields: One-loop results in the real-space matter density field

Science.gov (United States)

Hikage, Chiaki; Koyama, Kazuya; Heavens, Alan

2017-08-01

We compute the power spectrum at one-loop order in standard perturbation theory for the matter density field to which a standard Lagrangian baryonic acoustic oscillation (BAO) reconstruction technique is applied. The BAO reconstruction method corrects the bulk motion associated with the gravitational evolution using the inverse Zel'dovich approximation (ZA) for the smoothed density field. We find that the overall amplitude of one-loop contributions in the matter power spectrum substantially decreases after reconstruction. The reconstructed power spectrum thereby approaches the initial linear spectrum when the smoothed density field is close enough to linear, i.e., the smoothing scale Rs≳10 h-1 Mpc . On smaller Rs, however, the deviation from the linear spectrum becomes significant on large scales (k ≲Rs-1 ) due to the nonlinearity in the smoothed density field, and the reconstruction is inaccurate. Compared with N-body simulations, we show that the reconstructed power spectrum at one-loop order agrees with simulations better than the unreconstructed power spectrum. We also calculate the tree-level bispectrum in standard perturbation theory to investigate non-Gaussianity in the reconstructed matter density field. We show that the amplitude of the bispectrum significantly decreases for small k after reconstruction and that the tree-level bispectrum agrees well with N-body results in the weakly nonlinear regime.

Multireference second order perturbation theory with a simplified treatment of dynamical correlation.

Science.gov (United States)

Xu, Enhua; Zhao, Dongbo; Li, Shuhua

2015-10-13

A multireference second order perturbation theory based on a complete active space configuration interaction (CASCI) function or density matrix renormalized group (DMRG) function has been proposed. This method may be considered as an approximation to the CAS/A approach with the same reference, in which the dynamical correlation is simplified with blocked correlated second order perturbation theory based on the generalized valence bond (GVB) reference (GVB-BCPT2). This method, denoted as CASCI-BCPT2/GVB or DMRG-BCPT2/GVB, is size consistent and has a similar computational cost as the conventional second order perturbation theory (MP2). We have applied it to investigate a number of problems of chemical interest. These problems include bond-breaking potential energy surfaces in four molecules, the spectroscopic constants of six diatomic molecules, the reaction barrier for the automerization of cyclobutadiene, and the energy difference between the monocyclic and bicyclic forms of 2,6-pyridyne. Our test applications demonstrate that CASCI-BCPT2/GVB can provide comparable results with CASPT2 (second order perturbation theory based on the complete active space self-consistent-field wave function) for systems under study. Furthermore, the DMRG-BCPT2/GVB method is applicable to treat strongly correlated systems with large active spaces, which are beyond the capability of CASPT2.

Second-Order Perturbation Theory for Generalized Active Space Self-Consistent-Field Wave Functions.

Science.gov (United States)

Ma, Dongxia; Li Manni, Giovanni; Olsen, Jeppe; Gagliardi, Laura

2016-07-12

A multireference second-order perturbation theory approach based on the generalized active space self-consistent-field (GASSCF) wave function is presented. Compared with the complete active space (CAS) and restricted active space (RAS) wave functions, GAS wave functions are more flexible and can employ larger active spaces and/or different truncations of the configuration interaction expansion. With GASSCF, one can explore chemical systems that are not affordable with either CASSCF or RASSCF. Perturbation theory to second order on top of GAS wave functions (GASPT2) has been implemented to recover the remaining electron correlation. The method has been benchmarked by computing the chromium dimer ground-state potential energy curve. These calculations show that GASPT2 gives results similar to CASPT2 even with a configuration interaction expansion much smaller than the corresponding CAS expansion.

Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations.

Science.gov (United States)

Lutnaes, Ola B; Teale, Andrew M; Helgaker, Trygve; Tozer, David J; Ruud, Kenneth; Gauss, Jürgen

2009-10-14

An accurate set of benchmark rotational g tensors and magnetizabilities are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster single-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the results obtained is established for the rotational g tensors by careful comparison with experimental data, taking into account zero-point vibrational corrections. After an analysis of the basis sets employed, extrapolation techniques are used to provide estimates of the basis-set-limit quantities, thereby establishing an accurate benchmark data set. The utility of the data set is demonstrated by examining a wide variety of density functionals for the calculation of these properties. None of the density-functional methods are competitive with the CCSD or CCSD(T) methods. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of density-functional calculations constrained to give the same electronic density. The importance of current dependence in exchange-correlation functionals is discussed in light of this comparison.

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.

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.

Cluster perturbation theory for calculation of electronic properties of ensembles of metal nanoclusters

Science.gov (United States)

Zhumagulov, Yaroslav V.; Krasavin, Andrey V.; Kashurnikov, Vladimir A.

2018-05-01

The method is developed for calculation of electronic properties of an ensemble of metal nanoclusters with the use of cluster perturbation theory. This method is applied to the system of gold nanoclusters. The Greens function of single nanocluster is obtained by ab initio calculations within the framework of the density functional theory, and then is used in Dyson equation to group nanoclusters together and to compute the Greens function as well as the electron density of states of the whole ensemble. The transition from insulator state of a single nanocluster to metallic state of bulk gold is observed.

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

Science.gov (United States)

Gillespie, Dirk

2014-11-01

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

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

Closed form bound-state perturbation theory

Directory of Open Access Journals (Sweden)

Ollie J. Rose

1980-01-01

Full Text Available The perturbed Schrödinger eigenvalue problem for bound states is cast into integral form using Green's Functions. A systematic algorithm is developed and applied to the resulting equation giving rise to approximate solutions expressed as functions of the given perturbation parameter. As a by-product, convergence radii for the traditional Rayleigh-Schrödinger and Brillouin-Wigner perturbation theories emerge in a natural way.

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.

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

Science.gov (United States)

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

2017-07-15

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

Reduced density matrix functional theory via a wave function based approach

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-01

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

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.

Analytic cubic and quartic force fields using density-functional theory

Energy Technology Data Exchange (ETDEWEB)

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

2014-01-21

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

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.

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

International Nuclear Information System (INIS)

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

1999-01-01

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

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.

Perturbation theory

International Nuclear Information System (INIS)

Bartlett, R.; Kirtman, B.; Davidson, E.R.

1978-01-01

After noting some advantages of using perturbation theory some of the various types are related on a chart and described, including many-body nonlinear summations, quartic force-field fit for geometry, fourth-order correlation approximations, and a survey of some recent work. Alternative initial approximations in perturbation theory are also discussed. 25 references

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

International Nuclear Information System (INIS)

Evans, R.; Kumaravadivel, R.

1976-01-01

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

Adler function for light quarks in analytic perturbation theory

International Nuclear Information System (INIS)

Milton, K. A.; Solovtsov, I. L.; Solovtsova, O. P.

2001-01-01

The method of analytic perturbation theory, which avoids the problem of ghost-pole-type singularities and gives a self-consistent description of both spacelike and timelike regions, is applied to describe the 'light' Adler function corresponding to the nonstrange vector channel of the inclusive decay of the τ lepton. The role of threshold effects is investigated. The behavior of the quark-antiquark system near threshold is described by using a new relativistic resummation factor. It is shown that the method proposed leads to good agreement with the 'experimental' Adler function down to the lowest energy scale

Generation of density perturbations by inflation in scalar-tensor gravity theories

Science.gov (United States)

Seshadri, T. R.

1992-02-01

Density perturbations arising out of the quantum fluctuations in a Brans-Dicke field in the context of extended inflation have been studied. We have used a model in which the Brans-Dicke parameter varies with time. We find that the density perturbations are large in magnitude and have a scale invariant spectrum. The origin of these is discussed and it is shown that these place further constraints on the model. Address after 15 Octobr 1991: Department of Physics and Astrophysics, University of Delhi 110 007, India.

Significance of constraints associated with Green's functions in Hamiltonian perturbation theory

International Nuclear Information System (INIS)

Maharana, L.; Muller-Kirsten, H.J.W.; Wiedemann, A.

1987-01-01

In many formulations of Hamiltonian perturbation theory a Green's function becomes undefined when some parameter is allowed to vanish. Here various examples are discussed to illustrate this phenomenon, and it is shown that they are all realizations of a general theorem. The cases considered are examples in classical mechanics, quantum mechanics, electrodynamics and field theory. The prime object is to illustrate the unity of the examples and thus to make the application of the procedure to field theory models of current interest more transparent. One example that it is referred to is the skyrmion model

New mechanism for generating density perturbations from inflation

International Nuclear Information System (INIS)

Dvali, Gia; Gruzinov, Andrei; Zaldarriaga, Matias

2004-01-01

We propose a new mechanism to generate density perturbations in inflationary models. Spatial fluctuations in the decay rate of the inflaton field to ordinary matter lead to fluctuations in the reheating temperature. We argue that in most realistic models of inflation the coupling of the inflaton to normal matter is determined by the vacuum expectation values of fields in the theory. If those fields are light during inflation (this is a generic situation in the minimal models of supersymmetric inflation) they will fluctuate leading to density perturbations through the proposed mechanism. We show that these fluctuations could easily dominate over the ones generated through the standard mechanism. The new scenario has several consequences for inflation model building and observations. The proposed mechanism allows us to generate the observed level of density perturbations with a much lower scale of inflation and thus generically predicts a smaller level of gravitational waves. The relation between the slope of the spectrum of the produced density perturbations and the potential of the inflaton field is different from the standard relations obtained in the context of slow roll inflation. Because the field responsible for the fluctuations is not the inflaton, it can have significantly larger self-couplings and thus density perturbations could be non-Gaussian. The non-Gaussianity can be large enough to be detectable by CMB and large scale structure observations

Geometric perturbation theory and plasma physics

International Nuclear Information System (INIS)

Omohundro, S.M.

1985-01-01

Modern differential geometric techniques are used to unify the physical asymptotics underlying mechanics, wave theory, and statistical mechanics. The approach gives new insights into the structure of physical theories and is suited to the needs of modern large-scale computer simulation and symbol manipulation systems. A coordinate-free formulation of non-singular perturbation theory is given, from which a new Hamiltonian perturbation structure is derived and related to the unperturbed structure in five different ways. The theory of perturbations in the presence of symmetry is developed, and the method of averaging is related to reduction by a circle-group action. The pseudo-forces and magnetic Poisson bracket terms due to reduction are given a natural asymptotic interpretation. Similar terms due to changing reference frames are related to the method of variation of parameters, which is also given a Hamiltonian formulation. These methods are used to answer a long-standing question posed by Kruskal about nearly periodic systems. The answer leads to a new secular perturbation theory that contains no adhoc elements, which is then applied to gyromotion. Eikonal wave theory is given a Hamiltonian formulation that generalizes Whitham's Lagrangian approach. The evolution of wave action density on ray phase space is given a Hamiltonian structure using a Lie-Poisson bracket. The relationship between dissipative and Hamiltonian systems is discussed. A theory motivated by free electron lasers gives new restrictions on the change of area of projected parallelepipeds under canonical transformations

Green's functions for theories with massless particles (in perturbation theory). [Growth properties, momentum space, mass renormalization

Energy Technology Data Exchange (ETDEWEB)

Blanchard, P [European Organization for Nuclear Research, Geneva (Switzerland); Seneor, R [European Organization for Nuclear Research, Geneva (Switzerland); Ecole Polytechnique, 75 - Paris (France). Centre de Physique Theorique)

1975-01-01

With the method of perturbative renormalization developed by Epstein and Glaser it is shown that Green's functions exist for theories with massless particles such as Q.E.D. and lambda:PHI/sup 2n/ theories. Growth properties are given in momentum space. In the case of Q.E.D., it is also shown that one can perform the physical mass renormalization.

Very high order lattice perturbation theory for Wilson loops

International Nuclear Information System (INIS)

Horsley, R.

2010-10-01

We calculate perturbativeWilson loops of various sizes up to loop order n=20 at different lattice sizes for pure plaquette and tree-level improved Symanzik gauge theories using the technique of Numerical Stochastic Perturbation Theory. This allows us to investigate the behavior of the perturbative series at high orders. We observe differences in the behavior of perturbative coefficients as a function of the loop order. Up to n=20 we do not see evidence for the often assumed factorial growth of the coefficients. Based on the observed behavior we sum this series in a model with hypergeometric functions. Alternatively we estimate the series in boosted perturbation theory. Subtracting the estimated perturbative series for the average plaquette from the non-perturbative Monte Carlo result we estimate the gluon condensate. (orig.)

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.

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.

Generalized nuclear Fukui functions in the framework of spin-polarized density-functional theory

International Nuclear Information System (INIS)

Chamorro, E.; Proft, F. de; Geerlings, P.

2005-01-01

An extension of Cohen's nuclear Fukui function is presented in the spin-polarized framework of density-functional theory (SP-DFT). The resulting new nuclear Fukui function indices Φ Nα and Φ Sα are intended to be the natural descriptors for the responses of the nuclei to changes involving charge transfer at constant multiplicity and also the spin polarization at constant number of electrons. These generalized quantities allow us to gain new insights within a perturbative scheme based on DFT. Calculations of the electronic and nuclear SP-DFT quantities are presented within a Kohn-Sham framework of chemical reactivity for a sample of molecules, including H 2 O, H 2 CO, and some simple nitrenes (NX) and phosphinidenes (PX), with X=H, Li, F, Cl, OH, SH, NH 2 , and PH 2 . Results have been interpreted in terms of chemical bonding in the context of Berlin's theorem, which provides a separation of the molecular space into binding and antibinding regions

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)

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

Reduced density-matrix functional theory: Correlation and spectroscopy.

Science.gov (United States)

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

2015-07-14

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

Superfield perturbation theory and renormalization

International Nuclear Information System (INIS)

Delbourgo, R.

1975-01-01

The perturbation theory graphs and divergences in super-symmetric Lagrangian models are studied by using superfield techniques. In super PHI 3 -theory very little effort is needed to arrive at the single infinite (wave function) renormalization counterterm, while in PHI 4 -theory the method indicates the counter-Lagrangians needed at the one-loop level and possibly beyond

New Approaches and Applications for Monte Carlo Perturbation Theory

Energy Technology Data Exchange (ETDEWEB)

Aufiero, Manuele; Bidaud, Adrien; Kotlyar, Dan; Leppänen, Jaakko; Palmiotti, Giuseppe; Salvatores, Massimo; Sen, Sonat; Shwageraus, Eugene; Fratoni, Massimiliano

2017-02-01

This paper presents some of the recent and new advancements in the extension of Monte Carlo Perturbation Theory methodologies and application. In particular, the discussed problems involve Brunup calculation, perturbation calculation based on continuous energy functions, and Monte Carlo Perturbation Theory in loosely coupled systems.

Communication: Random phase approximation renormalized many-body perturbation theory

International Nuclear Information System (INIS)

Bates, Jefferson E.; Furche, Filipp

2013-01-01

We derive a renormalized many-body perturbation theory (MBPT) starting from the random phase approximation (RPA). This RPA-renormalized perturbation theory extends the scope of single-reference MBPT methods to small-gap systems without significantly increasing the computational cost. The leading correction to RPA, termed the approximate exchange kernel (AXK), substantially improves upon RPA atomization energies and ionization potentials without affecting other properties such as barrier heights where RPA is already accurate. Thus, AXK is more balanced than second-order screened exchange [A. Grüneis et al., J. Chem. Phys. 131, 154115 (2009)], which tends to overcorrect RPA for systems with stronger static correlation. Similarly, AXK avoids the divergence of second-order Møller-Plesset (MP2) theory for small gap systems and delivers a much more consistent performance than MP2 across the periodic table at comparable cost. RPA+AXK thus is an accurate, non-empirical, and robust tool to assess and improve semi-local density functional theory for a wide range of systems previously inaccessible to first-principles electronic structure calculations

Pion parameters in nuclear medium from chiral perturbation theory and virial expansion

International Nuclear Information System (INIS)

Mallik, S.; Sarkar, Sourav

2004-01-01

We consider two methods to find the effective parameters of the pion traversing a nuclear medium. One is the first order chiral perturbation theoretic evaluation of the pion pole contribution to the two-point function of the axial-vector current. The other is the exact, first order virial expansion of the pion self-energy. We find that, although the results of chiral perturbation theory are not valid at normal nuclear density, those from the virial expansion may be reliable at such density. The latter predicts both the mass shift and the in-medium decay width of the pion to be small, of about a few MeV

Vibrational properties of SrCu{sub 2}O{sub 2} studied via Density Functional Theory calculations and compared to Raman and infrared spectroscopy measurements

Energy Technology Data Exchange (ETDEWEB)

Even, J., E-mail: jacky.even@insa.rennes.fr [Université Européenne de Bretagne, INSA, FOTON, UMR CNRS 6082, 20 Avenue des Buttes de Coësmes, F-35708 Rennes (France); Pedesseau, L.; Durand, O. [Université Européenne de Bretagne, INSA, FOTON, UMR CNRS 6082, 20 Avenue des Buttes de Coësmes, F-35708 Rennes (France); Modreanu, M. [Tyndall National Institute, Lee Maltings, Prospect Row, Cork (Ireland); Huyberechts, G. [FLAMAC, Technologiepark 903, 9052 Zwijnaarde (Belgium); Servet, B. [Thales Research and Technology France, Campus Polytechnique, 1, avenue Augustin Fresnel, 91767 Palaiseau cedex France (France); Chaix-Pluchery, O. [Laboratoire des Matériaux et du Génie Physique, Grenoble INP—Minatec, 3, parvis Louis Néel, BP 257, 38016 Grenoble Cedex 1 (France)

2013-08-31

The SrCu{sub 2}O{sub 2} material is a p-type transparent conductive oxide. A theoretical study of the SrCu{sub 2}O{sub 2} crystal is performed with a state of the art implementation of the Density Functional Theory. The simulated crystal structure is compared with available X-ray diffraction data and previous theoretical modeling. Density Functional Perturbation Theory is used to study the vibrational properties of the SrCu{sub 2}O{sub 2} crystal. A symmetry analysis of the optical phonon eigenvectors at the Brillouin zone center is proposed. The Raman spectra simulated using the derivatives of the dielectric susceptibility, show a good agreement with Raman scattering experimental results. - Highlights: ► The symmetry properties of the optical phonons of the SrCu{sub 2}O{sub 2} crystal are analyzed. ► Born charges and the dynamical matrix are calculated at the Brillouin zone center. ► Density Functional Perturbation Theory (DFPT) is used to compute Raman spectrum. ► DFPT Raman spectrum is compared with experimental results.

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

Effect of the nonlocal exchange on the performance of the orbital-dependent correlation functionals from second-order perturbation theory.

Science.gov (United States)

Schweigert, Igor V; Bartlett, Rodney J

2008-09-28

Adding a fraction of the nonlocal exchange operator to the local orbital-dependent exchange potential improves the many-body perturbation expansion based on the Kohn-Sham determinant. The effect of such a hybrid scheme on the performance of the orbital-dependent correlation functional from the second-order perturbation theory (PT2H) is investigated numerically. A small fraction of the nonlocal exchange is often sufficient to ensure the existence of the self-consistent solution for the PT2H potential. In the He and Be atoms, including 37% of the nonlocal exchange leads to the correlation energies and electronic densities that are very close to the exact ones. In molecules, varying the fraction of the nonlocal exchange may result in the PT2H energy closely reproducing the CCSD(T) value; however such a fraction depends on the system and does not always result in an accurate electronic density. We also numerically verify that the "semicanonical" perturbation series includes most of the beneficial effects of the nonlocal exchange without sacrificing the locality of the exchange potential.

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

Science.gov (United States)

Juhasz, Tamas; Mazziotti, David A

2004-07-15

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

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.

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.

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.

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.

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

Science.gov (United States)

Liang, Haozhao; Niu, Yifei; Hatsuda, Tetsuo

2018-04-01

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

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 ...

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...

Second-order generalized perturbation theory for source-driven systems

International Nuclear Information System (INIS)

Greenspan, E.; Gilai, D.; Oblow, E.M.

1978-01-01

A second-order generalized perturbation theory (GPT) for the effect of multiple system variations on a general flux functional in source-driven systems is derived. The derivation is based on a functional Taylor series in which second-order derivatives are retained. The resulting formulation accounts for the nonlinear effect of a given variation accurate to third order in the flux and adjoint perturbations. It also accounts for the effect of interaction between any number of variations. The new formulation is compared with exact perturbation theory as well as with perturbation theory for altered systems. The usefulnes of the second-order GPT formulation is illustrated by applying it to optimization problems. Its applicability to areas of cross-section sensitivity analysis and system design and evaluation is also discussed

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.

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...

Dynamic density functional theory with hydrodynamic interactions: Theoretical development and application in the study of phase separation in gas-liquid systems

International Nuclear Information System (INIS)

Kikkinides, E. S.; Monson, P. A.

2015-01-01

Building on recent developments in dynamic density functional theory, we have developed a version of the theory that includes hydrodynamic interactions. This is achieved by combining the continuity and momentum equations eliminating velocity fields, so the resulting model equation contains only terms related to the fluid density and its time and spatial derivatives. The new model satisfies simultaneously continuity and momentum equations under the assumptions of constant dynamic or kinematic viscosity and small velocities and/or density gradients. We present applications of the theory to spinodal decomposition of subcritical temperatures for one-dimensional and three-dimensional density perturbations for both a van der Waals fluid and for a lattice gas model in mean field theory. In the latter case, the theory provides a hydrodynamic extension to the recently studied dynamic mean field theory. We find that the theory correctly describes the transition from diffusive phase separation at short times to hydrodynamic behaviour at long times

Geometric perturbation theory and plasma physics

Energy Technology Data Exchange (ETDEWEB)

Omohundro, S.M.

1985-04-04

Modern differential geometric techniques are used to unify the physical asymptotics underlying mechanics, wave theory and statistical mechanics. The approach gives new insights into the structure of physical theories and is suited to the needs of modern large-scale computer simulation and symbol manipulation systems. A coordinate-free formulation of non-singular perturbation theory is given, from which a new Hamiltonian perturbation structure is derived and related to the unperturbed structure. The theory of perturbations in the presence of symmetry is developed, and the method of averaging is related to reduction by a circle group action. The pseudo-forces and magnetic Poisson bracket terms due to reduction are given a natural asymptotic interpretation. Similar terms due to changing reference frames are related to the method of variation of parameters, which is also given a Hamiltonian formulation. These methods are used to answer a question about nearly periodic systems. The answer leads to a new secular perturbation theory that contains no ad hoc elements. Eikonal wave theory is given a Hamiltonian formulation that generalizes Whitham's Lagrangian approach. The evolution of wave action density on ray phase space is given a Hamiltonian structure using a Lie-Poisson bracket. The relationship between dissipative and Hamiltonian systems is discussed. A new type of attractor is defined which attracts both forward and backward in time and is shown to occur in infinite-dimensional Hamiltonian systems with dissipative behavior. The theory of Smale horseshoes is applied to gyromotion in the neighborhood of a magnetic field reversal and the phenomenon of reinsertion in area-preserving horseshoes is introduced. The central limit theorem is proved by renormalization group techniques. A natural symplectic structure for thermodynamics is shown to arise asymptotically from the maximum entropy formalism.

Geometric perturbation theory and plasma physics

International Nuclear Information System (INIS)

Omohundro, S.M.

1985-01-01

Modern differential geometric techniques are used to unify the physical asymptotics underlying mechanics, wave theory and statistical mechanics. The approach gives new insights into the structure of physical theories and is suited to the needs of modern large-scale computer simulation and symbol manipulation systems. A coordinate-free formulation of non-singular perturbation theory is given, from which a new Hamiltonian perturbation structure is derived and related to the unperturbed structure. The theory of perturbations in the presence of symmetry is developed, and the method of averaging is related to reduction by a circle group action. The pseudo-forces and magnetic Poisson bracket terms due to reduction are given a natural asymptotic interpretation. Similar terms due to changing reference frames are related to the method of variation of parameters, which is also given a Hamiltonian formulation. These methods are used to answer a question about nearly periodic systems. The answer leads to a new secular perturbation theory that contains no ad hoc elements. Eikonal wave theory is given a Hamiltonian formulation that generalizes Whitham's Lagrangian approach. The evolution of wave action density on ray phase space is given a Hamiltonian structure using a Lie-Poisson bracket. The relationship between dissipative and Hamiltonian systems is discussed. A new type of attractor is defined which attracts both forward and backward in time and is shown to occur in infinite-dimensional Hamiltonian systems with dissipative behavior. The theory of Smale horseshoes is applied to gyromotion in the neighborhood of a magnetic field reversal and the phenomenon of reinsertion in area-preserving horseshoes is introduced. The central limit theorem is proved by renormalization group techniques. A natural symplectic structure for thermodynamics is shown to arise asymptotically from the maximum entropy formalism

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) ...

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

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

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.

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.

Chiral perturbation theory

International Nuclear Information System (INIS)

Ecker, G.

1996-06-01

After a general introduction to the structure of effective field theories, the main ingredients of chiral perturbation theory are reviewed. Applications include the light quark mass ratios and pion-pion scattering to two-loop accuracy. In the pion-nucleon system, the linear σ model is contrasted with chiral perturbation theory. The heavy-nucleon expansion is used to construct the effective pion-nucleon Lagrangian to third order in the low-energy expansion, with applications to nucleon Compton scattering. (author)

JDFTx: Software for joint density-functional theory

Directory of Open Access Journals (Sweden)

Ravishankar Sundararaman

2017-01-01

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

Multiple exciton generation in chiral carbon nanotubes: Density functional theory based computation

Science.gov (United States)

Kryjevski, Andrei; Mihaylov, Deyan; Kilina, Svetlana; Kilin, Dmitri

2017-10-01

We use a Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory based on density functional theory simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of the relaxation. We apply this approach to chiral single-wall carbon nanotubes (SWCNTs), such as (6,2) and (6,5). We predict efficient MEG in the (6,2) and (6,5) SWCNTs within the solar spectrum range starting at the 2Eg energy threshold and with QE reaching ˜1.6 at about 3Eg, where Eg is the electronic gap.

Gribov ambiguity, perturbation theory, and confinement

International Nuclear Information System (INIS)

Greensite, J.P.

1978-01-01

The generating functional proposed for gauge theories by Bender, Eguchi, and Pagels (BEP) is shown to be equivalent to a truncated form of the functional integral, in which only one field configuration from each gauge-equivalent Gribov set contributes to the functional integration. The standard perturbation technique provides a method of realizing this truncation condition. It is shown that any gauge-covariant quantity (such as the quark N-point functions), evaluated by perturbating around a field configuration gauge-equivalent to A = 0, is related by a gauge transformation to the same quantity evaluated perturbatively around the trivial vacuum. It follows that, contrary to the conclusion of BEP, the existence of degeneracies in the Coulomb gauge-fixing condition (the Gribov ambiguity) is not directly related to the physics of confinement

Automated lattice perturbation theory in the Schroedinger functional. Implementation and applications in HQET

International Nuclear Information System (INIS)

Hesse, Dirk

2012-01-01

The author developed the pastor software package for automated lattice perturbation theory calculations in the Schroedinger functional scheme. The pastor code consists of two building blocks, dealing with the generation of Feynman rules and Feynman diagrams respectively. Accepting a rather generic class of lattice gauge and fermion actions, passed to the code in a symbolic form as input, a low level part of pastor will generate Feynman rules to an arbitrary order in the bare coupling with a trivial or an Abelian background field. The second, high level part of pastor is a code generator whose output relies on the vertex generator. It writes programs that evaluate Feynman diagrams for a class of Schroedinger functional observables up to one loop order automatically, the relevant O(a) improvement terms are taken into account. We will describe the algorithms used for implementation of both parts of the code in detail, and provide cross checks with perturbative and non-perturbative data to demonstrate the correctness of our code. We demonstrate the usefulness of the pastor package through various applications taken from the matching process of heavy quark effective theory with quantum chromodynamics. We have e.g. completed a one loop analysis for new candidates for matching observables timely and with rather small effort, highlighting two advantages of an automated software setup. The results that were obtained so far will be useful as a guideline for further non-perturbative studies.

Automated lattice perturbation theory in the Schroedinger functional. Implementation and applications in HQET

Energy Technology Data Exchange (ETDEWEB)

Hesse, Dirk

2012-07-13

The author developed the pastor software package for automated lattice perturbation theory calculations in the Schroedinger functional scheme. The pastor code consists of two building blocks, dealing with the generation of Feynman rules and Feynman diagrams respectively. Accepting a rather generic class of lattice gauge and fermion actions, passed to the code in a symbolic form as input, a low level part of pastor will generate Feynman rules to an arbitrary order in the bare coupling with a trivial or an Abelian background field. The second, high level part of pastor is a code generator whose output relies on the vertex generator. It writes programs that evaluate Feynman diagrams for a class of Schroedinger functional observables up to one loop order automatically, the relevant O(a) improvement terms are taken into account. We will describe the algorithms used for implementation of both parts of the code in detail, and provide cross checks with perturbative and non-perturbative data to demonstrate the correctness of our code. We demonstrate the usefulness of the pastor package through various applications taken from the matching process of heavy quark effective theory with quantum chromodynamics. We have e.g. completed a one loop analysis for new candidates for matching observables timely and with rather small effort, highlighting two advantages of an automated software setup. The results that were obtained so far will be useful as a guideline for further non-perturbative studies.

Theory of deep inelastic neutron scattering: Hard-core perturbation theory

International Nuclear Information System (INIS)

Silver, R.N.

1988-01-01

Details are presented of a new many-body theory for deep inelastic neutron scattering (DINS) experiments to measure momentum distributions in quantum fluids and solids. The high-momentum and energy-transfer scattering law in helium is shown to be a convolution of the impulse approximation with a final-state broadening function which depends on the scattering phase shifts and the radial distribution function. The predicted broadening satisfies approximate Y scaling, is neither Lorentzian nor Gaussian, and obeys the f, ω 2 , and ω 3 sum rules. The derivation uses a combination of Liouville perturbation theory, projection superoperators, and semiclassical methods which I term ''hard-core perturbation theory.'' A review is presented of the predictions of prior theories for DINS experiments in relation to the present work. A subsequent paper will present massive numerical predictions and a discussion of DINS experiments on superfluid 4 He

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...

Perturbation Theory of Embedded Eigenvalues

DEFF Research Database (Denmark)

Engelmann, Matthias

project gives a general and systematic approach to analytic perturbation theory of embedded eigenvalues. The spectral deformation technique originally developed in the theory of dilation analytic potentials in the context of Schrödinger operators is systematized by the use of Mourre theory. The group...... of dilations is thereby replaced by the unitary group generated y the conjugate operator. This then allows to treat the perturbation problem with the usual Kato theory.......We study problems connected to perturbation theory of embedded eigenvalues in two different setups. The first part deals with second order perturbation theory of mass shells in massive translation invariant Nelson type models. To this end an expansion of the eigenvalues w.r.t. fiber parameter up...

Cosmological perturbation theory and quantum gravity

Energy Technology Data Exchange (ETDEWEB)

Brunetti, Romeo [Dipartimento di Matematica, Università di Trento,Via Sommarive 14, 38123 Povo TN (Italy); Fredenhagen, Klaus [II Institute für Theoretische Physik, Universität Hamburg,Luruper Chaussee 149, 22761 Hamburg (Germany); Hack, Thomas-Paul [Institute für Theoretische Physik, Universität Leipzig,Brüderstr. 16, 04103 Leipzig (Germany); Pinamonti, Nicola [Dipartimento di Matematica, Università di Genova,Via Dodecaneso 35, 16146 Genova (Italy); INFN, Sezione di Genova,Via Dodecaneso 33, 16146 Genova (Italy); Rejzner, Katarzyna [Department of Mathematics, University of York,Heslington, York YO10 5DD (United Kingdom)

2016-08-04

It is shown how cosmological perturbation theory arises from a fully quantized perturbative theory of quantum gravity. Central for the derivation is a non-perturbative concept of gauge-invariant local observables by means of which perturbative invariant expressions of arbitrary order are generated. In particular, in the linearised theory, first order gauge-invariant observables familiar from cosmological perturbation theory are recovered. Explicit expressions of second order quantities are presented as well.

Optimized Perturbation Theory for Wave Functions of Quantum Systems

International Nuclear Information System (INIS)

Hatsuda, T.; Tanaka, T.; Kunihiro, T.

1997-01-01

The notion of the optimized perturbation, which has been successfully applied to energy eigenvalues, is generalized to treat wave functions of quantum systems. The key ingredient is to construct an envelope of a set of perturbative wave functions. This leads to a condition similar to that obtained from the principle of minimal sensitivity. Applications of the method to the quantum anharmonic oscillator and the double well potential show that uniformly valid wave functions with correct asymptotic behavior are obtained in the first-order optimized perturbation even for strong couplings. copyright 1997 The American Physical Society

Convergent perturbation expansions for Euclidean quantum field theory

International Nuclear Information System (INIS)

Mack, G.; Pordt, A.

1984-09-01

Mayer perturbation theory is designed to provide computable convergent expansions which permit calculation of Greens functions in Euclidean Quantum Field Theory to arbitrary accuracy, including 'nonperturbative' contributions from large field fluctuations. Here we describe the expansions at the example of 3-dimensional lambdaphi 4 -theory (in continuous space). They are not essentially more complicated than standard perturbation theory. The n-th order term is expressed in terms of 0(n)-dimensional integrals, and is of order lambda 4 if 4k-3<=n<=4k. (orig.)

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...

A new perturbative approximation applied to supersymmetric quantum field theory

International Nuclear Information System (INIS)

Bender, C.M.; Milton, K.A.; Pinsky, S.S.; Simmons, L.M. Jr.; Los Alamos National Lab.

1988-01-01

We show that a recently proposed graphical perturbative calculational scheme in quantum field theory is consistent with global supersymmetry invariance. We examine a two-dimensional supersymmetric quantum field theory in which we do not known of any other means for doing analytical calculations. We illustrate the power of this new technique by computing the ground-state energy density E to second order in this new perturbation theory. We show that there is a beautiful and delicate cancellation between infinite classes of graphs which leads to the result that E=0. (orig.)

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.

Nuclear energy density functional from chiral pion-nucleon dynamics revisited

OpenAIRE

Kaiser, N.; Weise, W.

2009-01-01

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

Level density approach to perturbation theory and inverse-energy-weighted sum-rules

International Nuclear Information System (INIS)

Halemane, T.R.

1983-01-01

The terms in the familiar Rayleigh-Schroedinger perturbation series involve eigenvalues and eigenfunctions of the unperturbed operator. A level density formalism, that does not involve computation of eigenvalues and eigenfunctions, is given here for the perturbation series. In the CLT (central limit theorem) limit the expressions take very simple linear forms. The evaluation is in terms of moments and traces of operators and operator products. 3 references

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

Science.gov (United States)

Petrosyan, Sahak A.

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

Perturbative algebraic quantum field theory at finite temperature

Energy Technology Data Exchange (ETDEWEB)

Lindner, Falk

2013-08-15

We present the algebraic approach to perturbative quantum field theory for the real scalar field in Minkowski spacetime. In this work we put a special emphasis on the inherent state-independence of the framework and provide a detailed analysis of the state space. The dynamics of the interacting system is constructed in a novel way by virtue of the time-slice axiom in causal perturbation theory. This method sheds new light in the connection between quantum statistical dynamics and perturbative quantum field theory. In particular it allows the explicit construction of the KMS and vacuum state for the interacting, massive Klein-Gordon field which implies the absence of infrared divergences of the interacting theory at finite temperature, in particular for the interacting Wightman and time-ordered functions.

Perturbative algebraic quantum field theory at finite temperature

International Nuclear Information System (INIS)

Lindner, Falk

2013-08-01

We present the algebraic approach to perturbative quantum field theory for the real scalar field in Minkowski spacetime. In this work we put a special emphasis on the inherent state-independence of the framework and provide a detailed analysis of the state space. The dynamics of the interacting system is constructed in a novel way by virtue of the time-slice axiom in causal perturbation theory. This method sheds new light in the connection between quantum statistical dynamics and perturbative quantum field theory. In particular it allows the explicit construction of the KMS and vacuum state for the interacting, massive Klein-Gordon field which implies the absence of infrared divergences of the interacting theory at finite temperature, in particular for the interacting Wightman and time-ordered functions.

Perturbation theory for continuous stochastic equations

International Nuclear Information System (INIS)

Chechetkin, V.R.; Lutovinov, V.S.

1987-01-01

The various general perturbational schemes for continuous stochastic equations are considered. These schemes have many analogous features with the iterational solution of Schwinger equation for S-matrix. The following problems are discussed: continuous stochastic evolution equations for probability distribution functionals, evolution equations for equal time correlators, perturbation theory for Gaussian and Poissonian additive noise, perturbation theory for birth and death processes, stochastic properties of systems with multiplicative noise. The general results are illustrated by diffusion-controlled reactions, fluctuations in closed systems with chemical processes, propagation of waves in random media in parabolic equation approximation, and non-equilibrium phase transitions in systems with Poissonian breeding centers. The rate of irreversible reaction X + X → A (Smoluchowski process) is calculated with the use of general theory based on continuous stochastic equations for birth and death processes. The threshold criterion and range of fluctuational region for synergetic phase transition in system with Poissonian breeding centers are also considered. (author)

On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small water clusters: Benchmarks approaching the complete basis set limit

Science.gov (United States)

Santra, Biswajit; Michaelides, Angelos; Scheffler, Matthias

2007-11-01

The ability of several density-functional theory (DFT) exchange-correlation functionals to describe hydrogen bonds in small water clusters (dimer to pentamer) in their global minimum energy structures is evaluated with reference to second order Møller-Plesset perturbation theory (MP2). Errors from basis set incompleteness have been minimized in both the MP2 reference data and the DFT calculations, thus enabling a consistent systematic evaluation of the true performance of the tested functionals. Among all the functionals considered, the hybrid X3LYP and PBE0 functionals offer the best performance and among the nonhybrid generalized gradient approximation functionals, mPWLYP and PBE1W perform best. The popular BLYP and B3LYP functionals consistently underbind and PBE and PW91 display rather variable performance with cluster size.

Functional differential equation approach to the large N expansion and mean field perturbation theory

International Nuclear Information System (INIS)

Bender, C.M.; Cooper, F.

1985-01-01

An apparent difference between formulating mean field perturbation theory for lambdaphi 4 field theory via path integrals or via functional differential equations when there are external sources present is shown not to exist when mean field theory is considered as the N = 1 limit of the 0(N)lambdaphi 4 field theory. A simply method is given for determining the 1/N expansion for the Green's functions in the presence of external sources by directly solving the functional differential equations order by order in 1/N. The 1/N expansion for the effective action GAMMA(phi,chi) is obtained by directly integrating the functional differential equations for the fields phi and chi (equivalent1/2lambda/Nphi/sub α/phi/sup α/-μ 2 ) in the presence of two external sources j = -deltaGAMMA/deltaphi, S = -deltaGAMMA/deltachi

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.

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.

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.

The correlation function for density perturbations in an expanding universe. III The three-point and predictions of the four-point and higher order correlation functions

Science.gov (United States)

Mcclelland, J.; Silk, J.

1978-01-01

Higher-order correlation functions for the large-scale distribution of galaxies in space are investigated. It is demonstrated that the three-point correlation function observed by Peebles and Groth (1975) is not consistent with a distribution of perturbations that at present are randomly distributed in space. The two-point correlation function is shown to be independent of how the perturbations are distributed spatially, and a model of clustered perturbations is developed which incorporates a nonuniform perturbation distribution and which explains the three-point correlation function. A model with hierarchical perturbations incorporating the same nonuniform distribution is also constructed; it is found that this model also explains the three-point correlation function, but predicts different results for the four-point and higher-order correlation functions than does the model with clustered perturbations. It is suggested that the model of hierarchical perturbations might be explained by the single assumption of having density fluctuations or discrete objects all of the same mass randomly placed at some initial epoch.

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

Science.gov (United States)

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

2017-11-16

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

Dissipative motion perturbation theory and exact solutions

International Nuclear Information System (INIS)

Lodder, J.J.

1976-06-01

Dissipative motion of classical and quantum systems is described. In particular, attention is paid to systems coupled to the radiation field. A dissipative equation of motion for a particle in an arbitrary potential coupled to the radiation field is derived by means of perturbation theory. The usual divrgencies associated with the radiation field are eliminated by the application of a theory of generalized functions. This theory is developed as a subject in its own right and is presented independently. The introduction of classical zero-point energy makes the classical equa tion of motion for the phase density formally the same as its quantum counterpart. In particular, it is shown that the classical zero-point energy prevents the collapse of a classical H-atom and gives rise to a classical ground state. For systems with a quadratic Hamiltoian, the equation of motion can be solved exactly, even in the continuum limit for the radiation field, by means of the new generalized functions. Classically, the Fokker-Planck equation is found without any approximations, and quantum mechanically, the only approximation is the neglect of the change in the ground state caused by the interaction. The derivation is valid even for strong damping and arbitrarily short times. There is no transient time. For harmonic oscillators complete equivalence is shown to exist between quantum mechanics and classical mechanics with zero-point energy. A discussion of the derivation of the Pauli equation is given and perturbation theory is compared with the exact derivation. The exactly solvable models are used to calculate the Langevin force of the radiation field. The result is that the classical Langevin force is exactly delta-correlated, while the quantum Langevin force is not delta-correlated at all. The fluctuation-dissipation theorem is shown to be an exact consequence of the solution to the equations of motion

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.

Domain walls and perturbation theory in high-temperature gauge theory: SU(2) in 2+1 dimensions

International Nuclear Information System (INIS)

Korthals Altes, C.; Michels, A.; Teper, M.; Stephanov, M.

1997-01-01

We study the detailed properties of Z 2 domain walls in the deconfined high-temperature phase of the d=2+1 SU(2) gauge theory. These walls are studied both by computer simulations of the lattice theory and by one-loop perturbative calculations. The latter are carried out both in the continuum and on the lattice. We find that leading order perturbation theory reproduces the detailed properties of these domain walls remarkably accurately even at temperatures where the effective dimensionless expansion parameter g 2 /T is close to unity. The quantities studied include the surface tension, the action density profiles, roughening, and the electric screening mass. It is only for the last quantity that we find an exception to the precocious success of perturbation theory. All this shows that, despite the presence of infrared divergences at higher orders, high-T perturbation theory can be an accurate calculational tool. copyright 1997 The American Physical Society

Infrared problems in field perturbation theory

International Nuclear Information System (INIS)

David, Francois.

1982-12-01

The work presented mainly covers questions related to the presence of ''infrared'' divergences in perturbation expansions of the Green functions of certain massless field theories. It is important to determine the mathematical status of perturbation expansions in field theory in order to define the region in which they are valid. Renormalization and the symmetry of a theory are important factors in infrared problems. The main object of this thesis resides in the mathematical techniques employed: integral representations of the Feynman amplitudes; methods for desingularization, regularization and dimensional renormalization. Nonlinear two dimensional space-time sigma models describing Goldstone's low energy boson dynamics associated with a breaking of continuous symmetry are studied. Random surface models are then investigated followed by infrared divergences in super-renormalizable theories. Finally, nonperturbation effects in massless theories are studied by expanding the two-dimensional nonlinear sigma model in 1/N [fr

An improved thermodynamic perturbation theory for Mercedes-Benz water.

Science.gov (United States)

Urbic, T; Vlachy, V; Kalyuzhnyi, Yu V; Dill, K A

2007-11-07

We previously applied Wertheim's thermodynamic perturbation theory for associative fluids to the simple Mercedes-Benz model of water. We found that the theory reproduced well the physical properties of hot water, but was less successful in capturing the more structured hydrogen bonding that occurs in cold water. Here, we propose an improved version of the thermodynamic perturbation theory in which the effective density of the reference system is calculated self-consistently. The new theory is a significant improvement, giving good agreement with Monte Carlo simulations of the model, and predicting key anomalies of cold water, such as minima in the molar volume and large heat capacity, in addition to giving good agreement with the isothermal compressibility and thermal expansion coefficient.

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 ...

Large-order perturbation theory

International Nuclear Information System (INIS)

Wu, T.T.

1982-01-01

The original motivation for studying the asymptotic behavior of the coefficients of perturbation series came from quantum field theory. An overview is given of some of the attempts to understand quantum field theory beyond finite-order perturbation series. At least is the case of the Thirring model and probably in general, the full content of a relativistic quantum field theory cannot be recovered from its perturbation series. This difficulty, however, does not occur in quantum mechanics, and the anharmonic oscillator is used to illustrate the methods used in large-order perturbation theory. Two completely different methods are discussed, the first one using the WKB approximation, and a second one involving the statistical analysis of Feynman diagrams. The first one is well developed and gives detailed information about the desired asymptotic behavior, while the second one is still in its infancy and gives instead information about the distribution of vertices of the Feynman diagrams

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.

Higher order alchemical derivatives from coupled perturbed self-consistent field theory.

Science.gov (United States)

Lesiuk, Michał; Balawender, Robert; Zachara, Janusz

2012-01-21

We present an analytical approach to treat higher order derivatives of Hartree-Fock (HF) and Kohn-Sham (KS) density functional theory energy in the Born-Oppenheimer approximation with respect to the nuclear charge distribution (so-called alchemical derivatives). Modified coupled perturbed self-consistent field theory is used to calculate molecular systems response to the applied perturbation. Working equations for the second and the third derivatives of HF/KS energy are derived. Similarly, analytical forms of the first and second derivatives of orbital energies are reported. The second derivative of Kohn-Sham energy and up to the third derivative of Hartree-Fock energy with respect to the nuclear charge distribution were calculated. Some issues of practical calculations, in particular the dependence of the basis set and Becke weighting functions on the perturbation, are considered. For selected series of isoelectronic molecules values of available alchemical derivatives were computed and Taylor series expansion was used to predict energies of the "surrounding" molecules. Predicted values of energies are in unexpectedly good agreement with the ones computed using HF/KS methods. Presented method allows one to predict orbital energies with the error less than 1% or even smaller for valence orbitals. © 2012 American Institute of Physics

Invariant exchange perturbation theory for multicenter systems: Time-dependent perturbations

International Nuclear Information System (INIS)

Orlenko, E. V.; Evstafev, A. V.; Orlenko, F. E.

2015-01-01

A formalism of exchange perturbation theory (EPT) is developed for the case of interactions that explicitly depend on time. Corrections to the wave function obtained in any order of perturbation theory and represented in an invariant form include exchange contributions due to intercenter electron permutations in complex multicenter systems. For collisions of atomic systems with an arbitrary type of interaction, general expressions are obtained for the transfer (T) and scattering (S) matrices in which intercenter electron permutations between overlapping nonorthogonal states belonging to different centers (atoms) are consistently taken into account. The problem of collision of alpha particles with lithium atoms accompanied by the redistribution of electrons between centers is considered. The differential and total charge-exchange cross sections of lithium are calculated

Analytic perturbation theory for screened Coulomb potential: full continuum wave function

International Nuclear Information System (INIS)

Bechler, A.; Ennan, Mc J.; Pratt, R.H.

1979-01-01

An analytic perturbation theory developed previously is used to find a continuum screened-Coulomb wave function characterized by definite asymptotic momentum. This wave function satisfies an inhomogeneous partial differential equation which is solved in parabolic coordinates; the solution depends on both parabolic variables. We calculate partial wave projections of this solution and show that we can choose to add a solution of the homogeneous equation such that the partial wave projections become equal to the normalized continuum radial function found previously. However, finding the unique solution with given asymptotic linear momentum will require either using boundary conditions to determine the unique needed solution of the homogeneous equation or equivalently specifying the screened-Coulomb phase-shifts. (author)

Cosmological Perturbation Theory Using the Schrödinger Equation

Science.gov (United States)

Szapudi, István; Kaiser, Nick

2003-01-01

We introduce the theory of nonlinear cosmological perturbations using the correspondence limit of the Schrödinger equation. The resulting formalism is equivalent to using the collisionless Boltzmann (or Vlasov) equations, which remain valid during the whole evolution, even after shell crossing. Other formulations of perturbation theory explicitly break down at shell crossing, e.g., Eulerean perturbation theory, which describes gravitational collapse in the fluid limit. This Letter lays the groundwork by introducing the new formalism, calculating the perturbation theory kernels that form the basis of all subsequent calculations. We also establish the connection with conventional perturbation theories, by showing that third-order tree-level results, such as bispectrum, skewness, cumulant correlators, and three-point function, are exactly reproduced in the appropriate expansion of our results. We explicitly show that cumulants up to N=5 predicted by Eulerian perturbation theory for the dark matter field δ are exactly recovered in the corresponding limit. A logarithmic mapping of the field naturally arises in the Schrödinger context, which means that tree-level perturbation theory translates into (possibly incomplete) loop corrections for the conventional perturbation theory. We show that the first loop correction for the variance is σ2=σ2L+(-1.14- n)σ4L for a field with spectral index n. This yields 1.86 and 0.86 for n=-3 and -2, respectively, to be compared with the exact loop order corrections 1.82 and 0.88. Thus, our tree-level theory recovers the dominant part of first-order loop corrections of the conventional theory, while including (partial) loop corrections to infinite order in terms of δ.

Enforcing conservation laws in nonequilibrium cluster perturbation theory

Science.gov (United States)

Gramsch, Christian; Potthoff, Michael

2017-05-01

Using the recently introduced time-local formulation of the nonequilibrium cluster perturbation theory (CPT), we construct a generalization of the approach such that macroscopic conservation laws are respected. This is achieved by exploiting the freedom for the choice of the starting point of the all-order perturbation theory in the intercluster hopping. The proposed conserving CPT is a self-consistent propagation scheme which respects the conservation of energy, particle number, and spin, which treats short-range correlations exactly up to the linear scale of the cluster, and which represents a mean-field-like approach on length scales beyond the cluster size. Using Green's functions, conservation laws are formulated as local constraints on the local spin-dependent particle and the doublon density. We consider them as conditional equations to self-consistently fix the time-dependent intracluster one-particle parameters. Thanks to the intrinsic causality of the CPT, this can be set up as a step-by-step time propagation scheme with a computational effort scaling linearly with the maximum propagation time and exponentially in the cluster size. As a proof of concept, we consider the dynamics of the two-dimensional, particle-hole-symmetric Hubbard model following a weak interaction quench by simply employing two-site clusters only. Conservation laws are satisfied by construction. We demonstrate that enforcing them has strong impact on the dynamics. While the doublon density is strongly oscillating within plain CPT, a monotonic relaxation is observed within the conserving CPT.

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.

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.

Analysis of observables in Chern-Simons perturbation theory

International Nuclear Information System (INIS)

Alvarez, M.; Labastida, J.M.F.

1993-01-01

Chern-Simons theory with gauge group SU(N) is analyzed from a perturbation theory point of view. Computations up to order g 6 of the vacuum expectation value of the unknot are carried out and it is shown that agreement with the exact result by Witten implies no quantum correction at two loops for the two-point function. In addition, it is shown from a perturbation theory point of view that the framing dependence of the vacuum expectation value of an arbitrary knot factorizes in the form predicted by Witten. (orig.)

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.

Chiral perturbation theory

International Nuclear Information System (INIS)

Harada, Masayasu

2009-01-01

Chiral perturbation theory has been used for great number of phenomenological analyses in low energy QCD as well as the lattice QCD analyses since the creation of the theory by Weinberg in 1979 followed by its consolidation by Gasser and Leutwyler in 1984 and 85. The theory is now the highly established one as the approach based on the effective field theory to search for Green function including quantum correlations in the frame of the systematic expansion technique using Lagrangian which includes all of the terms allowed by the symmetry. This review has been intended to describe how systematically physical quantities are calculated in the framework of the chiral symmetry. Consequently many of the various phenomenological analyses are not taken up here for which other reports are to be referred. Further views are foreseen to be developed based on the theory in addition to numbers of results reported up to the present. Finally π-π scattering is taken up to discuss to what energy scale the theory is available. (S. Funahashi)

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.

An integral for second-order multiple scattering perturbation theory

International Nuclear Information System (INIS)

Hoffman, G.G.

1997-01-01

This paper presents the closed form evaluation of a six-dimensional integral. The integral arises in the application to many-electron systems of a multiple scattering perturbation expansion at second order when formulated in fourier space. The resulting function can be used for the calculation of both the electron density and the effective one-electron potential in an SCF calculations. The closed form expression derived here greatly facilitates these calculations. In addition, the evaluated integral can be used for the computation of second-order corrections to the open-quotes optimized Thomas-Fermi theory.close quotes 10 refs., 2 figs

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)

Factorization theorems in perturbative quantum field theory

International Nuclear Information System (INIS)

Date, G.D.

1982-01-01

This dissertation deals with factorization properties of Green functions and cross-sections in perturbation theory. It consists of two parts. Part I deals with the factorization theorem for the Drell-Yan cross-section. The new approach developed for this purpose is based upon a renormalization group equation with a generalized anomalous dimension. Using an alternate form of factorization for the Drell-Yan cross-section, derived in perturbation theory, a corresponding generalized anomalous dimension is defined, and explicit Feynman rules for its calculation are given. The resultant renormalization group equation is solved by a formal solution which is exhibited explicitly. Simple, explicit calculations are performed which verify Mueller's conjecture for the recovery of the usual parton model results for the Drell-Yan cross-section. The approach developed in this work offers a general framework to analyze the role played by the group factors in the cancellation of the soft divergences, and study their influence on the asymptotic behavior. Part II deals with factorization properties of the Green functions in position space. In this part, a Landau equation analysis is carried out for the singularities of the position space Green fucntions, in perturbation theory with the theta 4 interaction Lagrangian. A physical picture interpretation is given for the corresponding Landau equations. It is used to suggest a light-cone expansion. Using a power counting method, a formal derivation of the light-cone expansion for the two point function, the three point function and a product of two currents, is given without assuming a short distance expansion. Possible extensions to other theories is also considered

Plato: A localised orbital based density functional theory code

Science.gov (United States)

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

2009-12-01

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

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.

Orientation of rod molecules in selective slits: a density functional theory

International Nuclear Information System (INIS)

Xu Xiaofei; Cao Dapeng; Wang Wenchuan

2008-01-01

A density functional theory (DFT) is used to investigate molecular orientation of rod fluids in selective slits. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect, the first-order thermodynamics perturbation theory for chain connectivity and the mean-field approximation for van der Waals (vdW) attraction. To study the molecular orientation, the intramolecular bonding orientation function is introduced into the DFT. First, we investigate the orientation of the surfactant-like rod molecule of AB 6 (i.e. ABBBBBB) in a nanoslit of H 20σ, where the walls selectively adsorb segment 'A'. It is observed that, with the increase of the surface energy of the wall to head segment (i.e. 'A' segment) of the rod molecule, the rod molecules adsorbed on the wall present the perpendicular orientation gradually, and assemble into a smectic-A-like monolayer finally. In addition, we also explore the molecular orientation of the rods with both end segments preferring to the wall, i.e. AB 8 A and AB 7 A, in a nanoslit of H = 10σ. Interestingly, the AB 8 A rod monolayer is compatible with either a smectic-A-like or a smectic-C-like organization, but AB 7 A rod molecules exhibit the smectic-A-like organization. The orientation factor of the AB 7 A rod molecule reaches 1, suggesting that AB 7 A rod molecules self-assemble into an ordered structure with perfectly perpendicular orientation to the wall.

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.

Perturbation theory around the Wess-Zumino-Witten model

International Nuclear Information System (INIS)

Hasseln, H. v.

1991-05-01

We consider a perturbation of the Wess-Zumino-Witten model in 2D by a current-current interaction. The β-function is computed to third order in the coupling constant and a nontrivial fixedpoint is found. By non-abelian bosonization, this perturbed WZW-model is shown to have the same β-function (at least to order g 2 ) as the fermionic theory with a four-fermion interaction. (orig.) [de

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.)

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.

Nonperturbative Quantum Physics from Low-Order Perturbation Theory.

Science.gov (United States)

Mera, Héctor; Pedersen, Thomas G; Nikolić, Branislav K

2015-10-02

The Stark effect in hydrogen and the cubic anharmonic oscillator furnish examples of quantum systems where the perturbation results in a certain ionization probability by tunneling processes. Accordingly, the perturbed ground-state energy is shifted and broadened, thus acquiring an imaginary part which is considered to be a paradigm of nonperturbative behavior. Here we demonstrate how the low order coefficients of a divergent perturbation series can be used to obtain excellent approximations to both real and imaginary parts of the perturbed ground state eigenenergy. The key is to use analytic continuation functions with a built-in singularity structure within the complex plane of the coupling constant, which is tailored by means of Bender-Wu dispersion relations. In the examples discussed the analytic continuation functions are Gauss hypergeometric functions, which take as input fourth order perturbation theory and return excellent approximations to the complex perturbed eigenvalue. These functions are Borel consistent and dramatically outperform widely used Padé and Borel-Padé approaches, even for rather large values of the coupling constant.

Non-hard sphere thermodynamic perturbation theory.

Science.gov (United States)

Zhou, Shiqi

2011-08-21

A non-hard sphere (HS) perturbation scheme, recently advanced by the present author, is elaborated for several technical matters, which are key mathematical details for implementation of the non-HS perturbation scheme in a coupling parameter expansion (CPE) thermodynamic perturbation framework. NVT-Monte Carlo simulation is carried out for a generalized Lennard-Jones (LJ) 2n-n potential to obtain routine thermodynamic quantities such as excess internal energy, pressure, excess chemical potential, excess Helmholtz free energy, and excess constant volume heat capacity. Then, these new simulation data, and available simulation data in literatures about a hard core attractive Yukawa fluid and a Sutherland fluid, are used to test the non-HS CPE 3rd-order thermodynamic perturbation theory (TPT) and give a comparison between the non-HS CPE 3rd-order TPT and other theoretical approaches. It is indicated that the non-HS CPE 3rd-order TPT is superior to other traditional TPT such as van der Waals/HS (vdW/HS), perturbation theory 2 (PT2)/HS, and vdW/Yukawa (vdW/Y) theory or analytical equation of state such as mean spherical approximation (MSA)-equation of state and is at least comparable to several currently the most accurate Ornstein-Zernike integral equation theories. It is discovered that three technical issues, i.e., opening up new bridge function approximation for the reference potential, choosing proper reference potential, and/or using proper thermodynamic route for calculation of f(ex-ref), chiefly decide the quality of the non-HS CPE TPT. Considering that the non-HS perturbation scheme applies for a wide variety of model fluids, and its implementation in the CPE thermodynamic perturbation framework is amenable to high-order truncation, the non-HS CPE 3rd-order or higher order TPT will be more promising once the above-mentioned three technological advances are established. © 2011 American Institute of Physics

Algebraic perturbation theory for dense liquids with discrete potentials

Science.gov (United States)

Adib, Artur B.

2007-06-01

A simple theory for the leading-order correction g1(r) to the structure of a hard-sphere liquid with discrete (e.g., square-well) potential perturbations is proposed. The theory makes use of a general approximation that effectively eliminates four-particle correlations from g1(r) with good accuracy at high densities. For the particular case of discrete perturbations, the remaining three-particle correlations can be modeled with a simple volume-exclusion argument, resulting in an algebraic and surprisingly accurate expression for g1(r) . The structure of a discrete “core-softened” model for liquids with anomalous thermodynamic properties is reproduced as an application.

PREFACE: Classical density functional theory methods in soft and hard matter Classical density functional theory methods in soft and hard matter

Science.gov (United States)

Haataja, Mikko; Gránásy, László; Löwen, Hartmut

2010-08-01

, about a half of which are related to the theoretical materials science community and the other half came from the soft-matter community. We begin by discussing papers related to PFC. Diverse subjects related to the phase-field crystal model include exciting topics such as predicting/controlling the equilibrium phase behavior [19, 18, 17] and kinetics of epitaxial island formation on nano-membranes [20]. Moreover, phase-field crystal modeling has proved to be very successful in simulating homogeneous and heterogeneous crystal nucleation and growth, and several aspects of these phenomena are discussed in this issue [18, 21]. Finally, it is shown how to incorporate additional orientational degrees of freedom within the PFC approach to model liquid crystals [22]. On the DFT side, the other papers in this special issue deal with problems associated with advanced DFT techniques and applications. The existence of a structural instability in sub-critical crystalline fluctuations in a supercooled liquid within a square-gradient theory is discussed in [23]. Fundamental measure theory for hard-body systems is improved by discussing a correction term in detail, as discussed in [24]. A mean-field-like density functional for charges is applied to the effective interaction between charged colloids obtained within a cell model [25]. The remaining articles provide fundamental insight into how to supplement DDFT-type methods with hydrodynamics [26, 27], highlight the role of the projection operator technique in deriving dynamical density functional theories [28], and demonstrate how perturbation methods can be employed to compute the properties of solid-liquid interfaces [29]. This particular collection of papers demonstrates rather convincingly the significant potential that classical density functional techniques possess in modeling complex systems built of either soft or hard matter (or combinations thereof). While the PFC approach offers a simple and appealing means to simulate

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.

Adiabaticity and gravity theory independent conservation laws for cosmological perturbations

Science.gov (United States)

Romano, Antonio Enea; Mooij, Sander; Sasaki, Misao

2016-04-01

We carefully study the implications of adiabaticity for the behavior of cosmological perturbations. There are essentially three similar but different definitions of non-adiabaticity: one is appropriate for a thermodynamic fluid δPnad, another is for a general matter field δPc,nad, and the last one is valid only on superhorizon scales. The first two definitions coincide if cs2 = cw2 where cs is the propagation speed of the perturbation, while cw2 = P ˙ / ρ ˙ . Assuming the adiabaticity in the general sense, δPc,nad = 0, we derive a relation between the lapse function in the comoving slicing Ac and δPnad valid for arbitrary matter field in any theory of gravity, by using only momentum conservation. The relation implies that as long as cs ≠cw, the uniform density, comoving and the proper-time slicings coincide approximately for any gravity theory and for any matter field if δPnad = 0 approximately. In the case of general relativity this gives the equivalence between the comoving curvature perturbation Rc and the uniform density curvature perturbation ζ on superhorizon scales, and their conservation. This is realized on superhorizon scales in standard slow-roll inflation. We then consider an example in which cw =cs, where δPnad = δPc,nad = 0 exactly, but the equivalence between Rc and ζ no longer holds. Namely we consider the so-called ultra slow-roll inflation. In this case both Rc and ζ are not conserved. In particular, as for ζ, we find that it is crucial to take into account the next-to-leading order term in ζ's spatial gradient expansion to show its non-conservation, even on superhorizon scales. This is an example of the fact that adiabaticity (in the thermodynamic sense) is not always enough to ensure the conservation of Rc or ζ.

Site-occupation embedding theory using Bethe ansatz local density approximations

Science.gov (United States)

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

2018-06-01

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

Perturbation theory in large order

International Nuclear Information System (INIS)

Bender, C.M.

1978-01-01

For many quantum mechanical models, the behavior of perturbation theory in large order is strikingly simple. For example, in the quantum anharmonic oscillator, which is defined by -y'' + (x 2 /4 + ex 4 /4 - E) y = 0, y ( +- infinity) = 0, the perturbation coefficients, A/sub n/, in the expansion for the ground-state energy, E(ground state) approx. EPSILON/sub n = 0//sup infinity/ A/sub n/epsilon/sup n/, simplify dramatically as n → infinity: A/sub n/ approx. (6/π 3 )/sup 1/2/(-3)/sup n/GAMMA(n + 1/2). Methods of applied mathematics are used to investigate the nature of perturbation theory in quantum mechanics and show that its large-order behavior is determined by the semiclassical content of the theory. In quantum field theory the perturbation coefficients are computed by summing Feynman graphs. A statistical procedure in a simple lambda phi 4 model for summing the set of all graphs as the number of vertices → infinity is presented. Finally, the connection between the large-order behavior of perturbation theory in quantum electrodynamics and the value of α, the charge on the electron, is discussed. 7 figures

Perturbation theories for the dipolar fluids

International Nuclear Information System (INIS)

Lee, L.L.; Chung, T.H.

1983-01-01

We derive here four different perturbation equations for the calculation of the angular pair correlation functions of dipolar fluids; namely, the first order y-expansion, the modified Percus--Yevik (MPY) expansion, the modified hypernetted chain (MHNC) expansion, and the modified linearized hypernetted chain (MLHNC) equation. Both the method of the functional expansion and the method of the cluster integrals are utilized. Comparison with other perturbation theories (e.g., the Melnyk--Smith equation) is made. While none of the theories is exact, as shown by the cluster diagrams, the MLHNC and the MHNC contain more diagrams than, say, the MPY and y-expansion. The y-expansion equation can be improved by including the correction terms to the Kirkwood superposition approximation for the triplet correlation function. For example, the inclusion of the correction term rho∫d4h(14)h(24)h(34) in a formula given by Henderson, is shown to improve substantially the y-expansion equation. We examine the performance of two of the theories: the y-expansion and the MLHNC equation for a Stockmayer (dipolar) fluid with a reduced dipole moment μ/sup asterisk2/ [ = μ 2 /(epsilonsigma 3 )] = 1.0. Comparison with Monte Carlo simulation results of Adams et al. and with other theories (e.g., the QHNC equation) shows that our results are reasonable. Further improvements of the equations are also pointed out

Perturbation theory in light-cone gauge

International Nuclear Information System (INIS)

Vianello, Eliana

2000-01-01

Perturbation calculations are presented for the light-cone gauge Schwinger model. Eigenstates can be calculated perturbatively but the perturbation theory is nonstandard. We hope to extend the work to QCD 2 to resolve some outstanding issues in those theories

Green’s functions for spin boson systems: Beyond conventional perturbation theories

Energy Technology Data Exchange (ETDEWEB)

Liu, Junjie [State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433 (China); Xu, Hui [Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China); Wu, Chang-Qin [State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433 (China); Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China)

2016-12-20

Unraveling general properties of Green’s functions of quantum dissipative systems is of both experimental relevance and theoretical interest. Here, we study the spin-boson model as a prototype. By utilizing the Majorana-fermion representation together with the polaron transformation, we establish a theoretical approach to analyze Green’s functions of the spin-boson model. In contrast to conventional perturbation theories either in the tunneling energy or in the system-bath coupling strength, the proposed scheme gives reliable results over wide regimes of the coupling strength, bias, as well as temperature. To demonstrate the utility of the approach, we consider the susceptibility as well as the symmetrized spin correlation function (SSCF) which can be expressed in terms of Green’s functions. Thorough investigations are made on systems embedded in Ohmic or sub-Ohmic bosonic baths. We found the so-obtained SSCF is the same as that of the non-interacting blip approximation (NIBA) in unbiased systems while it is applicable for a wider range of temperature in the biased systems compared with the NIBA. We also show that a previous perturbation result is recovered as a weak coupling limit of the so-obtained SSCF. Furthermore, by studying the quantum criticality of the susceptibility, we confirm the validity of the quantum-to-classical mapping in the whole sub-Ohmic regime.

Comparisons of perturbation and integral equation theories for the angular pair correlation function in molecular fluids

International Nuclear Information System (INIS)

Murad, S.; Gubbins, K.E.; Gray, C.G.

1983-01-01

We compare several recently proposed theories for the angular pair correlation function g(rω 1 ω 2 ), including first- and second-order perturbation theory (the u-expansion), a Pade approximant to this series, first-order f-expansion, the single superchain, generalized mean field, linearized hypernetted chain, and quadratic hypernetted chain approximations. Numerical results from these theories are compared with available computer simulation data for four model fluids whose intermolecular pair potential is of the form u 0 +usub(a), where u 0 is a hard-sphere of Lennard-Jones model, while usub(a) is a dipole-dipole or quadrupole-quadrupole interaction; we refer to these model fluids as HS+μμ, HS+QQ, LJ+μμ, and LJ+QQ. Properties studied include the angular pair correlation function and its spherical harmonic components, the thermodynamic properties, and the angular correlation parameters G 1 and G 2 that are related to the dielectric and Kerr constants. The second-order perturbation theory is superior to the integral equation theories for the thermodynamic harmonics of g(rω 1 ω 2 ) and for the thermodynamic properties themselves at moderate multipole strengths. For other harmonics and properties, the integral equation theories are better, with the quadratic hypernetted chain approximation being the best overall. (orig.)

Perturbation theory and coupling constant analyticity in two-dimensional field theories

International Nuclear Information System (INIS)

Simon, B.

1973-01-01

Conjectural material and results over a year old are presented in the discussion of perturbation theory and coupling constant analyticity in two-dimensional field theories. General properties of perturbation series are discussed rather than questions of field theory. The question is interesting for two reasons: First, one would like to understand why perturbation theory is such a good guide (to show that perturbation theory determines the theory in some way). Secondly, one hopes to prove that some or all of the theories are nontrivial. (U.S.)

Second-Order Moller-Plesset Perturbation Theory for Molecular Dirac-Hartree-Fock Wave Functions

Science.gov (United States)

Dyall, Kenneth G.; Arnold, James O. (Technical Monitor)

1994-01-01

Moller-Plesset perturbation theory is developed to second order for a selection of Kramers restricted Dirac-Hartree-Fock closed and open-shell reference wave functions. The open-shell wave functions considered are limited to those with no more than two electrons in open shells, but include the case of a two-configuration SCF reference. Denominator shifts are included in the style of Davidson's OPT2 method. An implementation which uses unordered integrals with labels is presented, and results are given for a few test cases.

Wilson loops to 20th order numerical stochastic perturbation theory

Energy Technology Data Exchange (ETDEWEB)

Horsley, R. [Edinburgh Univ. (United Kingdom). School of Physics; Hotzel, G.; Perlt, H.; Schiller, A. [Leipzig Univ. (Germany). Inst. fuer Theoretische Physik; Ilgenfritz, E.M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Physik; Joint Institute for Nuclear Research, VBLHEP, Dubna (Russian Federation); Millo, R.; Rakow, P.E.L. [Liverpool Univ. (Germany). Theoretical Physics Div.; Nakamura, Y. [RIKEN Advanced Institute for Computational Science, Kobe, Hyogo (Japan); Schierholz, G. [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)

2012-05-15

We calculate Wilson loops of various sizes up to 20 loops in SU(3) pure lattice gauge theory at different lattice sizes for Wilson gauge action using the technique of numerical stochastic perturbation theory. This allows us to investigate the perturbative series for various Wilson loops at high loop orders. We observe differences in the behavior of those series as function of the loop order. Up to n=20 we do not find evidence for the factorial growth of the expansion coefficients often assumed to characterize an asymptotic series. Based on the actually observed behavior we sum the series in a model parametrized by hypergeometric functions. Alternatively we estimate the total series in boosted perturbation theory using information from the first 14 loops. We introduce generalized ratios of Wilson loops of different sizes. Together with the corresponding Wilson loops from standard Monte Carlo measurements they enable us to assess their non-perturbative parts.

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.

Extended multi-configuration quasi-degenerate perturbation theory: the new approach to multi-state multi-reference perturbation theory.

Science.gov (United States)

Granovsky, Alexander A

2011-06-07

The distinctive desirable features, both mathematically and physically meaningful, for all partially contracted multi-state multi-reference perturbation theories (MS-MR-PT) are explicitly formulated. The original approach to MS-MR-PT theory, called extended multi-configuration quasi-degenerate perturbation theory (XMCQDPT), having most, if not all, of the desirable properties is introduced. The new method is applied at the second order of perturbation theory (XMCQDPT2) to the 1(1)A(')-2(1)A(') conical intersection in allene molecule, the avoided crossing in LiF molecule, and the 1(1)A(1) to 2(1)A(1) electronic transition in cis-1,3-butadiene. The new theory has several advantages compared to those of well-established approaches, such as second order multi-configuration quasi-degenerate perturbation theory and multi-state-second order complete active space perturbation theory. The analysis of the prevalent approaches to the MS-MR-PT theory performed within the framework of the XMCQDPT theory unveils the origin of their common inherent problems. We describe the efficient implementation strategy that makes XMCQDPT2 an especially useful general-purpose tool in the high-level modeling of small to large molecular systems. © 2011 American Institute of Physics

Perturbation theory via Feynman diagrams in classical mechanics

OpenAIRE

Penco, R.; Mauro, D.

2006-01-01

In this paper we show how Feynman diagrams, which are used as a tool to implement perturbation theory in quantum field theory, can be very useful also in classical mechanics, provided we introduce also at the classical level concepts like path integrals and generating functionals.

A simple extrapolation of thermodynamic perturbation theory to infinite order

International Nuclear Information System (INIS)

Ghobadi, Ahmadreza F.; Elliott, J. Richard

2015-01-01

Recent analyses of the third and fourth order perturbation contributions to the equations of state for square well spheres and Lennard-Jones chains show trends that persist across orders and molecular models. In particular, the ratio between orders (e.g., A 3 /A 2 , where A i is the ith order perturbation contribution) exhibits a peak when plotted with respect to density. The trend resembles a Gaussian curve with the peak near the critical density. This observation can form the basis for a simple recursion and extrapolation from the highest available order to infinite order. The resulting extrapolation is analytic and therefore cannot fully characterize the critical region, but it remarkably improves accuracy, especially for the binodal curve. Whereas a second order theory is typically accurate for the binodal at temperatures within 90% of the critical temperature, the extrapolated result is accurate to within 99% of the critical temperature. In addition to square well spheres and Lennard-Jones chains, we demonstrate how the method can be applied semi-empirically to the Perturbed Chain - Statistical Associating Fluid Theory (PC-SAFT)

Generalized perturbation theory (GPT) methods. A heuristic approach

International Nuclear Information System (INIS)

Gandini, A.

1987-01-01

Wigner first proposed a perturbation theory as early as 1945 to study fundamental quantities such as the reactivity worths of different materials. The first formulation, CPT, for conventional perturbation theory is based on universal quantum mechanics concepts. Since that early conception, significant contributions have been made to CPT, in particular, Soodak, who rendered a heuristic interpretation of the adjoint function, (referred to as the GPT method for generalized perturbation theory). The author illustrates the GPT methodology in a variety of linear and nonlinear domains encountered in nuclear reactor analysis. The author begins with the familiar linear neutron field and then generalizes the methodology to other linear and nonlinear fields, using heuristic arguments. The author believes that the inherent simplicity and elegance of the heuristic derivation, although intended here for reactor physics problems might be usefully adopted in collateral fields and includes such examples

Singular perturbation theory for interacting fermions in two dimensions

International Nuclear Information System (INIS)

Chubukov, A.V.; Maslov, D.L.; Gangadharaiah, S.; Glazman, L.I.

2004-11-01

We consider a system of interacting fermions in two dimensions beyond the second-order perturbation theory in the interaction. It is shown that the mass-shell singularities in the self-energy, arising already at the second order of the perturbation theory, manifest a nonperturbative effect: an interaction with the zero-sound mode. Resuming the perturbation theory for a weak, short-range interaction and accounting for a finite curvature of the fermion spectrum, we eliminate the singularities and obtain the results for the quasi-particle self-energy and the spectral function to all orders in the interaction with the zero-sound mode. A threshold for emission of zero-sound waves leads a non-monotonic variation of the self-energy with energy (or momentum) near the mass shell. Consequently, the spectral function has a kink-like feature. We also study in detail a non-analytic temperature dependence of the specific heat, C(T) ∝T 2 . It turns out that although the interaction with the collective mode results in an enhancement of the fermion self-energy, this interaction does not affect the non-analytic term in C(T) due to a subtle cancellation between the contributions from the real and imaginary parts of the self-energy. For a short-range and weak interaction, this implies that the second-order perturbation theory suffices to determine the non-analytic part of C(T). We also obtain a general form of the non-analytic term in C(T), valid for the case of a generic Fermi liquid, i.e., beyond the perturbation theory. (author)

Calculation of the exchange coupling constants of copper binuclear systems based on spin-flip constricted variational density functional theory.

Science.gov (United States)

Zhekova, Hristina R; Seth, Michael; Ziegler, Tom

2011-11-14

We have recently developed a methodology for the calculation of exchange coupling constants J in weakly interacting polynuclear metal clusters. The method is based on unrestricted and restricted second order spin-flip constricted variational density functional theory (SF-CV(2)-DFT) and is here applied to eight binuclear copper systems. Comparison of the SF-CV(2)-DFT results with experiment and with results obtained from other DFT and wave function based methods has been made. Restricted SF-CV(2)-DFT with the BH&HLYP functional yields consistently J values in excellent agreement with experiment. The results acquired from this scheme are comparable in quality to those obtained by accurate multi-reference wave function methodologies such as difference dedicated configuration interaction and the complete active space with second-order perturbation theory. © 2011 American Institute of Physics

Internal wave energy flux from density perturbations in nonlinear stratifications

Science.gov (United States)

Lee, Frank M.; Allshouse, Michael R.; Swinney, Harry L.; Morrison, P. J.

2017-11-01

Tidal flow over the topography at the bottom of the ocean, whose density varies with depth, generates internal gravity waves that have a significant impact on the energy budget of the ocean. Thus, understanding the energy flux (J = p v) is important, but it is difficult to measure simultaneously the pressure and velocity perturbation fields, p and v . In a previous work, a Green's-function-based method was developed to calculate the instantaneous p, v , and thus J , given a density perturbation field for a constant buoyancy frequency N. Here we extend the previous analytic Green's function work to include nonuniform N profiles, namely the tanh-shaped and linear cases, because background density stratifications that occur in the ocean and some experiments are nonlinear. In addition, we present a finite-difference method for the general case where N has an arbitrary profile. Each method is validated against numerical simulations. The methods we present can be applied to measured density perturbation data by using our MATLAB graphical user interface EnergyFlux. PJM was supported by the U.S. Department of Energy Contract DE-FG05-80ET-53088. HLS and MRA were supported by ONR Grant No. N000141110701.

Distribution function approach to redshift space distortions. Part V: perturbation theory applied to dark matter halos

Energy Technology Data Exchange (ETDEWEB)

Vlah, Zvonimir; Seljak, Uroš [Institute for Theoretical Physics, University of Zürich, Zürich (Switzerland); Okumura, Teppei [Institute for the Early Universe, Ewha Womans University, Seoul, S. Korea (Korea, Republic of); Desjacques, Vincent, E-mail: zvlah@physik.uzh.ch, E-mail: seljak@physik.uzh.ch, E-mail: teppei@ewha.ac.kr, E-mail: Vincent.Desjacques@unige.ch [Département de Physique Théorique and Center for Astroparticle Physics (CAP) Université de Genéve, Genéve (Switzerland)

2013-10-01

Numerical simulations show that redshift space distortions (RSD) introduce strong scale dependence in the power spectra of halos, with ten percent deviations relative to linear theory predictions even on relatively large scales (k < 0.1h/Mpc) and even in the absence of satellites (which induce Fingers-of-God, FoG, effects). If unmodeled these effects prevent one from extracting cosmological information from RSD surveys. In this paper we use Eulerian perturbation theory (PT) and Eulerian halo biasing model and apply it to the distribution function approach to RSD, in which RSD is decomposed into several correlators of density weighted velocity moments. We model each of these correlators using PT and compare the results to simulations over a wide range of halo masses and redshifts. We find that with an introduction of a physically motivated halo biasing, and using dark matter power spectra from simulations, we can reproduce the simulation results at a percent level on scales up to k ∼ 0.15h/Mpc at z = 0, without the need to have free FoG parameters in the model.

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)

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

Perturbation theory with instantons

International Nuclear Information System (INIS)

Carruthers, P.; Pinsky, S.S.; Zachariasen, F.

1977-05-01

''Perturbation theory'' rules are developed for calculating the effect of instantons in a pure Yang-Mills theory with no fermions, in the ''dilute gas'' approximation in which the N-instanton solution is assumed to be the sum of N widely separated one-instanton solutions. These rules are then used to compute the gluon propagator and proper vertex function including all orders of the instanton interaction but only to lowest order in the gluon coupling. It is to be expected that such an approximation is valid only for momenta q larger than the physical mass μ. The result is that in this regime instantons cause variations in the propagator and vertex of the form (μ 2 /q 2 )/sup -8π 2 b/ where b is the coefficient in the expansion of the β function: β = bg 3 +...

Generalized chiral perturbation theory

International Nuclear Information System (INIS)

Knecht, M.; Stern, J.

1994-01-01

The Generalized Chiral Perturbation Theory enlarges the framework of the standard χPT (Chiral Perturbation Theory), relaxing certain assumptions which do not necessarily follow from QCD or from experiment, and which are crucial for the usual formulation of the low energy expansion. In this way, experimental tests of the foundations of the standard χPT become possible. Emphasis is put on physical aspects rather than on formal developments of GχPT. (author). 31 refs

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

Science.gov (United States)

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

2009-10-29

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

Regular perturbation theory for two-electron atoms

International Nuclear Information System (INIS)

Feranchuk, I.D.; Triguk, V.V.

2011-01-01

Regular perturbation theory (RPT) for the ground and excited states of two-electron atoms or ions is developed. It is shown for the first time that summation of the matrix elements from the electron-electron interaction operator over all intermediate states can be calculated in a closed form by means of the two-particle Coulomb Green's function constructed in the Letter. It is shown that the second order approximation of RPT includes the main part of the correlation energy both for the ground and excited states. This approach can be also useful for description of two-electron atoms in external fields. -- Highlights: → We develop regular perturbation theory for the two-electron atoms or ions. → We calculate the sum of the matrix elements over all intermediate states. → We construct the two-particle Coulomb Green's function.

Cumulants in perturbation expansions for non-equilibrium field theory

International Nuclear Information System (INIS)

Fauser, R.

1995-11-01

The formulation of perturbation expansions for a quantum field theory of strongly interacting systems in a general non-equilibrium state is discussed. Non-vanishing initial correlations are included in the formulation of the perturbation expansion in terms of cumulants. The cumulants are shown to be the suitable candidate for summing up the perturbation expansion. Also a linked-cluster theorem for the perturbation series with cumulants is presented. Finally a generating functional of the perturbation series with initial correlations is studied. We apply the methods to a simple model of a fermion-boson system. (orig.)

Development of New Open-Shell Perturbation and Coupled-Cluster Theories Based on Symmetric Spin Orbitals

Science.gov (United States)

Lee, Timothy J.; Arnold, James O. (Technical Monitor)

1994-01-01

A new spin orbital basis is employed in the development of efficient open-shell coupled-cluster and perturbation theories that are based on a restricted Hartree-Fock (RHF) reference function. The spin orbital basis differs from the standard one in the spin functions that are associated with the singly occupied spatial orbital. The occupied orbital (in the spin orbital basis) is assigned the delta(+) = 1/square root of 2(alpha+Beta) spin function while the unoccupied orbital is assigned the delta(-) = 1/square root of 2(alpha-Beta) spin function. The doubly occupied and unoccupied orbitals (in the reference function) are assigned the standard alpha and Beta spin functions. The coupled-cluster and perturbation theory wave functions based on this set of "symmetric spin orbitals" exhibit much more symmetry than those based on the standard spin orbital basis. This, together with interacting space arguments, leads to a dramatic reduction in the computational cost for both coupled-cluster and perturbation theory. Additionally, perturbation theory based on "symmetric spin orbitals" obeys Brillouin's theorem provided that spin and spatial excitations are both considered. Other properties of the coupled-cluster and perturbation theory wave functions and models will be discussed.

Geometric Hamiltonian structures and perturbation theory

International Nuclear Information System (INIS)

Omohundro, S.

1984-08-01

We have been engaged in a program of investigating the Hamiltonian structure of the various perturbation theories used in practice. We describe the geometry of a Hamiltonian structure for non-singular perturbation theory applied to Hamiltonian systems on symplectic manifolds and the connection with singular perturbation techniques based on the method of averaging

Lattice regularized chiral perturbation theory

International Nuclear Information System (INIS)

Borasoy, Bugra; Lewis, Randy; Ouimet, Pierre-Philippe A.

2004-01-01

Chiral perturbation theory can be defined and regularized on a spacetime lattice. A few motivations are discussed here, and an explicit lattice Lagrangian is reviewed. A particular aspect of the connection between lattice chiral perturbation theory and lattice QCD is explored through a study of the Wess-Zumino-Witten term

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....

Analytical energy gradients for explicitly correlated wave functions. I. Explicitly correlated second-order Møller-Plesset perturbation theory

Science.gov (United States)

Győrffy, Werner; Knizia, Gerald; Werner, Hans-Joachim

2017-12-01

We present the theory and algorithms for computing analytical energy gradients for explicitly correlated second-order Møller-Plesset perturbation theory (MP2-F12). The main difficulty in F12 gradient theory arises from the large number of two-electron integrals for which effective two-body density matrices and integral derivatives need to be calculated. For efficiency, the density fitting approximation is used for evaluating all two-electron integrals and their derivatives. The accuracies of various previously proposed MP2-F12 approximations [3C, 3C(HY1), 3*C(HY1), and 3*A] are demonstrated by computing equilibrium geometries for a set of molecules containing first- and second-row elements, using double-ζ to quintuple-ζ basis sets. Generally, the convergence of the bond lengths and angles with respect to the basis set size is strongly improved by the F12 treatment, and augmented triple-ζ basis sets are sufficient to closely approach the basis set limit. The results obtained with the different approximations differ only very slightly. This paper is the first step towards analytical gradients for coupled-cluster singles and doubles with perturbative treatment of triple excitations, which will be presented in the second part of this series.

The statistics of maxima in primordial density perturbations

International Nuclear Information System (INIS)

Peacock, J.A.; Heavens, A.F.

1985-01-01

An investigation has been made of the hypothesis that protogalaxies/protoclusters form at the sites of maxima in a primordial field of normally distributed density perturbations. Using a mixture of analytic and numerical techniques, the properties of the maxima, have been studied. The results provide a natural mechanism for biased galaxy formation in which galaxies do not necessarily follow the large-scale density. Methods for obtained the true autocorrelation function of the density field and implications for Microwave Background studies are discussed. (author)

Application of perturbation theory to lattice calculations based on method of cyclic characteristics

Science.gov (United States)

Assawaroongruengchot, Monchai

computing time when both direct and adjoint solutions are required. A problem that arises for the generalized adjoint problem is that the direct use of the negative external generalized adjoint sources in the adjoint solution algorithm results in negative generalized adjoint functions. A coupled flux biasing/decontamination scheme is applied to make the generalized adjoint functions positive using the adjoint functions in such a way that it can be used for the multigroup rebalance technique. Next we consider the application of the perturbation theory to the reactor problems. Since the coolant void reactivity (CVR) is a important factor in reactor safety analysis, we have decided to select this parameter for optimization studies. We consider the optimization and adjoint sensitivity techniques for the adjustments of CVR at beginning of burnup cycle (BOC) and k eff at end of burnup cycle (EOC) for a 2D Advanced CANDU Reactor (ACR) lattice. The sensitivity coefficients are evaluated using the perturbation theory based on the integral transport equations. Three sets of parameters for CVR-BOC and keff-EOC adjustments are studied: (1) Dysprosium density in the central pin with Uranium enrichment in the outer fuel rings, (2) Dysprosium density and Uranium enrichment both in the central pin, and (3) the same parameters as in the first case but the objective is to obtain a negative checkerboard CVR at beginning of cycle (CBCVR-BOC). To approximate the sensitivity coefficient at EOC, we perform constant-power burnup/depletion calculations for 600 full power days (FPD) using a slightly perturbed nuclear library and the unperturbed neutron fluxes to estimate the variation of nuclide densities at EOC. Sensitivity analyses of CVR and eigenvalue are included in the study. In addition the optimization and adjoint sensitivity techniques are applied to the CBCVR-BOC and keff-EOC adjustment of the ACR lattices with Gadolinium in the central pin. Finally we apply these techniques to the CVR

Application of perturbation theory to lattice calculations based on method of cyclic characteristics

Energy Technology Data Exchange (ETDEWEB)

Assawaroongruengchot, M

2007-07-01

computing time when both direct and adjoint solutions are required. A problem that arises for the generalized adjoint problem is that the direct use of the negative external generalized adjoint sources in the adjoint solution algorithm results in negative generalized adjoint functions. A coupled flux biasing/decontamination scheme is applied to make the generalized adjoint functions positive using the adjoint functions in such a way that it can be used for the multigroup rebalance technique. Next we consider the application of the perturbation theory to the reactor problems. Since the coolant void reactivity (CVR) is a important factor in reactor safety analysis, we have decided to select this parameter for optimization studies. We consider the optimization and adjoint sensitivity techniques for the adjustments of CVR at beginning of burnup cycle (BOC) and k{sub eff} at end of burnup cycle (EOC) for a 2D Advanced CANDU Reactor (ACR) lattice. The sensitivity coefficients are evaluated using the perturbation theory based on the integral transport equations. Three sets of parameters for CVR-BOC and k{sub eff}-EOC adjustments are studied: (1) Dysprosium density in the central pin with Uranium enrichment in the outer fuel rings, (2) Dysprosium density and Uranium enrichment both in the central pin, and (3) the same parameters as in the first case but the objective is to obtain a negative checkerboard CVR at beginning of cycle (CBCVR-BOC). To approximate the sensitivity coefficient at EOC, we perform constant-power burnup/depletion calculations for 600 full power days (FPD) using a slightly perturbed nuclear library and the unperturbed neutron fluxes to estimate the variation of nuclide densities at EOC. Sensitivity analyses of CVR and eigenvalue are included in the study. In addition the optimization and adjoint sensitivity techniques are applied to the CBCVR-BOC and k{sub eff}-EOC adjustment of the ACR lattices with Gadolinium in the central pin. Finally we apply these

Application of perturbation theory to lattice calculations based on method of cyclic characteristics

International Nuclear Information System (INIS)

Assawaroongruengchot, M.

2007-01-01

computing time when both direct and adjoint solutions are required. A problem that arises for the generalized adjoint problem is that the direct use of the negative external generalized adjoint sources in the adjoint solution algorithm results in negative generalized adjoint functions. A coupled flux biasing/decontamination scheme is applied to make the generalized adjoint functions positive using the adjoint functions in such a way that it can be used for the multigroup rebalance technique. Next we consider the application of the perturbation theory to the reactor problems. Since the coolant void reactivity (CVR) is a important factor in reactor safety analysis, we have decided to select this parameter for optimization studies. We consider the optimization and adjoint sensitivity techniques for the adjustments of CVR at beginning of burnup cycle (BOC) and k eff at end of burnup cycle (EOC) for a 2D Advanced CANDU Reactor (ACR) lattice. The sensitivity coefficients are evaluated using the perturbation theory based on the integral transport equations. Three sets of parameters for CVR-BOC and k eff -EOC adjustments are studied: (1) Dysprosium density in the central pin with Uranium enrichment in the outer fuel rings, (2) Dysprosium density and Uranium enrichment both in the central pin, and (3) the same parameters as in the first case but the objective is to obtain a negative checkerboard CVR at beginning of cycle (CBCVR-BOC). To approximate the sensitivity coefficient at EOC, we perform constant-power burnup/depletion calculations for 600 full power days (FPD) using a slightly perturbed nuclear library and the unperturbed neutron fluxes to estimate the variation of nuclide densities at EOC. Sensitivity analyses of CVR and eigenvalue are included in the study. In addition the optimization and adjoint sensitivity techniques are applied to the CBCVR-BOC and k eff -EOC adjustment of the ACR lattices with Gadolinium in the central pin. Finally we apply these techniques to the CVR

Orbitally invariant internally contracted multireference unitary coupled cluster theory and its perturbative approximation: theory and test calculations of second order approximation.

Science.gov (United States)

Chen, Zhenhua; Hoffmann, Mark R

2012-07-07

A unitary wave operator, exp (G), G(+) = -G, is considered to transform a multiconfigurational reference wave function Φ to the potentially exact, within basis set limit, wave function Ψ = exp (G)Φ. To obtain a useful approximation, the Hausdorff expansion of the similarity transformed effective Hamiltonian, exp (-G)Hexp (G), is truncated at second order and the excitation manifold is limited; an additional separate perturbation approximation can also be made. In the perturbation approximation, which we refer to as multireference unitary second-order perturbation theory (MRUPT2), the Hamiltonian operator in the highest order commutator is approximated by a Mo̸ller-Plesset-type one-body zero-order Hamiltonian. If a complete active space self-consistent field wave function is used as reference, then the energy is invariant under orbital rotations within the inactive, active, and virtual orbital subspaces for both the second-order unitary coupled cluster method and its perturbative approximation. Furthermore, the redundancies of the excitation operators are addressed in a novel way, which is potentially more efficient compared to the usual full diagonalization of the metric of the excited configurations. Despite the loss of rigorous size-extensivity possibly due to the use of a variational approach rather than a projective one in the solution of the amplitudes, test calculations show that the size-extensivity errors are very small. Compared to other internally contracted multireference perturbation theories, MRUPT2 only needs reduced density matrices up to three-body even with a non-complete active space reference wave function when two-body excitations within the active orbital subspace are involved in the wave operator, exp (G). Both the coupled cluster and perturbation theory variants are amenable to large, incomplete model spaces. Applications to some widely studied model systems that can be problematic because of geometry dependent quasidegeneracy, H4, P4

Continual integral in perturbation theory

International Nuclear Information System (INIS)

Slavnov, A.A.

1975-01-01

It is shown that all results obtained by means of continual integration within the framework of perturbation theory are completely equivalent to those obtained by the usual diagram technique and are therfore just as rigorous. A rigorous justification is given for the rules for operating with continual integrals in perturbation theory. (author)

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)

Adapting SAFT-γ perturbation theory to site-based molecular dynamics simulation. II. Confined fluids and vapor-liquid interfaces

International Nuclear Information System (INIS)

Ghobadi, Ahmadreza F.; Elliott, J. Richard

2014-01-01

In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-γ WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-γ refers to the particular form of “statistical associating fluid theory” that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH 2 and CH 3 and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ∼2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ∼1% from simulation data while the theory reproduces

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.

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

International Nuclear Information System (INIS)

Cafiero, Mauricio; Gonzalez, Carlos

2005-01-01

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

Perturbation theory of effective Hamiltonians

International Nuclear Information System (INIS)

Brandow, B.H.

1975-01-01

This paper constitutes a review of the many papers which have used perturbation theory to derive ''effective'' or ''model'' Hamiltonians. It begins with a brief review of nondegenerate and non-many-body perturbation theory, and then considers the degenerate but non-many-body problem in some detail. It turns out that the degenerate perturbation problem is not uniquely defined, but there are some practical criteria for choosing among the various possibilities. Finally, the literature dealing with the linked-cluster aspects of open-shell many-body systems is reviewed. (U.S.)

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

Science.gov (United States)

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

2018-01-01

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

Non-Perturbative Asymptotic Improvement of Perturbation Theory and Mellin-Barnes Representation

Directory of Open Access Journals (Sweden)

Samuel Friot

2010-10-01

Full Text Available Using a method mixing Mellin-Barnes representation and Borel resummation we show how to obtain hyperasymptotic expansions from the (divergent formal power series which follow from the perturbative evaluation of arbitrary ''N-point'' functions for the simple case of zero-dimensional φ4 field theory. This hyperasymptotic improvement appears from an iterative procedure, based on inverse factorial expansions, and gives birth to interwoven non-perturbative partial sums whose coefficients are related to the perturbative ones by an interesting resurgence phenomenon. It is a non-perturbative improvement in the sense that, for some optimal truncations of the partial sums, the remainder at a given hyperasymptotic level is exponentially suppressed compared to the remainder at the preceding hyperasymptotic level. The Mellin-Barnes representation allows our results to be automatically valid for a wide range of the phase of the complex coupling constant, including Stokes lines. A numerical analysis is performed to emphasize the improved accuracy that this method allows to reach compared to the usual perturbative approach, and the importance of hyperasymptotic optimal truncation schemes.

Application of functional analysis to perturbation theory of differential equations. [nonlinear perturbation of the harmonic oscillator

Science.gov (United States)

Bogdan, V. M.; Bond, V. B.

1980-01-01

The deviation of the solution of the differential equation y' = f(t, y), y(O) = y sub O from the solution of the perturbed system z' = f(t, z) + g(t, z), z(O) = z sub O was investigated for the case where f and g are continuous functions on I x R sup n into R sup n, where I = (o, a) or I = (o, infinity). These functions are assumed to satisfy the Lipschitz condition in the variable z. The space Lip(I) of all such functions with suitable norms forms a Banach space. By introducing a suitable norm in the space of continuous functions C(I), introducing the problem can be reduced to an equivalent problem in terminology of operators in such spaces. A theorem on existence and uniqueness of the solution is presented by means of Banach space technique. Norm estimates on the rate of growth of such solutions are found. As a consequence, estimates of deviation of a solution due to perturbation are obtained. Continuity of the solution on the initial data and on the perturbation is established. A nonlinear perturbation of the harmonic oscillator is considered a perturbation of equations of the restricted three body problem linearized at libration point.

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

Directory of Open Access Journals (Sweden)

V. Sergiievskyi

2017-12-01

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

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.

Supersymmetry restoration in superstring perturbation theory

International Nuclear Information System (INIS)

Sen, Ashoke

2015-01-01

Superstring perturbation theory based on the 1PI effective theory approach has been useful for addressing the problem of mass renormalization and vacuum shift. We derive Ward identities associated with space-time supersymmetry transformation in this approach. This leads to a proof of the equality of renormalized masses of bosons and fermions and identities relating fermionic amplitudes to bosonic amplitudes after taking into account the effect of mass renormalization. This also relates unbroken supersymmetry to a given order in perturbation theory to absence of tadpoles of massless scalars to higher order. The results are valid at the perturbative vacuum as well as in the shifted vacuum when the latter describes the correct ground state of the theory. We apply this to SO(32) heterotic string theory on Calabi-Yau 3-folds where a one loop Fayet-Iliopoulos term apparently breaks supersymmetry at one loop, but analysis of the low energy effective field theory indicates that there is a nearby vacuum where supersymmetry is restored. We explicitly prove that the perturbative amplitudes of this theory around the shifted vacuum indeed satisfy the Ward identities associated with unbroken supersymmetry. We also test the general arguments by explicitly verifying the equality of bosonic and fermionic masses at one loop order in the shifted vacuum, and the appearance of two loop dilaton tadpole in the perturbative vacuum where supersymmetry is expected to be broken.

Supersymmetry restoration in superstring perturbation theory

Energy Technology Data Exchange (ETDEWEB)

Sen, Ashoke [Harish-Chandra Research Institute,Chhatnag Road, Jhusi, Allahabad 211019 (India)

2015-12-14

Superstring perturbation theory based on the 1PI effective theory approach has been useful for addressing the problem of mass renormalization and vacuum shift. We derive Ward identities associated with space-time supersymmetry transformation in this approach. This leads to a proof of the equality of renormalized masses of bosons and fermions and identities relating fermionic amplitudes to bosonic amplitudes after taking into account the effect of mass renormalization. This also relates unbroken supersymmetry to a given order in perturbation theory to absence of tadpoles of massless scalars to higher order. The results are valid at the perturbative vacuum as well as in the shifted vacuum when the latter describes the correct ground state of the theory. We apply this to SO(32) heterotic string theory on Calabi-Yau 3-folds where a one loop Fayet-Iliopoulos term apparently breaks supersymmetry at one loop, but analysis of the low energy effective field theory indicates that there is a nearby vacuum where supersymmetry is restored. We explicitly prove that the perturbative amplitudes of this theory around the shifted vacuum indeed satisfy the Ward identities associated with unbroken supersymmetry. We also test the general arguments by explicitly verifying the equality of bosonic and fermionic masses at one loop order in the shifted vacuum, and the appearance of two loop dilaton tadpole in the perturbative vacuum where supersymmetry is expected to be broken.

Magnetizability and rotational g tensors for density fitted local second-order Møller-Plesset perturbation theory using gauge-including atomic orbitals

International Nuclear Information System (INIS)

Loibl, Stefan; Schütz, Martin

2014-01-01

In this paper, we present theory and implementation of an efficient program for calculating magnetizabilities and rotational g tensors of closed-shell molecules at the level of local second-order Møller-Plesset perturbation theory (MP2) using London orbitals. Density fitting is employed to factorize the electron repulsion integrals with ordinary Gaussians as fitting functions. The presented program for the calculation of magnetizabilities and rotational g tensors is based on a previous implementation of NMR shielding tensors reported by S. Loibl and M. Schütz [J. Chem. Phys. 137, 084107 (2012)]. Extensive test calculations show (i) that the errors introduced by density fitting are negligible, and (ii) that the errors of the local approximation are still rather small, although larger than for nuclear magnetic resonance (NMR) shielding tensors. Electron correlation effects for magnetizabilities are tiny for most of the molecules considered here. MP2 appears to overestimate the correlation contribution of magnetizabilities such that it does not constitute an improvement over Hartree-Fock (when comparing to higher-order methods like CCSD(T)). For rotational g tensors the situation is different and MP2 provides a significant improvement in accuracy over Hartree-Fock. The computational performance of the new program was tested for two extended systems, the larger comprising about 2200 basis functions. It turns out that a magnetizability (or rotational g tensor) calculation takes about 1.5 times longer than a corresponding NMR shielding tensor calculation

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

Science.gov (United States)

Guidez, Emilie B; Gordon, Mark S

2015-03-12

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

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

Adapting SAFT-γ perturbation theory to site-based molecular dynamics simulation. II. Confined fluids and vapor-liquid interfaces

Science.gov (United States)

Ghobadi, Ahmadreza F.; Elliott, J. Richard

2014-07-01

In this work, a new classical density functional theory is developed for group-contribution equations of state (EOS). Details of implementation are demonstrated for the recently-developed SAFT-γ WCA EOS and selective applications are studied for confined fluids and vapor-liquid interfaces. The acronym WCA (Weeks-Chandler-Andersen) refers to the characterization of the reference part of the third-order thermodynamic perturbation theory applied in formulating the EOS. SAFT-γ refers to the particular form of "statistical associating fluid theory" that is applied to the fused-sphere, heteronuclear, united-atom molecular models of interest. For the monomer term, the modified fundamental measure theory is extended to WCA-spheres. A new chain functional is also introduced for fused and soft heteronuclear chains. The attractive interactions are taken into account by considering the structure of the fluid, thus elevating the theory beyond the mean field approximation. The fluctuations of energy are also included via a non-local third-order perturbation theory. The theory includes resolution of the density profiles of individual groups such as CH2 and CH3 and satisfies stoichiometric constraints for the density profiles. New molecular simulations are conducted to demonstrate the accuracy of each Helmholtz free energy contribution in reproducing the microstructure of inhomogeneous systems at the united-atom level of coarse graining. At each stage, comparisons are made to assess where the present theory stands relative to the current state of the art for studying inhomogeneous fluids. Overall, it is shown that the characteristic features of real molecular fluids are captured both qualitatively and quantitatively. For example, the average pore density deviates ˜2% from simulation data for attractive pentadecane in a 2-nm slit pore. Another example is the surface tension of ethane/heptane mixture, which deviates ˜1% from simulation data while the theory reproduces the excess

Perturbation theory of a symmetric center within Liénard equations

Science.gov (United States)

Françoise, Jean-Pierre; Xiao, Dongmei

2015-09-01

In this article, we introduce the use of Lambert function to develop further the global perturbation theory of an integrable Liénard equation which displays a symmetric center. We prove a global Morse lemma for the first integral and deduce the existence of an associated Picard-Fuchs system. We revisit previous contributions to first-order perturbation theory with the help of these new analytic techniques and in particular, we check that the fundamental integrals are linearly independent. The Lambert function allows to find an expansion formula for these integrals. We also study the possibility to develop a higher-order perturbation theory. The algorithm of the successive derivatives works in general in the class of analytic functions on the domain D where the level sets of the first integral are ovals. We end the article with some results on the first integral of a symmetric Liénard equation deduced from the algorithm of successive derivatives.

Advances in heuristically based generalized perturbation theory

International Nuclear Information System (INIS)

Gandini, A.

1994-01-01

A distinctive feature of heuristically based generalized perturbation theory methodology consists in the systematic use of importance conservation concepts. As well known, this use leads to fundamental reciprocity relationship. Instead, the alternative variational and differential one approaches make a consistent use of the properties and adjoint functions. The equivalence between the importance and the adjoint functions have been demonstrated in important cases. There are some instances, however, in which the commonly known operator governing the adjoint function are not adequate. In this paper ways proposed to generalize this rules, as adopted with the heuristic generalized perturbation theory methodology, are illustrated. When applied to the neutron/nuclide field characterizing the core evolution in a power reactor system, in which also an intensive control variable (ρ) is defined, these rules leas to an orthogonality relationship connected to this same control variable. A set of ρ-mode eigenfunctions may be correspondingly defined and an extended concept of reactivity (generalizing that commonly associated with the multiplication factor) proposed as more directly indicative of the controllability of a critical reactor system. (author). 25 refs

Statistical theory of electron densities

International Nuclear Information System (INIS)

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

1988-01-01

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

Density perturbations in a braneworld universe with dark radiation

International Nuclear Information System (INIS)

Gumjudpai, Burin; Maartens, Roy; Gordon, Christopher

2003-01-01

We investigate the effects on cosmological density perturbations of dark radiation in a Randall-Sundrum 2-type braneworld. Dark radiation in the background is limited by observational constraints to be a small fraction of the radiation energy density, but it has an interesting qualitative effect in the radiation era. On large scales, it serves to slightly suppress the radiation density perturbations at late times, while boosting the perturbations in dark radiation. In a kinetic (stiff) era, the suppression is much stronger, and drives the density perturbations to zero

Operator Decomposition Framework for Perturbation Theory

Energy Technology Data Exchange (ETDEWEB)

Abdel-Khalik, Hany S.; Wang, Congjian; Bang, Young Suk [North Carolina State University, Raleigh (United States)

2012-05-15

This summary describes a new framework for perturbation theory intended to improve its performance, in terms of the associated computational cost and the complexity of implementation, for routine reactor calculations in support of design, analysis, and regulation. Since its first introduction in reactor analysis by Winger, perturbation theory has assumed an aura of sophistication with regard to its implementation and its capabilities. Only few reactor physicists, typically mathematically proficient, have contributed to its development, with the general body of the nuclear engineering community remaining unaware of its current status, capabilities, and challenges. Given its perceived sophistication and the small body of community users, the application of perturbation theory has been limited to investigatory analyses only. It is safe to say that the nuclear community is split into two groups, a small one which understands the theory and, and a much bigger group with the perceived notion that perturbation theory is nothing but a fancy mathematical approach that has very little use in practice. Over the past three years, research has demonstrated two goals. First, reduce the computational cost of perturbation theory in order to enable its use for routine reactor calculations. Second, expose some of the myth about perturbation theory and present it in a form that is simple and relatable in order to stimulate the interest of nuclear practitioners, especially those who are currently working on the development of next generation reactor design and analysis tools. The operator decomposition approach has its roots in linear algebra and can be easily understood by code developers, especially those involved in the design of iterative numerical solution strategies

Intermolecular symmetry-adapted perturbation theory study of large organic complexes

International Nuclear Information System (INIS)

Heßelmann, Andreas; Korona, Tatiana

2014-01-01

Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atom-atom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies

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

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

Science.gov (United States)

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

2017-09-21

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

Quenched Chiral Perturbation Theory to one loop

NARCIS (Netherlands)

Colangelo, G.; Pallante, E.

The divergences of the generating functional of quenched Chiral Perturbation theory (qCHPT) to one loop are computed in closed form. We show how the quenched chiral logarithms can be reabsorbed in the renormalization of the B0 parameter of the leading order Lagrangian. Finally, we do the chiral

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.

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

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.

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...

Spectral zeta function and non-perturbative effects in ABJM Fermi-gas

International Nuclear Information System (INIS)

Hatsuda, Yasuyuki

2015-03-01

The exact partition function in ABJM theory on three-sphere can be regarded as a canonical partition function of a non-interacting Fermi-gas with an unconventional Hamiltonian. All the information on the partition function is encoded in the discrete spectrum of this Hamiltonian. We explain how (quantum mechanical) non-perturbative corrections in the Fermi-gas system appear from a spectral consideration. Basic tools in our analysis are a Mellin-Barnes type integral representation and a spectral zeta function. From a consistency with known results, we conjecture that the spectral zeta function in the ABJM Fermi-gas has an infinite number of ''non-perturbative'' poles, which are invisible in the semi-classical expansion of the Planck constant. We observe that these poles indeed appear after summing up perturbative corrections. As a consequence, the perturbative resummation of the spectral zeta function causes non-perturbative corrections to the grand canonical partition function. We also present another example associated with a spectral problem in topological string theory. A conjectured non-perturbative free energy on the resolved conifold is successfully reproduced in this framework.

Density-functional theory simulation of large quantum dots

Science.gov (United States)

Jiang, Hong; Baranger, Harold U.; Yang, Weitao

2003-10-01

Kohn-Sham spin-density functional theory provides an efficient and accurate model to study electron-electron interaction effects in quantum dots, but its application to large systems is a challenge. Here an efficient method for the simulation of quantum dots using density-function theory is developed; it includes the particle-in-the-box representation of the Kohn-Sham orbitals, an efficient conjugate-gradient method to directly minimize the total energy, a Fourier convolution approach for the calculation of the Hartree potential, and a simplified multigrid technique to accelerate the convergence. We test the methodology in a two-dimensional model system and show that numerical studies of large quantum dots with several hundred electrons become computationally affordable. In the noninteracting limit, the classical dynamics of the system we study can be continuously varied from integrable to fully chaotic. The qualitative difference in the noninteracting classical dynamics has an effect on the quantum properties of the interacting system: integrable classical dynamics leads to higher-spin states and a broader distribution of spacing between Coulomb blockade peaks.

't Hooft loops and perturbation theory

CERN Document Server

De Forcrand, Philippe; Noth, D; Forcrand, Philippe de; Lucini, Biagio; Noth, David

2005-01-01

We show that high-temperature perturbation theory describes extremely well the area law of SU(N) spatial 't Hooft loops, or equivalently the tension of the interface between different Z_N vacua in the deconfined phase. For SU(2), the disagreement between Monte Carlo data and lattice perturbation theory for sigma(T)/T^2 is less than 2%, down to temperatures O(10) T_c. For SU(N), N>3, the ratios of interface tensions, (sigma_k/sigma_1)(T), agree with perturbation theory, which predicts tiny deviations from the ratio of Casimirs, down to nearly T_c. In contrast, individual tensions differ markedly from the perturbative expression. In all cases, the required precision Monte Carlo measurements are made possible by a simple but powerful modification of the 'snake' algorithm.

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

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.)

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.)

Local and linear chemical reactivity response functions at finite temperature in density functional theory

International Nuclear Information System (INIS)

Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L.; Vela, Alberto

2015-01-01

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

S-duality invariant perturbation theory improved by holography

Energy Technology Data Exchange (ETDEWEB)

Chowdhury, Abhishek [Harish-Chandra Research Institute,Chhatnag Road, Jhusi, Allahabad 211019 (India); Honda, Masazumi [Department of Particle Physics and Astrophysics,Weizmann Institute of Science, Rehovot 7610001 (Israel); Thakur, Somyadip [Tata Institute of Fundamental Research,Mumbai 400005 (India)

2017-04-26

We study anomalous dimensions of unprotected low twist operators in the four-dimensional SU (N)N=4 supersymmetric Yang-Mills theory. We construct a class of interpolating functions to approximate the dimensions of the leading twist operators for arbitrary gauge coupling τ. The interpolating functions are consistent with previous results on the perturbation theory, holographic computation and full S-duality. We use our interpolating functions to test a recent conjecture by the N=4 superconformal bootstrap that upper bounds on the dimensions are saturated at one of the duality-invariant points τ=i and τ=e{sup iπ/3}. It turns out that our interpolating functions have maximum at τ=e{sup iπ/3}, which are close to the conjectural values by the conformal bootstrap. In terms of the interpolating functions, we draw the image of conformal manifold in the space of the dimensions. We find that the image is almost a line despite the conformal manifold is two-dimensional. We also construct interpolating functions for the subleading twist operator and study level crossing phenomenon between the leading and subleading twist operators. Finally we study the dimension of the Konishi operator in the planar limit. We find that our interpolating functions match with numerical result obtained by Thermodynamic Bethe Ansatz very well. It turns out that analytic properties of the interpolating functions reflect an expectation on a radius of convergence of the perturbation theory.

Inclusion of Dispersion Effects in Density Functional Theory

DEFF Research Database (Denmark)

Møgelhøj, Andreas

on fitting to high-level ab initio and experimental results. The fitting scheme, based on Baysian theory, focuses on the three aspects: a) model space, b) datasets, and c) model selection. The model space consists of a flexible expansion of the exchange enhancement factor in the generalized gradient......In this thesis, applications and development will be presented within the field of van der Waals interactions in density functional theory. The thesis is based on the three projects: i) van der Waals interactions effect on the structure of liquid water at ambient conditions, ii) development......-range van der Waals interactions is essential to describe the adsorption/desorption process and commonly used generalized gradient approximation functionals are seen to be incapable of this....

Perturbative spacetimes from Yang-Mills theory

Energy Technology Data Exchange (ETDEWEB)

Luna, Andrés [School of Physics and Astronomy, University of Glasgow,Glasgow G12 8QQ, Scotland (United Kingdom); Monteiro, Ricardo [Theoretical Physics Department, CERN,Geneva (Switzerland); Nicholson, Isobel; Ochirov, Alexander; O’Connell, Donal [Higgs Centre for Theoretical Physics,School of Physics and Astronomy, The University of Edinburgh,Edinburgh EH9 3JZ, Scotland (United Kingdom); Westerberg, Niclas [Institute of Photonics and Quantum Sciences,School of Engineering and Physical Sciences, Heriot-Watt University,Edinburgh (United Kingdom); Higgs Centre for Theoretical Physics,School of Physics and Astronomy, The University of Edinburgh,Edinburgh EH9 3JZ, Scotland (United Kingdom); White, Chris D. [Centre for Research in String Theory,School of Physics and Astronomy, Queen Mary University of London,327 Mile End Road, London E1 4NS (United Kingdom)

2017-04-12

The double copy relates scattering amplitudes in gauge and gravity theories. In this paper, we expand the scope of the double copy to construct spacetime metrics through a systematic perturbative expansion. The perturbative procedure is based on direct calculation in Yang-Mills theory, followed by squaring the numerator of certain perturbative diagrams as specified by the double-copy algorithm. The simplest spherically symmetric, stationary spacetime from the point of view of this procedure is a particular member of the Janis-Newman-Winicour family of naked singularities. Our work paves the way for applications of the double copy to physically interesting problems such as perturbative black-hole scattering.

International Workshop on Electronic Density Functional Theory : Recent Progress and New Directions

CERN Document Server

Vignale, Giovanni; Das, Mukunda

1998-01-01

This book is an outcome of the International Workshop on Electronic Density Functional Theory, held at Griffith University in Brisbane, Australia, in July 1996. Density functional theory, standing as it does at the boundary between the disciplines of physics, chemistry, and materials science, is a great mixer. Invited experts from North America, Europe, and Australia mingled with students from several disciplines, rapidly taking up the informal style for which Australia is famous. A list of participants is given at the end of the book. Density functional theory (DFT) is a subtle approach to the very difficult problem of predicting the behavior of many interacting particles. A major application is the study of many-electron systems. This was the workshop theme, embracing inter alia computational chemistry and condensed matter physics. DFT circumvents the more conceptually straightforward (but more computationally intensive) approach in which one solves the many-body Schrodinger equation. It relies instead on r...

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...

Variational cluster perturbation theory for Bose-Hubbard models

International Nuclear Information System (INIS)

Koller, W; Dupuis, N

2006-01-01

We discuss the application of the variational cluster perturbation theory (VCPT) to the Mott-insulator-to-superfluid transition in the Bose-Hubbard model. We show how the VCPT can be formulated in such a way that it gives a translation invariant excitation spectrum-free of spurious gaps-despite the fact that it formally breaks translation invariance. The phase diagram and the single-particle Green function in the insulating phase are obtained for one-dimensional systems. When the chemical potential of the cluster is taken as a variational parameter, the VCPT reproduces the dimensional dependence of the phase diagram even for one-site clusters. We find a good quantitative agreement with the results of the density-matrix renormalization group when the number of sites in the cluster becomes of order 10. The extension of the method to the superfluid phase is discussed

A-centers in silicon studied with hybrid density functional theory

KAUST Repository

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

2013-01-01

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

A-centers in silicon studied with hybrid density functional theory

KAUST Repository

Wang, Hao

2013-07-29

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

Perturbation Theory for Open Two-Level Nonlinear Quantum Systems

International Nuclear Information System (INIS)

Zhang Zhijie; Jiang Dongguang; Wang Wei

2011-01-01

Perturbation theory is an important tool in quantum mechanics. In this paper, we extend the traditional perturbation theory to open nonlinear two-level systems, treating decoherence parameter γ as a perturbation. By this virtue, we give a perturbative solution to the master equation, which describes a nonlinear open quantum system. The results show that for small decoherence rate γ, the ratio of the nonlinear rate C to the tunneling coefficient V (i.e., r = C/V) determines the validity of the perturbation theory. For small ratio r, the perturbation theory is valid, otherwise it yields wrong results. (general)

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

International Nuclear Information System (INIS)

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

2017-01-01

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

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

Science.gov (United States)

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

2017-03-01

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

Time-Sliced Perturbation Theory for Large Scale Structure I: General Formalism

CERN Document Server

Blas, Diego; Ivanov, Mikhail M.; Sibiryakov, Sergey

2016-01-01

We present a new analytic approach to describe large scale structure formation in the mildly non-linear regime. The central object of the method is the time-dependent probability distribution function generating correlators of the cosmological observables at a given moment of time. Expanding the distribution function around the Gaussian weight we formulate a perturbative technique to calculate non-linear corrections to cosmological correlators, similar to the diagrammatic expansion in a three-dimensional Euclidean quantum field theory, with time playing the role of an external parameter. For the physically relevant case of cold dark matter in an Einstein--de Sitter universe, the time evolution of the distribution function can be found exactly and is encapsulated by a time-dependent coupling constant controlling the perturbative expansion. We show that all building blocks of the expansion are free from spurious infrared enhanced contributions that plague the standard cosmological perturbation theory. This pave...

Algebraic quantum field theory, perturbation theory, and the loop expansion

International Nuclear Information System (INIS)

Duetsch, M.; Fredenhagen, K.

2001-01-01

The perturbative treatment of quantum field theory is formulated within the framework of algebraic quantum field theory. We show that the algebra of interacting fields is additive, i.e. fully determined by its subalgebras associated to arbitrary small subregions of Minkowski space. We also give an algebraic formulation of the loop expansion by introducing a projective system A (n) of observables ''up to n loops'', where A (0) is the Poisson algebra of the classical field theory. Finally we give a local algebraic formulation for two cases of the quantum action principle and compare it with the usual formulation in terms of Green's functions. (orig.)

Higher order perturbation theory - An example for discussion

International Nuclear Information System (INIS)

Lewins, J.D.; Parks, G.; Babb, A.L.

1986-01-01

Higher order perturbation theory is developed in the form of a Taylor series expansion to third order to calculate the thermal utilization of a nonuniform cell. The development takes advantage of the self-adjoint property of the diffusion operator to provide a simple development of this illustration of generalized perturbation theory employing scalar perturbation parameters. The results show how a designer might employ a second-order theory to quantify proposed design improvements, together with the limitations of second- and third-order theory. The chosen example has an exact optimization solution and thus provides a clear understanding of the role of perturbation theory at its various orders. Convergence and the computational advantages and disadvantages of the method are discussed

New perturbative approach to renormalizable field theories

International Nuclear Information System (INIS)

Dhar, A.; Gupta, V.

1984-01-01

A new method for obtaining perturbative predictions in quantum field theory is developed. Our method gives finite predictions, which are free from scheme ambiguities, for any quantity of interest (like a cross section or a Green's function) starting directly from the bare regularized Lagrangian. The central idea in our approach is to incorporate directly the consequences of dimensional transmutation for the predictions of the theory. We thus completely bypass the conventional renormalization procedure and the ambiguities associated with it. The case of massless theories with a single dimensionless coupling constant is treated in detail to illustrate our approach

Probing non-perturbative effects in M-theory

International Nuclear Information System (INIS)

Hatsuda, Yasuyuki; Okuyama, Kazumi

2014-07-01

The AdS/CFT correspondence enables us to probe M-theory on various backgrounds from the corresponding dual gauge theories. Here we investigate in detail a three-dimensional U(N) N=4 super Yang-Mills theory coupled to one adjoint hypermultiplet and N f fundamental hypermultiplets, which is large N dual to M-theory on AdS 4 x S 7 /Z N f . Using the localization and the Fermi-gas formulation, we explore non-perturbative corrections to the partition function. As in the ABJM theory, we find that there exists a non-trivial pole cancellation mechanism, which guarantees the theory to be well-defined, between worldsheet instantons and membrane instantons for all rational (in particular, physical or integral) values of N f .

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 ...

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.

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

Quantum field theory with a momentum space of constant curvature (perturbation theory)

International Nuclear Information System (INIS)

Mir-Kasimov, R.M.

1978-01-01

In the framework of the field-theoretical approach in which the off-the-mass shell extension proceeds in the p-space of constant curvature, the perburbation theory is developed. The configurational representation of the de Sitter space is introduced with the help of the Fourier transformation of the group of motions. On the basis of a natural generalization of the Bogolyubov causality condition to the case of the new configurational representation a perturbation theory is constructed with the local in xi space Lagrangian density fucntion. The obtained S matrix obeys the reguirement of translation invariance. The S matrix elements are given by convergent expressions

Instantaneous stochastic perturbation theory

International Nuclear Information System (INIS)

Lüscher, Martin

2015-01-01

A form of stochastic perturbation theory is described, where the representative stochastic fields are generated instantaneously rather than through a Markov process. The correctness of the procedure is established to all orders of the expansion and for a wide class of field theories that includes all common formulations of lattice QCD.

On perturbation theory for distance dependent statistics.

Energy Technology Data Exchange (ETDEWEB)

Mashkevich, S V

1994-12-31

It is known that perturbation theory for anyons has to be modified near Bose statistics in order to get correct finite results. For ``distance dependent statistics`` or anyons with smeared flux tubes, perturbation theory is in principle applicable directly but gives results which hold for too small values of the statistical parameter and, in particular, are not valid as the flux tube radius tends to zero. In this paper we discuss the way to modify perturbation theory for this situation, which allows to obtain the appropriate results. (author). 6 refs.

Perturbation theory and nonperturbative effects: a happy marriage?

International Nuclear Information System (INIS)

Chyla, J.

1992-01-01

Perturbation expansions in renormalized quantum theories are reformulated in a way that permits a straightforward handling of situations when in the conventional approach, i.e. in fixed renormalization scheme, these expansions are factorially divergent and even of asymptotically constant sign. The result takes the form of convergent (under certain circumstances) expansions in a set of functions Z k (a,χ) of the couplant and the free parameter χ specifies the procedure involved. The value of χ is shown to be correlated to the basic properties of nonperturbative effects as embodied in power corrections. A close connection of this procedure to the Borel summation technique is demonstrated and its relation to conventional perturbation theory in fixed renormalization schemes elucidated. (author) 3 figs., 17 refs

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

DEFF Research Database (Denmark)

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

2013-01-01

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

Generalized Møller-Plesset Multiconfiguration Perturbation Theory Applied to an Open-Shell Antisymmetric Product of Strongly Orthogonal Geminals Reference Wave Function.

Science.gov (United States)

Tarumi, Moto; Kobayashi, Masato; Nakai, Hiromi

2012-11-13

The antisymmetric product of strongly orthogonal geminals (APSG) method is a wave function theory that can effectively treat the static electron correlation. Recently, we proposed the open-shell APSG method using one-electron orbitals for open-shell parts. In this paper, we have extended the perturbation correction to the open-shell APSG calculations through Møller-Plesset-type multiconfiguration perturbation theory (MP-MCPT). Numerical applications demonstrate that the present open-shell MP-MCPT can reasonably reproduce the dissociation energies or equilibrium distances for open-shell systems.

Gluon and ghost correlation functions of 2-color QCD at finite density

Science.gov (United States)

Hajizadeh, Ouraman; Boz, Tamer; Maas, Axel; Skullerud, Jon-Ivar

2018-03-01

2-color QCD, i. e. QCD with the gauge group SU(2), is the simplest non-Abelian gauge theory without sign problem at finite quark density. Therefore its study on the lattice is a benchmark for other non-perturbative approaches at finite density. To provide such benchmarks we determine the minimal-Landau-gauge 2-point and 3-gluon correlation functions of the gauge sector and the running gauge coupling at finite density. We observe no significant effects, except for some low-momentum screening of the gluons at and above the supposed high-density phase transition.

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

Non-perturbative unitarity constraints on the ratio of shear viscosity to entropy density in UV complete theories with a gravity dual

CERN Document Server

Brustein, Ram

2011-01-01

We reconsider, from a novel perspective, how unitarity constrains the corrections to the ratio of shear viscosity \\eta\\ to entropy density s. We start with higher-derivative extensions of Einstein gravity in asymptotically anti-de Sitter spacetimes. It is assumed that these theories are derived from string theory and thus have a unitary UV completion that is dual to a unitary, UV-complete boundary gauge theory. We then propose that the gravitational perturbations about a solution of the UV complete theory are described by an effective theory whose linearized equations of motion have at most two time derivatives. Our proposal leads to a concrete prescription for the calculation of \\eta/s for theories of gravity with arbitrary higher-derivative corrections. The resulting ratio can take on values above or below 1/4\\pi\\ and is consistent with all the previous calculations, even though our reasoning is substantially different. For the purpose of calculating \\eta/s, our proposal also leads to only two possible cand...

Perturbation theory for the effective diffusion constant in a medium of random scatterers

International Nuclear Information System (INIS)

Dean, D S; Drummond, I T; Horgan, R R; Lefevre, A

2004-01-01

We develop perturbation theory and physically motivated resummations of the perturbation theory for the problem of a tracer particle diffusing in a random medium. The random medium contains point scatterers of density ρ uniformly distributed throughout the material. The tracer is a Langevin particle subjected to the quenched random force generated by the scatterers. Via our perturbative analysis, we determine when the random potential can be approximated by a Gaussian random potential. We also develop a self-similar renormalization group approach based on thinning out the scatterers; this scheme is similar to that used with success for diffusion in Gaussian random potentials and agrees with known exact results. To assess the accuracy of this approximation scheme, its predictions are confronted with results obtained by numerical simulation

Matter density perturbations in modified gravity models with arbitrary coupling between matter and geometry

DEFF Research Database (Denmark)

Nesseris, Savvas

2009-01-01

We consider theories with an arbitrary coupling between matter and gravity and obtain the perturbation equation of matter on subhorizon scales. Also, we derive the effective gravitational constant $G_{eff}$ and two parameters $\\Sigma$ and $\\eta$, which along with the perturbation equation...... of the matter density are useful to constrain the theory from growth factor and weak lensing observations. Finally, we use a completely solvable toy model which exhibits nontrivial phenomenology to investigate specific features of the theory. We obtain the analytic solution of the modified Friedmann equation...... for the scale factor $a$ in terms of time $t$ and use the age of the oldest star clusters and the primordial nucleosynthesis bounds in order to constrain the parameters of our toy model....

Matter density perturbations in modified gravity models with arbitrary coupling between matter and geometry

International Nuclear Information System (INIS)

Nesseris, Savvas

2009-01-01

We consider theories with an arbitrary coupling between matter and gravity and obtain the perturbation equation of matter on subhorizon scales. Also, we derive the effective gravitational constant G eff and two parameters Σ and η, which along with the perturbation equation of the matter density are useful to constrain the theory from growth factor and weak lensing observations. Finally, we use a completely solvable toy model which exhibits nontrivial phenomenology to investigate specific features of the theory. We obtain the analytic solution of the modified Friedmann equation for the scale factor a in terms of time t and use the age of the oldest star clusters and the primordial nucleosynthesis bounds in order to constrain the parameters of our toy model.

Time-sliced perturbation theory for large scale structure I: general formalism

Energy Technology Data Exchange (ETDEWEB)

Blas, Diego; Garny, Mathias; Sibiryakov, Sergey [Theory Division, CERN, CH-1211 Genève 23 (Switzerland); Ivanov, Mikhail M., E-mail: diego.blas@cern.ch, E-mail: mathias.garny@cern.ch, E-mail: mikhail.ivanov@cern.ch, E-mail: sergey.sibiryakov@cern.ch [FSB/ITP/LPPC, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne (Switzerland)

2016-07-01

We present a new analytic approach to describe large scale structure formation in the mildly non-linear regime. The central object of the method is the time-dependent probability distribution function generating correlators of the cosmological observables at a given moment of time. Expanding the distribution function around the Gaussian weight we formulate a perturbative technique to calculate non-linear corrections to cosmological correlators, similar to the diagrammatic expansion in a three-dimensional Euclidean quantum field theory, with time playing the role of an external parameter. For the physically relevant case of cold dark matter in an Einstein-de Sitter universe, the time evolution of the distribution function can be found exactly and is encapsulated by a time-dependent coupling constant controlling the perturbative expansion. We show that all building blocks of the expansion are free from spurious infrared enhanced contributions that plague the standard cosmological perturbation theory. This paves the way towards the systematic resummation of infrared effects in large scale structure formation. We also argue that the approach proposed here provides a natural framework to account for the influence of short-scale dynamics on larger scales along the lines of effective field theory.

Perturbation theory and collision probability formalism. Vol. 2

Energy Technology Data Exchange (ETDEWEB)

Nasr, M [National Center for Nuclear Safety and Radiation Control, Atomic Energy Authority, Cairo (Egypt)

1996-03-01

Perturbation theory is commonly used in evaluating the activity effects, particularly those resulting from small and localized perturbation in multiplying media., e.g. in small sample reactivity measurements. The Boltzmann integral transport equation is generally used for evaluating the direct and adjoint fluxes in the heterogenous lattice cells to be used in the perturbation equations. When applying perturbation theory in this formalism, a term involving the perturbation effects on the special transfer kernel arises. This term is difficult to evaluate correctly, since it involves an integration all over the entire system. The main advantage of the perturbation theory which is the limitation of the integration procedure on the perturbation region is found to be of no practical use in such cases. In the present work, the perturbation equation in the collision probability formalism is analyzed. A mathematical treatment of the term in question is performed. A new mathematical expression for this term is derived. The new expression which can be estimated easily is derived.

Spin orientations of the spin-half Ir(4+) ions in Sr3NiIrO6, Sr2IrO4, and Na2IrO3: Density functional, perturbation theory, and Madelung potential analyses.

Science.gov (United States)

Gordon, Elijah E; Xiang, Hongjun; Köhler, Jürgen; Whangbo, Myung-Hwan

2016-03-21

The spins of the low-spin Ir(4+) (S = 1/2, d(5)) ions at the octahedral sites of the oxides Sr3NiIrO6, Sr2IrO4, and Na2IrO3 exhibit preferred orientations with respect to their IrO6 octahedra. We evaluated the magnetic anisotropies of these S = 1/2 ions on the basis of density functional theory (DFT) calculations including spin-orbit coupling (SOC), and probed their origin by performing perturbation theory analyses with SOC as perturbation within the LS coupling scheme. The observed spin orientations of Sr3NiIrO6 and Sr2IrO4 are correctly predicted by DFT calculations, and are accounted for by the perturbation theory analysis. As for the spin orientation of Na2IrO3, both experimental studies and DFT calculations have not been unequivocal. Our analysis reveals that the Ir(4+) spin orientation of Na2IrO3 should have nonzero components along the c- and a-axis directions. The spin orientations determined by DFT calculations are sensitive to the accuracy of the crystal structures employed, which is explained by perturbation theory analyses when interactions between adjacent Ir(4+) ions are taken into consideration. There are indications implying that the 5d electrons of Na2IrO3 are less strongly localized compared with those of Sr3NiIrO6 and Sr2IrO4. This implication was confirmed by showing that the Madelung potentials of the Ir(4+) ions are less negative in Na2IrO3 than in Sr3NiIrO6 and Sr2IrO4. Most transition-metal S = 1/2 ions do have magnetic anisotropies because the SOC induces interactions among their crystal-field split d-states, and the associated mixing of the states modifies only the orbital parts of the states. This finding cannot be mimicked by a spin Hamiltonian because this model Hamiltonian lacks the orbital degree of freedom, thereby leading to the spin-half syndrome. The spin-orbital entanglement for the 5d spin-half ions Ir(4+) is not as strong as has been assumed.

Geometry-based density functional theory an overview

CERN Document Server

Schmidt, M

2003-01-01

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

Geometry-based density functional theory: an overview

Science.gov (United States)

Schmidt, Matthias

2003-01-01

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

Geometry-based density functional theory: an overview

International Nuclear Information System (INIS)

Schmidt, Matthias

2003-01-01

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

String perturbation theory diverges

International Nuclear Information System (INIS)

Gross, D.J.; Periwal, V.

1988-01-01

We prove that perturbation theory for the bosonic string diverges for arbitrary values of the coupling constant and is not Borel summable. This divergence is independent of the existence of the infinities that occur in the theory due to the presence of tachyons and dilaton tadpoles. We discuss the physical implications of such a divergence

Reducing Systematic Errors in Oxide Species with Density Functional Theory Calculations

DEFF Research Database (Denmark)

Christensen, Rune; Hummelshøj, Jens S.; Hansen, Heine Anton

2015-01-01

Density functional theory calculations can be used to gain valuable insight into the fundamental reaction processes in metal−oxygen systems, e.g., metal−oxygen batteries. Here, the ability of a range of different exchange-correlation functionals to reproduce experimental enthalpies of formation...

Perturbative coherence in field theory

International Nuclear Information System (INIS)

Aldrovandi, R.; Kraenkel, R.A.

1987-01-01

A general condition for coherent quantization by perturbative methods is given, because the basic field equations of a fild theory are not always derivable from a Lagrangian. It's seen that non-lagrangian models way have well defined vertices, provided they satisfy what they call the 'coherence condition', which is less stringent than the condition for the existence of a Lagrangian. They note that Lagrangian theories are perturbatively coherent, in the sense that they have well defined vertices, and that they satisfy automatically that condition. (G.D.F.) [pt

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

Science.gov (United States)

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

2014-06-05

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

2nd derivatives of the electronic energy in density functional theory

Energy Technology Data Exchange (ETDEWEB)

Dam, H. van

2001-08-01

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

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

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

The spectrum of density perturbations in an expanding universe

Science.gov (United States)

Silk, J.

1974-01-01

The basic dynamic equations that govern the evolution of perturbations in a Friedmann-Lemaitre universe are derived. General solutions describing the evolution of adiabatic perturbations in the density of matter are obtained, and the choice of the appropriate initial conditions is examined. The various perturbation modes are compared, and the effects of decoupling on the perturbation spectrum are studied. The scheme used to follow the evolution of density perturbations through decoupling is based on an extension of the Eddington approximation to the radiative transfer equation, and is strictly valid in both optically thick and thin limits.

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

Directory of Open Access Journals (Sweden)

M. M.

2000-12-01

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

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.

A global numerical solution of the radial Schroedinger equation by second-order perturbation theory

International Nuclear Information System (INIS)

Adam, G.

1979-01-01

A global numerical method, which uses second-order perturbation theory, is described for the solution of the radial Schroedinger equation. The perturbative numerical (PN) solution is derived in two stages: first, the original potential is approximated by a piecewise continuous parabolic function, and second, the resulting Schroedinger equation is solved on each integration step by second-order perturbation theory, starting with a step function reference approximation for the parabolic potential. We get a manageable PN algorithm, which shows an order of accuracy equal to six in the solution of the original Schroedinger equation, and is very stable against round off errors. (author)

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.

Spin Density Distribution in Open-Shell Transition Metal Systems: A Comparative Post-Hartree-Fock, Density Functional Theory, and Quantum Monte Carlo Study of the CuCl2 Molecule.

Science.gov (United States)

Caffarel, Michel; Giner, Emmanuel; Scemama, Anthony; Ramírez-Solís, Alejandro

2014-12-09

We present a comparative study of the spatial distribution of the spin density of the ground state of CuCl2 using Density Functional Theory (DFT), quantum Monte Carlo (QMC), and post-Hartree-Fock wave function theory (WFT). A number of studies have shown that an accurate description of the electronic structure of the lowest-lying states of this molecule is particularly challenging due to the interplay between the strong dynamical correlation effects in the 3d shell and the delocalization of the 3d hole over the chlorine atoms. More generally, this problem is representative of the difficulties encountered when studying open-shell metal-containing molecular systems. Here, it is shown that qualitatively different results for the spin density distribution are obtained from the various quantum-mechanical approaches. At the DFT level, the spin density distribution is found to be very dependent on the functional employed. At the QMC level, Fixed-Node Diffusion Monte Carlo (FN-DMC) results are strongly dependent on the nodal structure of the trial wave function. Regarding wave function methods, most approaches not including a very high amount of dynamic correlation effects lead to a much too high localization of the spin density on the copper atom, in sharp contrast with DFT. To shed some light on these conflicting results Full CI-type (FCI) calculations using the 6-31G basis set and based on a selection process of the most important determinants, the so-called CIPSI approach (Configuration Interaction with Perturbative Selection done Iteratively) are performed. Quite remarkably, it is found that for this 63-electron molecule and a full CI space including about 10(18) determinants, the FCI limit can almost be reached. Putting all results together, a natural and coherent picture for the spin distribution is proposed.

Effective field theory of cosmological perturbations

International Nuclear Information System (INIS)

Piazza, Federico; Vernizzi, Filippo

2013-01-01

The effective field theory of cosmological perturbations stems from considering a cosmological background solution as a state displaying spontaneous breaking of time translations and (adiabatic) perturbations as the related Nambu–Goldstone modes. With this insight, one can systematically develop a theory for the cosmological perturbations during inflation and, with minor modifications, also describe in full generality the gravitational interactions of dark energy, which are relevant for late-time cosmology. The formalism displays a unique set of Lagrangian operators containing an increasing number of cosmological perturbations and derivatives. We give an introductory description of the unitary gauge formalism for theories with broken gauge symmetry—that allows us to write down the most general Lagrangian—and of the Stückelberg ‘trick’—that allows to recover gauge invariance and to make the scalar field explicit. We show how to apply this formalism to gravity and cosmology and we reproduce the detailed analysis of the action in the ADM variables. We also review some basic applications to inflation and dark energy. (paper)

Effective field theory of cosmological perturbations

Science.gov (United States)

Piazza, Federico; Vernizzi, Filippo

2013-11-01

The effective field theory of cosmological perturbations stems from considering a cosmological background solution as a state displaying spontaneous breaking of time translations and (adiabatic) perturbations as the related Nambu-Goldstone modes. With this insight, one can systematically develop a theory for the cosmological perturbations during inflation and, with minor modifications, also describe in full generality the gravitational interactions of dark energy, which are relevant for late-time cosmology. The formalism displays a unique set of Lagrangian operators containing an increasing number of cosmological perturbations and derivatives. We give an introductory description of the unitary gauge formalism for theories with broken gauge symmetry—that allows us to write down the most general Lagrangian—and of the Stückelberg ‘trick’—that allows to recover gauge invariance and to make the scalar field explicit. We show how to apply this formalism to gravity and cosmology and we reproduce the detailed analysis of the action in the ADM variables. We also review some basic applications to inflation and dark energy.

Structure of solvent-free grafted nanoparticles: Molecular dynamics and density-functional theory

KAUST Repository

Chremos, Alexandros

2011-01-01

The structure of solvent-free oligomer-grafted nanoparticles has been investigated using molecular dynamics simulations and density-functional theory. At low temperatures and moderate to high oligomer lengths, the qualitative features of the core particle pair probability, structure factor, and the oligomer brush configuration obtained from the simulations can be explained by a density-functional theory that incorporates the configurational entropy of the space-filling oligomers. In particular, the structure factor at small wave numbers attains a value much smaller than the corresponding hard-sphere suspension, the first peak of the pair distribution function is enhanced due to entropic attractions among the particles, and the oligomer brush expands with decreasing particle volume fraction to fill the interstitial space. At higher temperatures, the simulations reveal effects that differ from the theory and are likely caused by steric repulsions of the expanded corona chains. © 2011 American Institute of Physics.

Extended Møller-Plesset perturbation theory for dynamical and static correlations

International Nuclear Information System (INIS)

Tsuchimochi, Takashi; Van Voorhis, Troy

2014-01-01

We present a novel method that appropriately handles both dynamical and static electron correlations in a balanced manner, using a perturbation theory on a spin-extended Hartree-Fock (EHF) wave function reference. While EHF is a suitable candidate for degenerate systems where static correlation is ubiquitous, it is known that most of dynamical correlation is neglected in EHF. In this work, we derive a perturbative correction to a fully spin-projected self-consistent wave function based on second-order Møller-Plesset perturbation theory (MP2). The proposed method efficiently captures the ability of EHF to describe static correlation in degeneracy, combined with MP2's ability to treat dynamical correlation effects. We demonstrate drastic improvements on molecular ground state and excited state potential energy curves and singlet-triplet splitting energies over both EHF and MP2 with similar computational effort to the latter

Block correlated second order perturbation theory with a generalized valence bond reference function

International Nuclear Information System (INIS)

Xu, Enhua; Li, Shuhua

2013-01-01

The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a “multi-orbital” block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Møller–Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods

Block correlated second order perturbation theory with a generalized valence bond reference function.

Science.gov (United States)

Xu, Enhua; Li, Shuhua

2013-11-07

The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a "multi-orbital" block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Mo̸ller-Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-07-28

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

Sensitivity calculations of integral parameters by a generalyzed perturbation theory

International Nuclear Information System (INIS)

Santo, A.C.F. de.

1981-12-01

In this work, we first revise some concepts, concerning the neutron transport in nuclear systems. We derive the balance and importance equation. Then we discuss the neutron importance in subcritical, critical and supercritical systems. The adjoint flux is estabilished as the neutron importance for the fission process. The conventional perturbation theory is later presented. We developed a sistematic perturbative formulation in the first order variation in the distribution functions calculate the reactivity due to a system perturbation. We present in detail the flux difference and generalized functions methos. The above formulation is then extended for altered systems. We consider integral parameters of the type ratio of bilinear functionals (for which the reactivity is a particular case). We define sensitivity coeficients, for any integral parameter, corresponding to a especific system alterations. Possible aplication of the method are also discussed. In the last part of this work, we apply the perturbative formulation to the doppler reacitivity sensibility calculation, utilizing the generalized functions method. We describe in detail the compiler program written for this and some other possible aplications. (Author) [pt

The theory of singular perturbations

CERN Document Server

De Jager, E M

1996-01-01

The subject of this textbook is the mathematical theory of singular perturbations, which despite its respectable history is still in a state of vigorous development. Singular perturbations of cumulative and of boundary layer type are presented. Attention has been given to composite expansions of solutions of initial and boundary value problems for ordinary and partial differential equations, linear as well as quasilinear; also turning points are discussed. The main emphasis lies on several methods of approximation for solutions of singularly perturbed differential equations and on the mathemat

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)

Melting slope of MgO from molecular dynamics and density functional theory

Science.gov (United States)

Tangney, Paul; Scandolo, Sandro

2009-09-01

We combine density functional theory (DFT) with molecular dynamics simulations based on an accurate atomistic force field to calculate the pressure derivative of the melting temperature of magnesium oxide at ambient pressure—a quantity for which a serious disagreement between theory and experiment has existed for almost 15 years. We find reasonable agreement with previous DFT results and with a very recent experimental determination of the slope. We pay particular attention to areas of possible weakness in theoretical calculations and conclude that the long-standing discrepancy with experiment could only be explained by a dramatic failure of existing density functionals or by flaws in the original experiment.

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

Science.gov (United States)

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

2011-05-06

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

Application of linear and higher perturbation theory in reactor physics

International Nuclear Information System (INIS)

Woerner, D.

1978-01-01

For small perturbations in the material composition of a reactor according to the first approximation of perturbation theory the eigenvalue perturbation is proportional to the perturbation of the system. This assumption is true for the neutron flux not influenced by the perturbance. The two-dimensional code LINESTO developed for such problems in this paper on the basis of diffusion theory determines the relative change of the multiplication constant. For perturbations varying the neutron flux in the space of energy and position the eigenvalue perturbation is also influenced by this changed neutron flux. In such cases linear perturbation theory yields larger errors. Starting from the methods of calculus of variations there is additionally developed in this paper a perturbation method of calculation permitting in a quick and simple manner to assess the influence of flux perturbation on the eigenvalue perturbation. While the source of perturbations is evaluated in isotropic approximation of diffusion theory the associated inhomogeneous equation may be used to determine the flux perturbation by means of diffusion or transport theory. Possibilities of application and limitations of this method are studied in further systematic investigations on local perturbations. It is shown that with the integrated code system developed in this paper a number of local perturbations may be checked requiring little computing time. With it flux perturbations in first approximation and perturbations of the multiplication constant in second approximation can be evaluated. (orig./RW) [de

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

Massive states in chiral perturbation theory

Energy Technology Data Exchange (ETDEWEB)

Mallik, S [Saha Inst. of Nuclear Physics, Calcutta (India)

1995-08-01

It is shown that the chiral nonanalytic terms generated by {Delta}{sub 33} resonance in the nucleon self-energy is reproduced in chiral perturbation theory by perturbing appropriate local operators contained in the pion-nucleon effective Lagrangian itself. (orig.)

Thermodynamics as a Foundation for Density Functional Theory

International Nuclear Information System (INIS)

Argaman, Nathan

2014-01-01

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

SMD-based numerical stochastic perturbation theory

Science.gov (United States)

Dalla Brida, Mattia; Lüscher, Martin

2017-05-01

The viability of a variant of numerical stochastic perturbation theory, where the Langevin equation is replaced by the SMD algorithm, is examined. In particular, the convergence of the process to a unique stationary state is rigorously established and the use of higher-order symplectic integration schemes is shown to be highly profitable in this context. For illustration, the gradient-flow coupling in finite volume with Schrödinger functional boundary conditions is computed to two-loop (i.e. NNL) order in the SU(3) gauge theory. The scaling behaviour of the algorithm turns out to be rather favourable in this case, which allows the computations to be driven close to the continuum limit.

SMD-based numerical stochastic perturbation theory

Energy Technology Data Exchange (ETDEWEB)

Dalla Brida, Mattia [Universita di Milano-Bicocca, Dipartimento di Fisica, Milan (Italy); INFN, Sezione di Milano-Bicocca (Italy); Luescher, Martin [CERN, Theoretical Physics Department, Geneva (Switzerland); AEC, Institute for Theoretical Physics, University of Bern (Switzerland)

2017-05-15

The viability of a variant of numerical stochastic perturbation theory, where the Langevin equation is replaced by the SMD algorithm, is examined. In particular, the convergence of the process to a unique stationary state is rigorously established and the use of higher-order symplectic integration schemes is shown to be highly profitable in this context. For illustration, the gradient-flow coupling in finite volume with Schroedinger functional boundary conditions is computed to two-loop (i.e. NNL) order in the SU(3) gauge theory. The scaling behaviour of the algorithm turns out to be rather favourable in this case, which allows the computations to be driven close to the continuum limit. (orig.)

SMD-based numerical stochastic perturbation theory

International Nuclear Information System (INIS)

Dalla Brida, Mattia; Luescher, Martin

2017-01-01

The viability of a variant of numerical stochastic perturbation theory, where the Langevin equation is replaced by the SMD algorithm, is examined. In particular, the convergence of the process to a unique stationary state is rigorously established and the use of higher-order symplectic integration schemes is shown to be highly profitable in this context. For illustration, the gradient-flow coupling in finite volume with Schroedinger functional boundary conditions is computed to two-loop (i.e. NNL) order in the SU(3) gauge theory. The scaling behaviour of the algorithm turns out to be rather favourable in this case, which allows the computations to be driven close to the continuum limit. (orig.)

Perturbation theory for plasmonic modulation and sensing

KAUST Repository

Raman, Aaswath

2011-05-25

We develop a general perturbation theory to treat small parameter changes in dispersive plasmonic nanostructures and metamaterials. We specifically apply it to dielectric refractive index and metallic plasma frequency modulation in metal-dielectric nanostructures. As a numerical demonstration, we verify the theory\\'s accuracy against direct calculations for a system of plasmonic rods in air where the metal is defined by a three-pole fit of silver\\'s dielectric function. We also discuss new optical behavior related to plasma frequency modulation in such systems. Our approach provides new physical insight for the design of plasmonic devices for biochemical sensing and optical modulation and future active metamaterial applications. © 2011 American Physical Society.

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)

Gluon cascades and amplitudes in light-front perturbation theory

International Nuclear Information System (INIS)

Cruz-Santiago, C.A.; Staśto, A.M.

2013-01-01

We construct the gluon wave functions, fragmentation functions and scattering amplitudes within the light-front perturbation theory. Recursion relations on the light-front are constructed for the wave functions and fragmentation functions, which in the latter case are the light-front analogs of the Berends–Giele recursion relations. Using general relations between wave functions and scattering amplitudes it is demonstrated how to obtain the maximally-helicity violating amplitudes, and explicit verification of the results is based on simple examples.

The P(phi)2 Green's functions; asymptotic perturbation expansion

International Nuclear Information System (INIS)

Dimock, J.

1976-01-01

The real time Green's functions in the P(phi) 2 quantum field theory are infinitely differentiable functions of the coupling constant lambda up to and including lamba=0. It follows that the perturbation series are asymptotic as lambda→0 + . (Auth.)

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-21

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

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

International Nuclear Information System (INIS)

Lindgren, Ingvar; Salomonson, Sten

2004-01-01

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

Acoustic anisotropic wavefields through perturbation theory

KAUST Repository

Alkhalifah, Tariq Ali

2013-09-01

Solving the anisotropic acoustic wave equation numerically using finite-difference methods introduces many problems and media restriction requirements, and it rarely contributes to the ability to resolve the anisotropy parameters. Among these restrictions are the inability to handle media with η<0 and the presence of shear-wave artifacts in the solution. Both limitations do not exist in the solution of the elliptical anisotropic acoustic wave equation. Using perturbation theory in developing the solution of the anisotropic acoustic wave equation allows direct access to the desired limitation-free solutions, that is, solutions perturbed from the elliptical anisotropic background medium. It also provides a platform for parameter estimation because of the ability to isolate the wavefield dependency on the perturbed anisotropy parameters. As a result, I derive partial differential equations that relate changes in the wavefield to perturbations in the anisotropy parameters. The solutions of the perturbation equations represented the coefficients of a Taylor-series-type expansion of the wavefield as a function of the perturbed parameter, which is in this case η or the tilt of the symmetry axis. The expansion with respect to the symmetry axis allows use of an acoustic transversely isotropic media with a vertical symmetry axis (VTI) kernel to estimate the background wavefield and the corresponding perturbation coefficients. The VTI extrapolation kernel is about one-fourth the cost of the transversely isotropic model with a tilt in the symmetry axis kernel. Thus, for a small symmetry axis tilt, the cost of migration using a first-order expansion can be reduced. The effectiveness of the approach was demonstrated on the Marmousi model.

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.

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.

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.

Radical scavenging activity of some natural tropolones by density functional theory

Directory of Open Access Journals (Sweden)

A. G. Al-Sehemi

2017-07-01

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

Evolution of curvature perturbation in generalized gravity theories