arXiv subjects

Paola Gori-Giorgi

Publications and source records attributed to Paola Gori-Giorgi.

At least 73 records · Page 4Linked to original sources

arXiv2008

Degeneracy and size consistency in electronic density functional theory

The electronic structure calculations based upon energy density functionals are highly successful and widely used both in solid state physics and quantum chemistry. Moreover, the Hohenberg-Kohn theorems and the Kohn-Sham method provide them with a firm basis. However, several basic issues are not solved, and hamper the progress to achieve high accuracy. In this paper we focus on the conceptual problem of size consistency, basing our analysis on the non-intensive character of the (spin) electronic density in the presence of degeneracy. We also briefly discuss some of the issues concerning fractional electron numbers from the same point of view, analyzing the behavior of the exact functionals for the He and the Hooke's atom series when the number of electrons fluctuates between one and two.

cond-mat.mtrl-sci↗

arXiv2007

The high-density limit of two-electron systems: Results from the extended Overhauser approach

The ``extended Overhauser model'' [Overhauser, Can. J. Phys. 1995, 73, 683] for the calculation of the spherically and system-averaged pair density (APD) has been recently combined with the Kohn-Sham equations to yield realistic APD and correlation energies. In this work we test this approach in the high-density (weakly-correlated) limit of the He isoelectronic series and of the Hooke's atom isoelectronic series. Unlike many of the commonly used energy functionals, the Overhauser approach yields accurate correlation energies for both series.

physics.chem-ph↗

arXiv2007

Strictly correlated electrons in density functional theory: A general formulation with applications to spherical densities

We reformulate the strong-interaction limit of electronic density functional theory in terms of a classical problem with a degenerate minimum. This allows us to clarify many aspects of this limit, and to write a general solution, which is explicitly calculated for spherical densities. We then compare our results with previous approximate solutions and discuss the implications for density functional theory.

cond-mat.mtrl-sci↗

arXiv2006

A short-range correlation energy density functional with multi-determinantal reference

We introduce a short-range correlation density functional defined with respect to a multi-determinantal reference which is meant to be used in a multi-determinantal extension of the Kohn-Sham scheme of density functional theory based on a long-range/short-range decomposition of the Coulomb electron-electron interaction. We construct the local density approximation for this functional and discuss its performance on the He atom.

physics.chem-ph↗

arXiv2006

Kohn-Sham calculations combined with an average pair-density functional theory

A recently developed formalism in which Kohn-Sham calculations are combined with an ``average pair density functional theory'' is reviewed, and some new properties of the effective electron-electron interaction entering in this formalism are derived. A preliminary construction of a fully self-consitent scheme is also presented in this framework.

cond-mat.mtrl-sci↗

arXiv2006

Model hamiltonians in density functional theory

The formalism of Kohn and Sham uses a specific (model) hamiltonian which highly simplifies the many-electron problem to that of noninteracting fermions. The theorem of Hohenberg and Kohn tells us that, for a given ground state density, this hamiltonian is unique. In principle, this density can be chosen as that of the real, interacting system. To obtain the energy, or other properties of the real system, approximations are needed. Working with non interacting fermions is an important simplification, but it may be easier to produce approximations with different choices of the model hamiltonian. The feature that the exact density is (ideally) reproduced can be kept in the newly defined fictitious systems. Using model hamiltonians having the same form as the physical one, that is, being built of one- and two-body operators, allows to approach the physical hamiltonian arbitrarily close, and thus a systematic reduction of the approximations.

cond-mat.mtrl-sci↗

arXiv2006

Scaling relations, virial theorem and energy densities for long-range and short-range density functionals

We analyze a decomposition of the Coulomb electron-electron interaction into a long-range and a short-range part in the framework of density functional theory, deriving some scaling relations and the corresponding virial theorem. We study the behavior of the local density approximation in the high-density limit for the long-range and the short-range functionals by carrying out a detailed analysis of the correlation energy of a uniform electron gas interacting via a long-range only electron-electron repulsion. Possible definitions of exchange and correlation energy densities are discussed and clarified with some examples.

physics.chem-ph↗

arXiv2006

Local-spin-density functional for multideterminant density functional theory

Based on exact limits and quantum Monte Carlo simulations, we obtain, at any density and spin polarization, an accurate estimate for the energy of a modified homogeneous electron gas where electrons repel each other only with a long-range coulombic tail. This allows us to construct an analytic local-spin-density exchange-correlation functional appropriate to new, multideterminantal versions of the density functional theory, where quantum chemistry and approximate exchange-correlation functionals are combined to optimally describe both long- and short-range electron correlations.

cond-mat.mtrl-sci↗

arXiv2006

Properties of short-range and long-range correlation energy density functionals from electron-electron coalescence

The combination of density functional theory with other approaches to the many-electron problem through the separation of the electron-electron interaction into a short-range and a long-range contribution is a promising method, which is raising more and more interest in recent years. In this work some properties of the corresponding correlation energy functionals are derived by studying the electron-electron coalescence condition for a modified (long-range-only) interaction. A general relation for the on-top (zero electron-electron distance) pair density is derived, and its usefulness is discussed with some examples. For the special case of the uniform electron gas, a simple parameterization of the on-top pair density for a long-range only interaction is presented and supported by calculations within the ``extended Overhauser model''. The results of this work can be used to build self-interaction corrected short-range correlation energy functionals.

cond-mat.mtrl-sci↗

arXiv2005

System-adapted correlation energy density functionals from effective pair interactions

We present and discuss some ideas concerning an ``average-pair-density functional theory'', in which the ground-state energy of a many-electron system is rewritten as a functional of the spherically and system-averaged pair density. These ideas are further clarified with simple physical examples. We then show that the proposed formalism can be combined with density functional theory to build system-adapted correlation energy functionals. A simple approximation for the unknown effective electron-electron interaction that enters in this combined approach is described, and results for the He series and for the uniform electron gas are briefly reviewed.

cond-mat.mtrl-sci↗

arXiv2005

Simple model for the spherically- and system-averaged pair density: Results for two-electron atoms

As shown by Overhauser and others, accurate pair densities for the uniform electron gas may be found by solving a two-electron scattering problem with an effective screened electron-electron repulsion. In this work we explore the extension of this approach to nonuniform systems, and we discuss its potential for density functional theory. For the spherically- and system-averaged pair density of two-electron atoms we obtain very accurate short-range properties, including, for nuclear charge $Z\ge 2$, ``on-top'' values (zero electron-electron distance) essentially indistinguishable from those coming from precise variational wavefunctions. By means of a nonlinear adiabatic connection that separates long- and short-range effects, we also obtain Kohn-Sham correlation energies whose error is less than 4 mHartree, again for $Z\ge 2$, and short-range-only correlation energies whose accuracy is one order of magnitude better.

cond-mat.mtrl-sci↗

arXiv2004

A local density functional for the short-range part of the electron-electron interaction

Motivated by recent suggestions --to split the electron-electron interaction into a short-range part, to be treated within the density functional theory, and a long-range part, to be handled by other techniques-- we compute, with a diffusion Monte Carlo method, the ground-state energy of a uniform electron gas with a modified, short-range-only electron-electron interaction $\erfc(μr)/r$, for different values of the cutoff parameter $μ$ and of the electron density. After deriving some exact limits, we propose an analytic representation of the correlation energy which accurately fits our Monte Carlo data and also includes, by construction, these exact limits, thus providing a reliable ``short-range local-density functional''.

cond-mat.mtrl-sci↗

arXiv2004

Pair-distribution functions of the two-dimensional electron gas

Based on its known exact properties and a new set of extensive fixed-node reptation quantum Monte Carlo simulations (both with and without backflow correlations, which in this case turn out to yield negligible improvements), we propose a new analytical representation of (i) the spin-summed pair-distribution function and (ii) the spin-resolved potential energy of the ideal two-dimensional interacting electron gas for a wide range of electron densities and spin polarization, plus (iii) the spin-resolved pair-distribution function of the unpolarized gas. These formulae provide an accurate reference for quantities previously not available in analytic form, and may be relevant to semiconductor heterostructures, metal-insulator transitions and quantum dots both directly, in terms of phase diagram and spin susceptibility, and indirectly, as key ingredients for the construction of new two-dimensional spin density functionals, beyond the local approximation.

cond-mat.str-el↗

arXiv2003

Spin Resolution of the Electron-Gas Correlation Energy: Positive same-spin contribution

The negative correlation energy per particle of a uniform electron gas of density parameter $r_s$ and spin polarization $ζ$ is well known, but its spin resolution into up-down, up-up, and down-down contributions is not. Widely-used estimates are incorrect, and hamper the development of reliable density functionals and pair distribution functions. For the spin resolution, we present interpolations between high- and low-density limits that agree with available Quantum Monte Carlo data. In the low-density limit for $ζ= 0$, we find that the same-spin correlation energy is unexpectedly positive, and we explain why. We also estimate the up and down contributions to the kinetic energy of correlation.

cond-mat↗

arXiv2003

Two-dimensional electron gas: correlation energy versus density and spin polarization

We propose a simple analytic representation of the correlation energy for the two-dimensional electron gas, as a function of the density and the spin polarization. This new parametrization includes most of the known high- and low- density limits and fits our new fixed-node diffusion Monte Carlo simulations, performed for a wide range of electron densities and spin-polarization states. In this way we provide a reliable local-spin-density energy functional for two-dimensional systems. The corresponding correlation potential is discussed and compared with previous models.

cond-mat.str-el↗

arXiv2003

Correlation energy and spin polarization in the 2D electron gas

The ground state energy of the two--dimensional uniform electron gas has been calculated with fixed--node diffusion Monte Carlo, including backflow correlations, for a wide range of electron densities as a function of spin polarization. We give a simple analytic representation of the correlation energy which fits the density and polarization dependence of the simulation data and includes several known high- and low-density limits. This parametrization provides a reliable local spin density energy functional for two-dimensional systems and an estimate for the spin susceptibility. Within the proposed model for the correlation energy, a weakly first--order polarization transition occurs shortly before Wigner crystallization as the density is lowered.

cond-mat.str-el↗

arXiv2003

Simple Physical Picture of the Overhauser Screened Electron-Electron Interaction

As shown by Overhauser and others, the pair-distribution function $g(r)$ of a many-electron system may be found by solving a two-electron scattering problem with an effective screened electron-electron repulsion $V(r)$. We propose a simple physical picture in which this screened repulsion is the ``dressed-dressed'' interaction between two neutral objects, each an electron surrounded by its full-coupling exchange-correlation hole. For the effective interaction between two electrons of antiparallel spin in a high-density uniform electron gas of arbitrary spin polarization, we confirm that this picture is qualitatively correct. In contrast, the ``bare-dressed'' interaction is too repulsive, and does not have the expected symmetry $V_{\ud}(r) = V_{\du}(r)$. The simple original Overhauser model interaction, independent of the relative spin polarization $ζ$, does not capture the $ζ$-dependence of the correlation contribution to $g(r=0)$.

cond-mat.mtrl-sci↗

arXiv2002

Momentum distribution of the uniform electron gas: improved parametrization and exact limits of the cumulant expansion

The momentum distribution of the unpolarized uniform electron gas in its Fermi-liquid regime, n(k,r_s), with the momenta k measured in units of the Fermi wave number k_F and with the density parameter r_s, is constructed with the help of the convex Kulik function G(x). It is assumed that $n(0,r_s), n(1^\pm, r_s)$, the on-top pair density g(0,r_s) and the kinetic energy t(r_s) are known (respectively, from effective-potential calculations, from the solution of the Overhauser model, and from Quantum Monte Carlo calculations via the virial theorem). Information from the high- and the low-density limit, corresponding to the random-phase approximation and to the Wigner crystal limit, is used. The result is an accurate parametrization of n(k,r_s), which fulfills most of the known exact constraints. It is in agreement with the effective-potential calculation of Takada and Yasuhara [1991 {\it Phys. Rev.} B {\bf 44} 7879], is compatible with Quantum Monte Carlo data, and is valid in the density range $r_s \lesssim 12$. The corresponding cumulant expansions of the pair density and of the static structure factor are discussed, and some exact limits are derived.

cond-mat↗