Exchange-correlation energy functional constructed from orbital-dependent coupling-constant-averaged pair correlation functions

TL;DR

This paper introduces a new exchange-correlation energy functional in density-functional theory based on orbital-dependent pair correlation functions, accurately capturing both local and asymptotic behaviors for atoms, molecules, and solids.

Contribution

It proposes an orbital-dependent functional using coupling-constant-averaged pair correlation functions that satisfy key physical properties and reproduce correct asymptotic potentials.

Findings

Functional fulfills symmetry, Pauli principle, and sum rules.

Reproduces exact asymptotic exchange potential of -e^2/r.

Can potentially model van der Waals interactions at large distances.

Abstract

An exchange-correlation energy functional $ E_{\mathrm xc} $ and the resultant exchange-correlation potential $ v_{\mathrm xc}({\bf r}) $ in density-functional theory are proposed using orbital-dependent coupling-constant-averaged pair correlation functions, $ {\bar{g}}^{\sigma \sigma'}({\bf r, r'})$ for electronic structure calculations of atoms, molecules, and solids. These orbital-dependent $ {\bar{g}}^{\sigma \sigma'}({\bf r, r'})$ fulfill the symmetric property, the Pauli principle and the sum rules. In the limit of uniform density $ {\bar{g}}^{\sigma \sigma'}({\bf r, r'})$ are reduced to the very accurate analogues of the electron liquid that are obtained from an interpolation between long- and short-range correlations involving the exchange corrections. The major contribution of $ v_{\mathrm xc}({\bf r}) $ is given in the form of the Coulomb interaction with the exchange-Coulomb hole around an electron. The present theory not only guarantees local charge neutrality, but also reproduces the exact asymptotic form of the exchange potential, $ v_{\mathrm x}({\bf r}) = - e^2 / r $ for finite systems. The present method of dealing with correlations, if properly applied to finite systems, can give even the asymptotic form of the correlation potential $ v_{\mathrm c}({\bf r}) $ of order $ r^{-4} $ as well as the van der Waals potential of order $ r^{-6} $ for large r.