Efficient and accurate calculation of exact exchange and RPA correlation energies in the Adiabatic-Connection Fluctuation-Dissipation theory

TL;DR

This paper introduces an efficient method for calculating exact exchange and RPA correlation energies within the ACFD framework, improving accuracy and convergence for realistic systems like silicon and beryllium dimer.

Contribution

It presents a novel iterative eigenmode approach for RPA dielectric matrices and addresses divergence issues in exchange energy calculations.

Findings

Efficient computation of RPA correlation energies using eigenmodes.

Improved convergence in exchange energy calculations.

Successful application to bulk silicon and atomic systems.

Abstract

Recently there has been a renewed interest in the calculation of exact-exchange and RPA correlation energies for realistic systems. These quantities are main ingredients of the so-called EXX/RPA+ scheme which has been shown to be a promising alternative approach to the standard LDA/GGA DFT for weakly bound systems where LDA and GGA perform poorly. In this paper, we present an efficient approach to compute the RPA correlation energy in the framework of the Adiabatic-Connection Fluctuation-Dissipation formalism. The method is based on the calculation of a relatively small number of eigenmodes of RPA dielectric matrix, efficiently computed by iterative density response calculations in the framework of Density Functional Perturbation Theory. We will also discuss a careful treatment of the integrable divergence in the exact-exchange energy calculation which alleviates the problem of its slow convergence with respect to Brillouin zone sampling. As an illustration of the method, we show the results of applications to bulk Si, Be dimer and atomic systems.