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

TL;DR

This paper introduces a renormalized kernel within TDDFT combined with ACFDT to achieve near chemical accuracy in ground state energies of solids and molecules, improving upon RPA methods.

Contribution

The authors develop a renormalization scheme for kernels in TDDFT that eliminates divergence issues, significantly enhancing the accuracy of ground state energy calculations.

Findings

Fourfold improvement in RPA binding energies for molecules and solids.

Renormalized kernels outperform or match RPA in barrier heights, adsorption, and surface interactions.

Method maintains similar computational cost to RPA.

Abstract

We demonstrate that ground state energies approaching chemical accuracy can be obtained by combining the adiabatic connection fluctuation-dissipation theorem (ACFDT) with time-dependent density functional theory (TDDFT). The key ingredient is a renormalization scheme, which eliminates the divergence of the correlation hole characteristic of any local kernel. This new class of renormalized kernels gives a significantly better description of the short-range correlations in covalent bonds compared to the random phase approximation (RPA) and yields a four fold improvement of RPA binding energies in both molecules and solids. We also consider examples of barrier heights in chemical reactions, molecular adsorption and graphene interacting with metal surfaces, which are three examples where RPA has been successful. In these cases, the renormalized kernel provides results that are of equal quality or even slightly better than RPA, with a similar computational cost.