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Faraday Discuss. [LCQ]

juin 18 2020

Abstract :

Gross--Oliveira--Kohn (GOK) ensemble density-functional theory (GOK-DFT) is a time-\textit{independent} extension of density-functional theory (DFT) which allows to compute excited-state energies via the derivatives of the ensemble energy with respect to the ensemble weights. Contrary to the time-dependent version of DFT (TD-DFT), double excitations can be easily computed within GOK-DFT. However, to take full advantage of this formalism, one must have access to a \textit{weight-dependent} exchange-correlation functional in order to model the infamous ensemble derivative contribution to the excitation energies. In the present article, we discuss the construction of first-rung (\textit{i.e.}, local) weight-dependent exchange-correlation density-functional approximations for two-electron atomic and molecular systems (He and H$_2$) specifically designed for the computation of double excitations within GOK-DFT. In the spirit of optimally-tuned range-separated hybrid functionals, a two-step system-dependent procedure is proposed to obtain accurate energies associated with double excitations.

Reference :

Clotilde Marut, Bruno Senjean, Emmanuel Fromager and Pierre-François Loos  

Weight Dependence of Local Exchange-Correlation Functionals in Ensemble Density-Functional Theory: Double Excitations in Two-Electron Systems

Faraday Discuss., 2020, First published 15 Jun 2020 - DOI :https://doi.org/10.1039/D0FD00059K

This article is part of the themed collection: New horizons in density functional theory


Contact chercheur :

Emmanuel Fromager, équipe LCQ, Institut de Chimie (UMR 7177).