Ensemble Density Functional Theory of Neutral and Charged Excitations

Abstract

Recent progress in the field of (time-independent) ensemble density-functional theory (DFT) for excited states are reviewed. Both Gross-Oliveira-Kohn (GOK) and $N$-centered ensemble formalisms, which are mathematically very similar and allow for an in-principle-exact description of neutral and charged electronic excitations, respectively, are discussed. Key exact results like, for example, the equivalence between the infamous derivative discontinuity problem and the description of weight dependencies in the ensemble exchange-correlation density functional, are highlighted. The variational evaluation of orbital-dependent ensemble Hartree-exchange (Hx) energies is discussed in detail. We show in passing that state-averaging individual exact Hx energies can lead to severe (solvable though) $v$-representability issues. Finally, we explore the possibility to use the concept of density-driven correlation, which has been recently introduced and does not exist in regular ground-state DFT, for improving state-of-the-art correlation density-functional approximations for ensembles. The present review reflects the efforts of a growing community to turn ensemble DFT into a rigorous and reliable low-cost computational method for excited states. We hope that, in the near future, this contribution will stimulate new formal and practical developments in the field.

The present review article (81 pages, 5 figures) is part of the "Topics in Current Chemistry'' topical collection entitled "New Horizon in Computational Chemistry Software''

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