Ensemble Density Functional Theory of Neutral and Charged Excitations Exact Formulations, Standard Approximations, and Open Questions

• Published in: Topics in current chemistry (2016) Vol. 380; no. 1; p. 4
• Main Authors: Cernatic, Filip, Senjean, Bruno, Robert, Vincent, Fromager, Emmanuel
• Format: Journal Article
• Language: English
• Published: Cham Springer International Publishing 01.02.2022
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Life Sciences; Materials Science; Molecular Medicine; New Horizon in Computational Chemistry Software; Physics; Review; Many-body ensembles; Excited states; Density-functional theory
• ISSN: 2365-0869; 2364-8961
• DOI: 10.1007/s41061-021-00359-1

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, 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 (although solvable) v -representability issues. Finally, we explore the possibility of using the concept of density-driven correlation, which has been introduced recently 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.