Ensemble density functional theory of excited states: Exact N-centered formalism and practical opportunities

TL;DR

This paper explores the exact formalism of N-centered ensemble density functional theory for excited states, proposing new strategies for practical computational approaches and extending the theoretical framework.

Contribution

It provides a detailed exposition of exact N-centered ensemble DFT and introduces three original strategies for practical computation and approximation.

Findings

Recycling ground-state functionals with weight-dependent scaling improves ensemble DFT calculations.

Proposes quasi-degenerate perturbation theory formulations for better excited state modeling.

Generalizes quantum bath concept for ensemble states, laying foundations for quantum embedding theory.

Abstract

Ground-state electronic structure calculations using Kohn-Sham density functional theory (KS-DFT) offer an unprecedented balance between efficiency and accuracy, now paradigmatic to the fields of quantum chemistry and condensed matter physics. KS-DFT can be extended to model electronic excitations through a density mapping onto a non-interacting ensemble state in which, unlike in thermal theories, the weights assigned to the excited states vary independently. Thanks to its numerous appeals, like the adequate treatment of multiple excitations for which the widely-used time-dependent extension of DFT struggles, ensemble DFT (eDFT) has lately become a vibrant area of research. Recently, an enlarged type of ensemble, referred to as N-centered (Nc) ensemble, has been introduced to describe within the same unified formalism both neutral and charged electronic excitations. This perspective paper provides a detailed exposition of exact Nc-eDFT, with a comprehensive review of its formal developments. To cut practical computational tools out of the exact theory, three original strategies are presented, complementing existing approaches. The first one, related to the design of ensemble density-functional approximations, consists in recycling regular ground-state functionals by dressing them with a weight-dependent scaling function deduced from exact properties of eDFT. We then explore quasi-degenerate formulations of ensemble density-functional perturbation theory, suggesting alternative definitions for the ensemble Hartree, exchange, and correlation energies, individually, and paving the way toward robust orbital-dependent eDFAs. Finally, we revisit and generalize the concept of quantum bath for an ensemble of non-interacting states, laying the foundations of an in-principle exact (in the sense of lattice eDFT) quantum embedding theory of excited states.