Neutral electronic excitations and derivative discontinuities: An extended $N$-centered ensemble density functional theory perspective

Abstract

This work merges two different types of many-electron ensembles, namely the Theophilou-Gross-Oliveira-Kohn ensembles of ground and neutrally-excited states, and the more recent $N$-centered ensembles of neutral and charged ground states. On that basis, an in-principle exact and general, so-called extended $N$-centered, ensemble density-functional theory of charged and neutral electronic excitations is derived. We revisit in this context the concept of density-functional derivative discontinuity for neutral excitations, without ever invoking nor using the asymptotic behavior of the ensemble electronic density. The present mathematical construction fully relies on the weight dependence of the ensemble Hartree-exchange-correlation density-functional energy, which makes the theory applicable to lattice models and opens new perspectives for the description of gaps in mesoscopic systems.

21 pages, second revision

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• Ensemble density functional theory of ground and excited energy levels
• Stationary conditions for excited states: the surprising impact of density-driven correlations
• Exact static linear response of excited states from ensemble density functional theory
• Ensemble density functional theory of excited states: Exact N-centered formalism and practical opportunities
• Approaching Periodic Systems in Ensemble Density Functional Theory via Finite One-Dimensional Models
• Solving one-body ensemble N-representability problems with spin
• Refining ensemble $N$-representability of one-body density matrices from partial information