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arXiv:2307.00187 · Physical review. B./Physical review. B

Exact conditions for ensemble density functional theory

Thais R. Scott, John Kozlowski, Steven Crisostomo, Aurora Pribram−Jones, Kieron Burke

Published May 7, 2024• 14 citations
arXivHTMLPDF

Abstract

Ensemble density functional theory (EDFT) offers a promising path for computing excitation energies via a theory of the ensemble density --- a weighted sum of interacting excited-state densities. Recovering excitation energies is theoretically simple, but practical application requires approximations dependent on weight choice. Here, the authors derive exact conditions for EDFT. Using an exactly solvable model, they illustrate violations of exact conditions, weight-dependent derivative discontinuities in the strong-interaction limit, and ultimately the significance of weight dependence for future functional design.

DOI
10.1103/physrevb.109.195120

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Ensemble density functional theory (EDFT) offers a promising path for computing excitation energies via a theory of the ensemble density --- a weighted sum of interacting excited-state densities. Recovering excitation energies is theoretically simple, but practical application requires approximations dependent on weight choice. Here, the authors derive exact conditions for EDFT. Using an exactly solvable model, they illustrate violations of exact conditions, weight-dependent derivative discontinuities in the strong-interaction limit, and ultimately the significance of weight dependence for future functional design.
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Time-dependent density functional theory (TDDFT) is a standard approach for calculating optical excitations of molecules and solids, while ensemble DFT (EDFT) is a promising alternative under development. We introduce ensemble TDDFT (ETDDFT), a practical theory that combines the two, generalizing both; we ensemble generalize the Gross-Kohn equation and the exchange-correlation kernel of TDDFT, and generalize EDFT to time-dependent problems. We relate coordinate scaling to the adiabatic connection. The new theory provides multiple avenues for constructing and using approximations. We illustrate these on the two-site Hubbard model. We connect our results to the more general case of nonperturbative time dependence.
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Ensemble density functional theory is a promising method for the efficient and accurate calculation of excitations of quantum systems, at least if useful functionals can be developed to broaden its domain of practical applicability. Here, we introduce a guaranteed single-valued "Hartree-exchange" ensemble density functional, E_{Hx}[n], in terms of the right derivative of the universal ensemble density functional with respect to the coupling constant at vanishing interaction. We show that E_{Hx}[n] is straightforwardly expressible using block eigenvalues of a simple matrix [Eq. (14)]. Specialized expressions for E_{Hx}[n] from the literature, including those involving superpositions of Slater determinants, can now be regarded as originating from the unifying picture presented here. We thus establish a clear and practical description for Hartree and exchange in ensemble systems.
The recent use of a new ensemble in density functional theory (DFT) to produce direct corrections to the Kohn-Sham transitions yields the elusive double excitations that are missed by time-dependent DFT (TDDFT) with the standard adiabatic approximation. But accuracies are lower than for single excitations, and formal arguments about TDDFT suggest that a correction kernel is needed. In principle, ensemble DFT with direct corrections at the exchange level must yield accurate doubles in the weakly correlated limit. We illustrate with exact calculations and analytic results on the Hubbard dimer. We also explain the error in formal arguments in TDDFT.