Ground-state densities from the Rayleigh--Ritz variation principle and from density-functional theory

TL;DR

This paper investigates the relationship between ground-state densities from the Rayleigh--Ritz principle and density-functional theory, establishing conditions for their equivalence and applying results to molecular systems within the Born-Oppenheimer approximation.

Contribution

It provides necessary and sufficient conditions for the equivalence of RR and HK ground-state densities, and demonstrates a one-to-one correspondence between their mixed and pure states using specific density functionals.

Findings

Established conditions for RR and HK density equivalence.

Proved a one-to-one correspondence between mixed densities.

Confirmed all physical densities are recoverable with the chosen functionals.

Abstract

The relationship between the densities of ground-state wave functions (i.e., the minimizers of the Rayleigh--Ritz (RR) variation principle) and the ground-state densities in density-functional theory (i.e., the minimizers of the Hohenberg--Kohn (HK) variation principle) is studied within the framework of convex conjugation, in a generic setting covering molecular systems, solid-state systems, and more. Having introduced admissible density functionals as functionals that produce the exact ground ground-state energy for a given external potential by minimizing over densities in the HK variation principle, necessary sufficient conditions on such functionals are established to ensure that the RR ground-state densities and the HK ground-state densities are identical. We apply the results to molecular systems in the BO-approximation. For any given potential $v \in L^{3/2}(\mathbb{R}^3) + L^{\infty}(\mathbb{R}^3)$, we establish a one-to-one correspondence between the mixed ground-state densities of the RR variation principle and the mixed ground-state densities of the HK variation principle when the Lieb density-matrix constrained-search universal density functional is taken as the admissible functional. A similar one-to-one correspondence is established between the pure ground-state densities of the RR variation principle and the pure ground-state densities obtained using the HK variation principle with the Levy--Lieb pure-state constrained-search functional. In other words, all physical ground-state densities (pure or mixed) are recovered with these functionals and no false densities (i.e., minimizing densities that are not physical) exist. The importance of topology (i.e., choice of Banach space of densities and potentials) is emphasized and illustrated. The relevance of these results for current-density-functional theory is examined.