Electronic zero-point oscillations in the strong-interaction limit of density functional theory

TL;DR

This paper analyzes the strong-interaction limit of density functional theory, focusing on zero-point oscillations of correlated electrons, and proposes improved functional approximations and interpolation formulas for exchange-correlation energy.

Contribution

It extends the exact treatment of the strong-interaction limit to include zero-point oscillations and introduces an improved functional and interpolation formula for better accuracy.

Findings

Derived the next leading term for zero-point oscillations in the strong-interaction limit.

Proposed an improved approximate functional for zero-point contributions.

Revised the interpolation formula to satisfy more exact constraints.

Abstract

The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron hamiltonian, this same operator is multiplied by a real parameter $\lambda$ varying between 0 (Kohn-Sham system) and 1 (physical system). In this process, usually called adiabatic connection, the one-electron density is kept fixed by a suitable local one-body potential. The strong-interaction limit of density functional theory, defined as the limit $\lambda\to\infty$, turns out to be, like the opposite non-interacting Kohn-Sham limit ($\lambda\to 0$) mathematically simpler than the physical ($\lambda=1$) case, and can be used to build an approximate interpolation formula between $\lambda\to 0$ and $\lambda\to\infty$ for the exchange-correlation energy. Here we extend the exact treatment of the $\lambda\to\infty$ limit [Phys. Rev. A {\bf 75}, 042511 (2007)] to the next leading term, describing zero-point oscillations of strictly correlated electrons, with numerical examples for small spherical atoms. We also propose an improved approximate functional for the zero-point term and a revised interpolation formula for the exchange-correlation energy satisfying more exact constraints.