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

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 $λ$ 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 $λ\to\infty$, turns out to be, like the opposite non-interacting Kohn-Sham limit ($λ\to 0$) mathematically simpler than the physical ($λ=1$) case, and can be used to build an approximate interpolation formula between $λ\to 0$ and $λ\to\infty$ for the exchange-correlation energy. Here we extend the exact treatment of the $λ\to\infty$ 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.

11 pages, submitted to J. Chem. Theory Comput