Natural occupation numbers: When do they vanish?

TL;DR

This paper investigates when natural orbital occupation numbers in many-body quantum systems vanish, linking their decay behavior to wave function differentiability and Coulomb cusps, with implications for density functional theories.

Contribution

It establishes a connection between wave function smoothness and the decay of natural occupations, providing criteria for their non-vanishing in two-particle systems.

Findings

Coulomb cusps lead to power law decay of occupations

Smooth wave functions decay exponentially

Hookium system's occupations never vanish

Abstract

The non-vanishing of the natural orbital occupation numbers of the one-particle density matrix of many-body systems has important consequences for the existence of a density matrix-potential mapping for nonlocal potentials in reduced density matrix functional theory and for the validity of the extended Koopmans' Theorem. On the basis of Weyl's theorem we give a connection between the differentiability properties of the ground state wave function and the rate at which the natural occupations approach zero when ordered as a descending series. We show, in particular, that the presence of a Coulomb cusp in the wave function leads, in general, to a power law decay of the natural occupations, whereas infinitely differentiable wave-functions typically have natural occupations that decay exponentially. We analyze for a number of explicit examples of two-particle systems that in case the wave function is non-analytic at its spatial diagonal (for instance, due to the presence of a Coulomb cusp) the natural orbital occupations are non-vanishing. We further derive a more general criterium for the non-vanishing of NO occupations for two-particle wave functions with a certain separability structure. On the basis of this criterium we show that for a two-particle system of harmonically confined electrons with a Coulombic interaction (the so-called Hookium) the natural orbital occupations never vanish.