Degenerate Density Perturbation Theory

TL;DR

This paper develops a perturbation theory for degenerate density functional systems with fractional occupation numbers, providing analytic solutions and insights into the role of the exchange-correlation functional's Hessian.

Contribution

It introduces a novel perturbation approach for degenerate density functional theory with fractional occupations, including analytic solutions and analysis of the exchange-correlation effects.

Findings

Analytic first-order density solution obtained.

First to third-order energy expansions as a function of alpha.

Insights into the impact of the XC Hessian's non-positivity.

Abstract

Fractional occupation numbers can be used in density functional theory to create a symmetric Kohn-Sham potential, resulting in orbitals with degenerate eigenvalues. We develop the corresponding perturbation theory and apply it to a system of $N_d$ degenerate electrons in a harmonic oscillator potential. The order-by-order expansions of both the fractional occupation numbers and unitary transformations within the degenerate subspace are determined by the requirement that a differentiable map exists connecting the initial and perturbed states. Using the X$\alpha$ exchange-correlation (XC) functional, we find an analytic solution for the first-order density and first through third-order energies as a function of $\alpha$, with and without a self-interaction correction. The fact that the XC Hessian is not positive definite plays an important role in the behavior of the occupation numbers.