Spherical vs. Non-Spherical and Symmetry-Preserving vs. Symmetry-Breaking Densities of Open-Shell Atoms in Density Functional Theory

TL;DR

This paper investigates how different density functional approximations affect the sensitivity to non-spherical densities in open-shell atoms and explores symmetry-preserving approaches versus symmetry-breaking in density functional theory calculations.

Contribution

It introduces a symmetry-preserving approach for open-shell atoms that maintains spatial symmetry after self-consistent calculations, and assesses its impact on molecular atomization energies.

Findings

Symmetry-preserving approach has minimal effect on atomization energies.

Standard symmetry-breaking in Kohn-Sham calculations is justified for common molecules.

Density functional improvements increase sensitivity to non-spherical densities.

Abstract

The atomization energies of molecules from first-principles density functional approximations improve from the local spin-density approximation (LSDA) to the Perdew-Burke-Ernzerhof (PBE)) generalized gradient approximation (GGA) to the strongly constrained and appropriately normed (SCAN) meta-GGA, and their sensitivities to non-spherical components of the density increase in the same order. Thus, these functional advances increase density sensitivity and imitate the exact constrained search over correlated wavefunctions better than that over ensembles. The diatomic molecules studied here, singlet C2 and F2 plus triplet B2 and O2, have cylindrically symmetric densities. Because the densities of the corresponding atoms are non-spherical, the approximate Kohn-Sham potentials for the atoms have a lower symmetry than that of the external (nuclear) potential, so that the non-interacting wavefunctions are not eigenstates of the square of total orbital angular momentum, breaking a symmetry that yields a feature of the exact ground-state density. That spatial symmetry can be preserved by a non-self-consistent approach in which a self-consistent equilibrium-ensemble calculation is followed by integer re-occupation of the Kohn-Sham orbitals, as the first of several steps. The symmetry-preserving approach is different from symmetry restoration based upon projection. First-step space- (and space-spin-) symmetry preservation in atoms is shown to have a small effect on the atomization energies of molecules, quantifying earlier observations by Fertig and Kohn. Thus, the standard Kohn-Sham way of calculating atomization energies, with self-consistent symmetry breaking to minimize the energy, is justified, at least for the common cases where the molecules cannot break symmetry.