Stretched or noded orbital densities and self-interaction correction in density functional theory

TL;DR

This paper investigates the limitations of semi-local density functional approximations and the Perdew-Zunger self-interaction correction, revealing how orbital nodality affects energy accuracy in one-electron and many-electron systems.

Contribution

It demonstrates that orbital nodality influences SIC errors and suggests the need for a generalized SIC approach, especially for the SCAN meta-GGA.

Findings

Noded orbital densities cause energy errors in SIC calculations.

Complex localized orbitals reduce but do not eliminate SIC errors.

PZ SIC improves energy barriers but worsens atomization energies.

Abstract

Semi-local approximations to the density functional for the exchange-correlation energy of a many-electron system necessarily fail for lobed one-electron densities, including not only the familiar stretched densities but also the less familiar but closely-related noded ones. The Perdew-Zunger (PZ) self-interaction correction (SIC) to a semi-local approximation makes that approximation exact for all one-electron ground- or excited-state densities and accurate for stretched bonds. When the minimization of the PZ total energy is made over real localized orbitals, the orbital densities can be noded, leading to energy errors in many-electron systems. Minimization over complex localized orbitals yields nodeless orbital densities, which reduce but typically do not eliminate the SIC errors of atomization energies. Other errors of PZ SIC remain, attributable to the loss of the exact constraints and appropriate norms that the semi-local approximations satisfy, and suggesting the need for a generalized SIC. These conclusions are supported by calculations for one-electron densities, and for many-electron molecules. While PZ SIC raises and improves the energy barriers of standard generalized gradient approximations (GGA's) and meta-GGA's, it reduces and often worsens the atomization energies of molecules. Thus PZ SIC raises the energy more as the nodality of the valence localized orbitals increases from atoms to molecules to transition states. PZ SIC is applied here in particular to the SCAN meta-GGA, for which the correlation part is already self-interaction-free. That property makes SCAN a natural first candidate for a generalized SIC.