Self-interaction-corrected Kohn-Sham effective potentials using the density-consistent effective potential method.

Abstract

Density functional theory (DFT) and beyond-DFT methods are often used in combination with photoelectron spectroscopy to obtain physical insights into the electronic structure of molecules and solids. The Kohn-Sham eigenvalues are not electron removal energies except for the highest occupied orbital. The eigenvalues of the highest occupied molecular orbitals often underestimate the electron removal or ionization energies due to the self-interaction (SI) errors in approximate density functionals. In this work, we adapt and implement the density-consistent effective potential method of Kohut, Ryabinkin, and Staroverov [J. Chem. Phys. 140, 18A535 (2014)] to obtain SI-corrected local effective potentials from the SI-corrected Fermi-Löwdin orbitals and density in the Fermi-Löwdin orbital self-interaction correction scheme. The implementation is used to obtain the density of states (photoelectron spectra) and HOMO-LUMO gaps for a set of molecules and polyacenes. Good agreement with experimental values is obtained compared to a range of SI uncorrected density functional approximations.