An alternative self‐interaction correction in the generalized exchange local‐density functional theory

Abstract

AbstractThe local‐density functional (LDF) theory does not accurately predict the total energy and the orbital energy of an atom, because of the incomplete cancellation of the self‐interaction in the Coulomb integral by that in the exchange integral. Recent investigations showed that the agreement of the total energy and one‐electron eigenvalue of an atom in the LDF and Hartree–Fock (HF) theories are remarkably improved by introducing a self‐interaction correction in the LDF theory. An alternative self‐interaction correction (ASIC) in the generalized exchange local‐density functional (GX‐LSD) theory is developed by equalizing the one‐electron eigenvalue with the ionization potential of the corresponding orbital. The ASIC is subsequently applied to some closed‐shell atoms and shown to give numerically better results than both the self‐interaction corrected (SIC) exchange‐only local‐spin‐density functional theory (SIC‐XO‐LSD) and the self‐interaction corrected GX‐LSD theory (SIC‐GX‐LSD).