Virial exchange energies from model exact-exchange potentials

Abstract

It is shown by the example of Slater's averaged exchange potential that a poor approximation to the optimized effective potential (OEP) can yield a deceptively accurate energy via the conventional Kohn-Sham energy functional. For a trial exchange potential to be correct, its Kohn-Sham energy must coincide with the value obtained by the Levy-Perdew virial relation. Significant discrepancies between Kohn-Sham and the virial exchange energies are found for self-consistent Slater, Becke-Johnson, and effective local potentials (ELPs); their relative magnitudes are used to argue that, as approximations to the exact-exchange OEP, ELPs are the most accurate. Virial energy discrepancies vanish for Yang-Wu OEPs when the orbital and auxiliary basis sets are balanced, and remain surprisingly small for oscillatory OEPs obtained with unbalanced basis sets.