Relation between exchange-only optimized potential and Kohn-Sham methods with finite basis sets; solution of a paradox

TL;DR

This paper clarifies why exchange-only optimized effective potential methods with finite basis sets often do not reproduce Hartree-Fock energies, highlighting the importance of basis set balance for physically meaningful exchange potentials.

Contribution

It demonstrates the conditions under which finite basis set xOEP methods can or cannot replicate Hartree-Fock energies and explains the origin of unphysical exchange potentials.

Findings

Finite basis xOEP methods generally do not yield Hartree-Fock energies.

Unphysical oscillations occur in exchange potentials when basis sets are not balanced.

Properly balanced basis sets enable xOEP to represent exact exchange-only Kohn-Sham methods.

Abstract

Arguments showing that exchange-only optimized effective potential (xOEP) methods, with finite basis sets, cannot in general yield the Hartree-Fock (HF) ground state energy, but a higher one, are given. While the orbital products of a complete basis are linearly dependent, the HF ground state energy can only be obtained via a basis set xOEP scheme in the special case that all products of occupied and unoccupied orbitals emerging from the employed orbital basis set are linearly independent from each other. In this case, however, exchange potentials leading to the HF ground state energy exhibit unphysical oscillations and do not represent a Kohn-Sham (KS) exchange potential. These findings solve the seemingly paradoxical results of Staroverov, Scuseria and Davidson that certain finite basis set xOEP calculations lead to the HF ground state energy despite the fact that within a real space (or complete basis) representation the xOEP ground state energy is always higher than the HF energy. Moreover, whether or not the occupied and unoccupied orbital products are linearly independent, it is shown that basis set xOEP methods only represent exact exchange-only (EXX) KS methods, i.e., proper density-functional methods, if the orbital basis set and the auxiliary basis set representing the exchange potential are balanced to each other, i.e., if the orbital basis is comprehensive enough for a given auxiliary basis. Otherwise xOEP methods do not represent EXX KS methods and yield unphysical exchange potentials.