Linear fractional charge behavior in density functional theory through dielectric tuning of conductor-like polarizable continuum model.

Abstract

A property of exact density functional theory is linear fractional charge behavior as electrons are added or removed from a molecule. Typical density functional approximations (DFAs) exhibit delocalization error, which overstabilizes this fractional charge. Conversely, solvent corrections have been shown to erroneously destabilize this fractional charge. This work will show that an implicit solvent correction with a tuned dielectric can be used as an ad hoc correction to offset the delocalizing character of DFAs and achieve linear fractional charge behavior. While desirable, in principle, we find that this linear charge behavior degrades the vertical ionization energies reported by DFAs. Our results reveal that the localizing character of the solvent correction and the Hartree-Fock (HF) exchange offset each other. This helps explain the decreased ratios of HF exchange to DFA exchange in long-range hybrid tuning studies that use a solvent correction.