Intermolecular induction and exchange-induction energies from coupled-perturbed Kohn–Sham density functional theory

Abstract

Coupled-perturbed Kohn–Sham theory has been used to calculate intermolecular induction and exchange-induction energies for the systems He 2, Ne 2, Ar 2, NeAr, NeHF, ArHF, (H 2) 2, (HF) 2, and (H 2O) 2. The approach is potentially exact for the induction energy. For a systematic choice of exchange-correlation potentials the results of the coupled approach were compared with an uncoupled sum-over-states approximation and with many-body symmetry-adapted perturbation theory. The asymptotically corrected PBE0AC exchange-correlation potential is found to yield very accurate induction and fairly accurate exchange-induction energies.