ZMP-SAPT: DFT-SAPT using ab initio densities

Abstract

Symmetry Adapted Perturbation Theory (SAPT) has become an important tool when predicting and analyzing intermolecular interactions. Unfortunately, Density Functional Theory (DFT)-SAPT, which uses DFT for the underlying monomers, has some arbitrariness concerning the exchange-correlation potential and the exchange-correlation kernel involved. By using ab initio Brueckner Doubles densities and constructing Kohn-Sham orbitals via the Zhao-Morrison-Parr (ZMP) method, we are able to lift the dependence of DFT-SAPT on DFT exchange-correlation potential models in first order. This way, we can compute the monomers at the coupled-cluster level of theory and utilize SAPT for the intermolecular interaction energy. The resulting ZMP-SAPT approach is tested for small dimer systems involving rare gas atoms, cations, and anions and shown to compare well with the Tang-Toennies model and coupled cluster results.