ZMP-SAPT: DFT-SAPT using ab initio Densities

TL;DR

This paper introduces ZMP-SAPT, a novel method combining ab initio densities with DFT-SAPT to reduce dependence on exchange-correlation models, enabling more accurate intermolecular interaction predictions.

Contribution

It presents a new approach that uses ab initio Brueckner densities and ZMP orbitals to improve DFT-SAPT accuracy and reduce arbitrariness in modeling intermolecular forces.

Findings

ZMP-SAPT compares well with coupled cluster results.

The method reduces dependence on exchange-correlation potential models.

Tests on small systems validate the approach.

Abstract

Symmetry Adapted Perturbation Theory (SAPT) has become an important tool when predicting and analyzing intermolecular interactions. Unfortunately, DFT-SAPT, which uses Density Functional Theory (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.