A DFT Approach to Non-Covalent Interactions via Monomer Polarization and Pauli Blockade

Rajchel, Łukasz; Żuchowski, Piotr S.; Szczęśniak, Małgorzata M.; Chałasiński, Grzegorz

A DFT Approach to Non-Covalent Interactions via Monomer Polarization and Pauli Blockade

Abstract

We propose a~"DFT+dispersion" treatment which avoids double counting of dispersion terms by deriving the dispersion-free density functional theory~(DFT) interaction energy and combining it with DFT-based dispersion. The formalism involves self-consistent polarization of DFT monomers restrained by the~exclusion principle via the~Pauli blockade technique. Any exchange-correlation potential can be used within monomers, but only the exchange operates between them. The applications to rare-gas dimers, ion-rare gas interactions and hydrogen bonds demonstrate that the interaction energies agree with benchmark values.