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

TL;DR

This paper introduces a novel DFT-based method for accurately modeling non-covalent interactions by combining dispersion-free DFT with dispersion corrections, utilizing monomer polarization and Pauli blockade to avoid double counting.

Contribution

It presents a new DFT approach that incorporates monomer polarization and Pauli blockade to improve non-covalent interaction energy calculations without double counting dispersion.

Findings

Interaction energies agree with benchmark values

Applicable to rare-gas dimers and hydrogen bonds

Effective in modeling ion-rare gas interactions

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.