Density Functional Theory Approach to Noncovalent Interactions via Monomer Polarization and Pauli Blockade

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.