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.
Highlights
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
The applicability of the density functional theory (DFT) to calculations of intermolecular potentials of van der Waals complexes depends upon a seamless inclusion of the dispersion energy, a long-range correlation effect, in the DFT treatment
Summary
The formalism involves self-consistent polarization of DFT monomers restrained by the exclusion principle via the Pauli blockade technique. The applicability of the density functional theory (DFT) to calculations of intermolecular potentials of van der Waals complexes depends upon a seamless inclusion of the dispersion energy, a long-range correlation effect, in the DFT treatment. One promising avenue consists of using an a posteriori dispersion correction added to supermolecular DFT calculations of interaction energy, in the spirit of Ahlrichs et al [8].
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