A post-Hartree–Fock model of intermolecular interactions

Abstract

Intermolecular interactions are of great importance in chemistry but are difficult to model accurately with computational methods. In particular, Hartree–Fock and standard density-functional approximations do not include the physics necessary to properly describe dispersion. These methods are sometimes corrected to account for dispersion by adding a pairwise C6∕R6 term, with C6 dispersion coefficients dependent on the atoms involved. We present a post-Hartree–Fock model in which C6 coefficients are generated by the instantaneous dipole moment of the exchange hole. This model relies on occupied orbitals only, and involves only one, universal, empirical parameter to limit the dispersion energy at small interatomic separations. The model is extensively tested on isotropic C6 coefficients of 178 intermolecular pairs. It is also applied to the calculation of the geometries and binding energies of 20 intermolecular complexes involving dispersion, dipole-induced dipole, dipole–dipole, and hydrogen-bonding interactions, with remarkably good results.