Physical mechanisms of intermolecular interactions from symmetry-adapted perturbation theory.

ABSTRACT

Symmetry-adapted perturbation theory (SAPT) is a method for computational studies of noncovalent interactions between molecules. This method will be discussed here from the perspective of establishing the paradigm for understanding mechanisms of intermolecular interactions. SAPT interaction energies are obtained as sums of several contributions. Each contribution possesses a clear physical interpretation as it results from some specific physical process. It also exhibits a specific dependence on the intermolecular separation R. The four major contributions are the electrostatic, induction, dispersion, and exchange energies, each due to a different mechanism, valid at any R. In addition, at large R, SAPT interaction energies are seamlessly connected with the corresponding terms in the asymptotic multipole expansion of interaction energy in inverse powers of R. Since such expansion explicitly depends on monomers' multipole moments and polarizabilities, this connection provides additional insights by rigorously relating interaction energies to monomers' properties.