Approximating quantum many-body intermolecular interactions in molecular clusters using classical polarizable force fields

摘要

Many-body intermolecular interaction expansions provide a promising avenue for the efficient quantum mechanical treatment of molecular clusters and condensed-phase systems, but the computationally expensive three-body and higher terms are often nontrivial. When polar molecules are involved, these many-body terms are typically dominated by electrostatic induction effects, which can be approximated relatively easily. We demonstrate an accurate and inexpensive hybrid quantum/classical model in which one- and two-body interactions are computed quantum mechanically, while the many-body induction effects are approximated with a simple classical polarizable force field. Whereas typical hybrid quantum/classical models partition a system spatially into distinct quantum and classical regions, the model demonstrated here partitions based on the order in the many-body interaction series. This enables a spatially homogeneous treatment of the entire system, which could prove advantageous in studying a wide range of condensed-phase molecular systems.