Accurate Induction Energies for Small Organic Molecules: 1. Theory.

Abstract

The induction energy often plays a very important role in determining the structure and properties of clusters of organic molecules, but only in recent years has an effort been made to include this energy in such calculations, notably in the field of organic crystal structure prediction. In this paper and the following one in this issue we provide ab initio methods suitable for the accurate inclusion of the induction energy for molecules containing as many as 30 atoms or so. These techniques are based on Symmetry-Adapted Perturbation Theory using Density Functional Theory [SAPT(DFT)] and use distributed polarizabilities computed using the recently developed density-fitting algorithm with constrained refinement. With this approach we are able to obtain induction models of varying complexity and study the effects of overlap and related numerical issues. Basis set effects on the exact and asymptotic induction energies are investigated, and the roles of higher-order induction energies and many-body effects are explored.