High-Accuracy Quantum Mechanical Studies of π−π Interactions in Benzene Dimers

Abstract

Although supramolecular chemistry and noncovalent interactions are playing an increasingly important role in modern chemical research, a detailed understanding of prototype noncovalent interactions remains lacking. In particular, π−π interactions, which are ubiquitous in biological systems, are not fully understood in terms of their strength, geometrical dependence, substituent effects, or fundamental physical nature. However, state-of-the-art quantum chemical methods are beginning to provide answers to these questions. Coupled-cluster theory through perturbative triple excitations in conjunction with large basis sets and extrapolations to the complete basis set limit have provided definitive results for the binding energy of several configurations of the benzene dimer, and benchmark-quality ab initio potential curves are being used to calibrate new density functional and force-field models for π−π interactions. Studies of substituted benzene dimers indicate flaws in the conventional wisdom about substituent effects in π−π interactions. Three-body and four-body interactions in benzene clusters have also been examined.