``Highly Accurate Coupled Cluster Potential Energy Curves for Benzene Dimer: The Sandwich, T-Shaped, and Parallel-Displaced Configurations,'' M. O. Sinnokrot and C. D. Sherrill, J. Phys. Chem. A. 108, 10200-10207 (2004).

State-of-the-art electronic structure theory has been applied to generate potential energy curves for the sandwich, T-shaped, and parallel-displaced configurations of the simplest prototype of aromatic pi-pi interactions, the benzene dimer. Results were obtained using second-order Moller-Plesset perturbation theory (MP2) and coupled-cluster with singles, doubles and perturbative triples [CCSD(T)] with different augmented, correlation-consistent basis sets. At the MP2 level, the smallest basis set used (a modified aug-cc-pVDZ basis) underestimates the binding by ~0.5 kcal/mol at equilibrium and by ~1 kcal/mol at smaller intermonomer distances compared to results with a modified aug-cc-pVQZ basis (denoted aug-cc-pVQZ*). The best MP2 binding energies differ from the more accurate CCSD(T) values by up to 2.0 kcal mol-1 at equilibrium and by more than 2.5 kcal mol-1 at smaller intermonomer distances, highlighting the importance of going beyond MP2 to achieve higher accuracy in binding energies. Symmetry adapted perturbation theory is used to analyze interaction energies in terms of electrostatic, dispersion, induction, and exchange-repulsion contributions. The high-quality estimates of the CCSD(T)/aug-cc-pVQZ* potential energy curves for benzene dimer presented here provide a better understanding of how the strength of pi-pi interactions varies with distance and orientation of the rings, and will assist in the development of approximate methods capable of modeling weakly bound pi-pi systems.