Communication: resolving the three-body contribution to the lattice energy of crystalline benzene: benchmark results from coupled-cluster theory

Matthew R Kennedy; Ashley Ringer McDonald; A Eugene DePrince 3rd; Michael S Marshall; Rafal Podeszwa; C David Sherrill

doi:10.1063/1.4869686

Communication: resolving the three-body contribution to the lattice energy of crystalline benzene: benchmark results from coupled-cluster theory

J Chem Phys. 2014 Mar 28;140(12):121104. doi: 10.1063/1.4869686.

Authors

Matthew R Kennedy¹, Ashley Ringer McDonald¹, A Eugene DePrince 3rd¹, Michael S Marshall¹, Rafal Podeszwa², C David Sherrill¹

Affiliations

¹ Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, and School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
² Institute of Chemistry, University of Silesia, Szkolna 9, 40-006, Katowice, Poland.

PMID: 24697416
DOI: 10.1063/1.4869686

Abstract

Coupled-cluster theory including single, double, and perturbative triple excitations [CCSD(T)] has been applied to trimers that appear in crystalline benzene in order to resolve discrepancies in the literature about the magnitude of non-additive three-body contributions to the lattice energy. The present results indicate a non-additive three-body contribution of 0.89 kcal mol(-1), or 7.2% of the revised lattice energy of -12.3 kcal mol(-1). For the trimers for which we were able to compute CCSD(T) energies, we obtain a sizeable difference of 0.63 kcal mol(-1) between the CCSD(T) and MP2 three-body contributions to the lattice energy, confirming that three-body dispersion dominates over three-body induction. Taking this difference as an estimate of three-body dispersion for the closer trimers, and adding an Axilrod-Teller-Muto estimate of 0.13 kcal mol(-1) for long-range contributions yields an overall value of 0.76 kcal mol(-1) for three-body dispersion, a significantly smaller value than in several recent studies.