Cluster integrals and virial coefficients for realistic molecular models

Phys Rev E. 2020 May;101(5-1):051301. doi: 10.1103/PhysRevE.101.051301.

Abstract

We present a concise, general, and efficient procedure for calculating the cluster integrals that relate thermodynamic virial coefficients to molecular interactions. The approach encompasses nonpairwise intermolecular potentials generated from quantum chemistry or other sources; a simple extension permits efficient evaluation of temperature and other derivatives of the virial coefficients. We demonstrate with a polarizable model of water. We argue that cluster-integral methods are a potent yet underutilized instrument for the development and application of first-principles molecular models and methods.