Optimized Cluster Expansions for Classical Fluids. II. Theory of Molecular Liquids

Abstract

The optimized cluster expansion methods developed in the first article of this series (I) are generalized to apply to molecular fluids. These methods make use of summations of ring and chain cluster diagrams. The summations are performed explicitly for certain classes of molecular models. The molecules in these classes contain several ``interaction sites,'' and the total interaction between two molecules is a sum of site‐site potentials that depend on the scalar distances between sites on the two molecules. The principal results of this work are computationally simple techniques for calculating the thermo‐dynamic properties and pair correlation functions of molecular fluids in which the intermolecular interactions are highly angular dependent. The techniques should be reliable since they arise from the same approximations that have been shown to be very accurate when applied to simple fluids.