Fluids with highly directional attractive forces. II. Thermodynamic perturbation theory and integral equations

Abstract

The formalism of statistical thermodynamics developed in the preceding paper is used as a basis for deriving tractable approximations. The system treated is one where repulsion and highly directional attraction due to a single molecular site combine to allow the formation of dimers, but no highers-mers. We derive thermodynamic perturbation theory, using the system interacting with only the repulsive potential as a reference system. Two distinct integral equations for the pair correlation are derived. The first one treats both parts of the interaction approximately; the other one employs the repulsive reference system used in perturbation theory. We show that each of these integral equations permits the calculation of an important thermodynamic function directly from the solution at a single state of density and temperature. In the first case this applies to a pressure consistent with the compressibility relation, in the second to the excess Helmholtz free energy over the reference system.