Fluids with highly directional attractive forces. III. Multiple attraction sites

We derive a reformulation of statistical thermodynamics for fluids of molecules which interact by highly directional attraction. The molecular model consists of a repulsive core and several sites of very short-ranged attraction. We explore the relationship between graph cancelation in the fugacity expansion and three types of steric incompatibility between repulsive and attractive interactions involving several molecules. The steric effects are used to best advantage in a limited regrouping of bonds. This controls the density parameters which appear when articulation points are eliminated in the graphical representation. Each density parameter is a singlet density for a species consisting of molecules with a specified set of sites bonded. The densities satisfy subsidiary conditions of internal consistency. These conditions are equivalent to a minimization of the Helmholtz free energyA. Graphical expressions forA and for the pressurep are derived. Analogs of thes-particle direct correlation functions and of the Ornstein-Zernike equation are found.