Modified thermodynamic perturbation theory for fused–sphere dimer fluids

Abstract

Wertheim's thermodynamic perturbation theory of first order (TPT1) is based on the approximation that the monomer–monomer distribution functions can be approximated by the reference fluid distribution functions regardless of the amount of bonding. This is remarkably accurate for chains formed by tangent spheres, but no longer valid for chains of fused spheres. This constitutes the reason for the inadequacy of TPT1 for fused sphere chains. We present a systematic modification of TPT1, the path integral perturbation method, that takes into account the variations of the distribution functions with extent of bonding. We demonstrate the accuracy of the theory for mixtures of hard spheres and diatomics over a range of extent of bonding (pure monomers to pure dimers) and degree of fusion (bond length 0–1). We found that the choice of reference fluid was decisive for the accuracy of the model's predictions. The proposed theory can accurately predict the properties of mixtures of hard spheres and diatomics, and of the pure fused diatomic fluids. The results from the path integral theory are in excellent agreement with simulation results, and compare favourably with the results from the Tildesley–Streett and the Boublík–Nezbeda equations of state.