A new, versatile, theoretically self-consistent procedure is proposed for determining the thermodynamic properties of a classical system in the condensed fluid phase. The method of complementary variational principles, developed by A. M. Arthurs and his colleagues, is used to generate reference state (hard core) correlation function data via analysis of a well known (non-linear) integral equation for the pair distribution function (namely, the Yvon-Born-Green equation). These data are then used within the context of the perturbation theory of classical fluids developed by Zwanzig, as implemented by Barker and Henderson, to investigate the role of attractive and repulsive perturbations in influencing the thermodynamics of the reference system. As a specific application of this procedure, one that leads to many new results, we focus on a classical system of particles whose effective interactions are confined to a space of two dimensions. We consider two classes of potential functions (the square well/square shoulder and linear well/linear shoulder potentials) and consider separately the effects of attractive and repulsive perturbations. Where possible, the predictions of the theory are compared against known results (specifically, the results obtained via molecular dynamics simulation); we find that the variational method accurately represents the thermodynamics of the reference state (the hard disc fluid) up to densities of σρ2 ≈0·8, and the variational method in tandem with perturbation theory adequately represents the thermodynamics of the square shoulder system over the same density range. The effects of increasing the strength and range parameters of the potential are explored in detail and quantified. Both for the case of attractive and repulsive perturbations, isotherms of the van der Waals type are found to develop below a certain critical temperature in the dense fluid regime. The possible significance of these mean field results is discussed.
Read full abstract