Calculation of inhomogeneous-fluid cluster expansions with application to the hard-sphere/hard-wall system

We examine the suitability of cluster expansion methods for the description of inhomogeneous fluids. In particular, we apply these methods to characterize the density profile, surface tension, and excess adsorption for a hard-sphere fluid near a hard wall. Coefficients for these series up to seventh order are evaluated by the Mayer-sampling Monte Carlo method. Comparison of the series to Monte Carlo simulations of these systems finds very good agreement up to bulk densities approaching the freezing point. This work indicates that knowledge of surface cluster integrals of inhomogeneous systems can be at least as useful as the bulk-phase virial expansions. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4798456]