Structure of hard particle fluids near a hard wall. II. y w(z) for hard spheres

Abstract
Predictions of the wall–cavity correlation function yw(z) for hard spheres against a hard wall are tested using the treatment that Smith and Speedy developed and examined for the case of hard disks in part I of this series, as well as an extension of this approach using an alternative procedure. yw(z) in the range 0≤z≤1 may be accurately predicted using only the thermodynamic properties of the bulk fluid, for which precise expressions are available. These predictions are tested by determining yw(z) and the cavity concentration profile nwo(z) in a computer simulation study. We also derive a new integral equation relating yw(z) near the wall to its values just outside the wall and illustrate this in examining the consistency of our computer simulation results.