Compressibility route to solvation structure

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Abstract
We discuss the basic model of structural colloidal pair-interactions, consisting of a simple fluid confined between a pair of planar walls. A compressibility route to solvation structure follows from the statistical mechanical hierarchy obtained by successive functional differentiation of the grand potential, with respect to the solute-medium interaction. In particular, for short-range wall-fluid forces a shielding approximation to an integral equation for the density profile yields a solution in terms of a product of profiles obtained from the limit of large wall-separation. In one-dimension the shielding solution is exact in the absence of non-nearest-neighbour fluid interactions. In the case of hard wall boundaries, the exact form of both the density profile and the solvation force can be deduced at small wall-separation. The shielding approximation with hard wall boundary conditions leads to a first-order differential equation for the solvation force.

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