Potential of mean force in confined colloids: Integral equations with fundamental measure bridge functions

Abstract

The potential of mean force for uncharged macroparticles suspended in a fluid confined by a wall or a narrow pore is computed for solvent-wall and solvent-macroparticle interactions with attractive forces. Bridge functions taken from Rosenfeld's density-functional theory are used in the reference hypernetted chain closure of the Ornstein-Zernike integral equations. The quality of this closure is assessed by comparison with simulation. As an illustration, the role of solvation forces is investigated. When the "residual" attractive tails are given a range appropriate to "hard sphere-like" colloids, the unexpected role of solvation forces previously observed in bulk colloids is confirmed in the confinement situation.