We investigate diffusion in fluids near surfaces that may be coated with polymer films. We first consider diffusion in hard sphere fluids near a planar hard wall. We specifically consider color diffusion, where hard spheres are labeled A or B but are otherwise identical in all respects. In this inhomogeneous fluid, we consider a surface reaction-diffusion problem. At the left wall, a particle of species A is converted to one of species B upon a wall collision. At the opposing wall, the reverse reaction takes place: B → A. Using molecular dynamics simulation, we study the steady state of this system. We demonstrate that in the homogeneous region, a diffusing particle is subject to an equilibrium oscillatory force, the solvation force, that arises from the interfacial structuring of the fluid at the wall. For the hard sphere/hard wall system, the solvation force can be determined in various ways. We use the solvation force [the potential of mean force (PMF)] to solve the continuum diffusion equation. This provides an adequate and accurate description of the reaction-diffusion problem. The analysis is then extended to consider both color diffusion in the presence of a slowly varying one-body field such as gravity and a more applied problem of diffusion of free species through a surface film consisting of tethered chains. In both cases, the PMF experienced by the free particles is affected, but the diffusion problem can be treated in the same way as for the simpler hard sphere color diffusion case.
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