Impact of surface charges on the solvation forces in confined colloidal solutions.

Combining computer simulations and experiments we address the impact of charged surfaces on the solvation forces of a confined, charged colloidal suspension (slit-pore geometry). Investigations based on the colloidal-probe atomic-force-microscope technique indicate that an increase in surface charges markedly enhances the oscillations of the force in terms of their amplitude. To understand this effect on a theoretical level we perform grand-canonical Monte-Carlo simulations (GCMC) of a coarse-grained model system. It turns out that various established approaches of the interaction between a charged colloid and a charged wall, such as linearized Poisson-Boltzmann (PB) theory involving the bulk screening length, do not reproduce the experimental observations. We thus introduce a modified PB potential with a space-dependent screening parameter. The latter takes into account, in an approximate way, the fact that the charged walls release additional (wall) counterions which accumulate in a thin layer at the surface(s). The resulting, still purely repulsive fluid-wall potential displays a nonmonotonic behavior as function of the surface potential with respect to the strength and range of repulsion. GCMC simulations based on this potential reproduce the experimentally observed charge-induced enhancement in the force oscillations. We also show, both by experiment and by simulations, that the asymptotic wave- and decay length of the oscillating force do not change with the wall charge, in agreement with predictions from density functional theory.