We study the effect of solvent granularity on the effective force between two
charged colloidal particles by computer simulations of the primitive model of
strongly asymmetric electrolytes with an explicitly added hard sphere solvent.
Apart from molecular oscillating forces for nearly touching colloids which
arise from solvent and counterion layering, the counterions are attracted
towards the colloidal surfaces by solvent depletion providing a simple
statistical description of hydration. This, in turn, has an important influence
on the effective forces for larger distances which are considerably reduced as
compared to the prediction based on the primitive model. When these forces are
repulsive, the long-distance behaviour can be described by an effective Yukawa
pair potential with a solvent-renormalized charge. As a function of colloidal
volume fraction and added salt concentration, this solvent-renormalized charge
behaves qualitatively similar to that obtained via the Poisson-Boltzmann cell
model but there are quantitative differences. For divalent counterions and
nano-sized colloids, on the other hand, the hydration may lead to overscreened
colloids with mutual attraction while the primitive model yields repulsive
forces. All these new effects can be accounted for through a solvent-averaged
primitive model (SPM) which is obtained from the full model by integrating out
the solvent degrees of freedom. The SPM was used to access larger colloidal
particles without simulating the solvent explicitly.Comment: 14 pages, 16 craphic