Ion size effect on colloidal forces within the primitive model

The effect of ion size on the mean force between a pair of isolated charged particles in an electrolyte solution is investigated using Monte Carlo simulations within the framework of the primitive model where both colloidal particles and small ions are represented by charged hard spheres and the solvent is treated as a dielectric continuum. It is found that the short-ranged attraction between like-charged macroions diminishes as the diameter of the intermediating divalent counterions and coions increases and the maximum attractive force is approximately a linear function of the counterion diameter. This size effect contradicts the prediction of the Asakura-Oosawa theory suggesting that an increase in the excluded volume of small ions would lead to a stronger depletion between colloidal particles. Interestingly, the simulation results indicate that both the hard-sphere collision and the electrostatic contributions to the mean force are insensitive to the size disparity of colloidal particles with the same average diameter.