Overcharging and Free Energy Barriers for Equally Charged Surfaces Immersed in Salt Solutions.

The stability of dispersions containing charged particles may obviously be regulated by salt. In some systems, the effective charge, as measured by the potential some small distance away from the particles, can have a sign opposite to the bare surface charge. If charge reversal takes place, there is typically a salt concentration regime within which colloidal stability increases with added salt. These experimental findings on dispersions have been corroborated by atomic force microscopy investigations, where an attraction is found at short separations. This attraction is stronger than expected from standard DLVO theory, and there has been considerable debate concerning its origin. In this work, we use simple coarse-grained models of these systems, where the bare surfaces carry a uniform charge density, and ion-specific adsorption is absent. Our hypothesis is that these experimental observations can be explained by such a simplistic pure Coulomb based model. Our approach entails grand canonical Metropolis Monte Carlo (MC) simulations as well as correlation-corrected Poisson-Boltzmann (cPB) calculations. In the former case, all ions have a common size, while the cPB utilizes a point-like model. We devote significant attention on apparent surface charge densities and interactions between large flat model surfaces immersed in either a 2:1 salt or a 3:1 salt. In contrast to most of the previous theoretical efforts in this area, we mainly focus on the weak long-ranged repulsion and its connection to an effective surface charge. We find a charge reversal and a concomitant development of a free energy barrier for both salts. The experimentally observed nonmonotonic dependence of colloidal stability on the salt concentration is reproduced using MC simulations as well as cPB calculations. A strong attraction is observed at short range for all investigated cases. We argue that in our model, all non-DLVO aspects can be traced to ion-ion correlations.