The conventional paradigm for characterizing surface overcharging and charge reversal is based on the so-called Stern layer, in which surface dissociation reaction and specific chemical adsorption are assumed to take place. In this article, a series of Monte Carlo simulations have been applied to obtain useful insights into the underlying physics responsible for these two kinds of anomalous phenomena at the interface of two dielectrics, with special emphasis on the case of divalent counterions that are more relevant in natural and biological environments. At a weakly charged surface, it is found that independent of the type of surface charge distribution and the dielectric response of the solution, the overcharging event is universally driven by the ion size-asymmetric effect. Exceptionally, the overcharging still persists when the surface is highly charged but is only restricted to the case of discrete surface charge in a relatively low dielectric medium. As compared to the adsorption onto the homogeneously smeared charge surface that has the same average affinity for counterions, on the other hand, charge reversal under the action of a dielectric response can be substantially enhanced in the discrete surface charge representation due to strong association of counterions with interfacial groups, and the degree of enhancement depends in a nontrivial way on the reduction of the medium dielectric constant and the steric effects of finite ion size. Rather interestingly, the charge reversal is of high relevance to the overcharging of interfaces because the overwhelming interfacial association forces the coions closer to the surface due to their smaller size than the counterions. Upon the addition of a monovalent salt to the solution, the interfacial association with divalent counterions makes surface overcharging and charge reversal widely unaffected, in contrast to the prevailing notion that screening of surface charge of a homogeneous nature is determined by the competitive effects between size-exclusion effects and energetic contributions. Overall, the present work highlights that the complex interplay between the electrostatic and steric interactions should be coupled to the realistic character of surface charge to establish a faithful description of the overcharging and charge reversal at heterophase interfaces.

No abstract

Monte Carlo simulations of a planar negatively charged dielectric interface in contact with a mixture of 1:1 and 3:1 electrolytes are carried out using the unrestricted primitive model under more realistic hydrated ion sizes. Two typical surface charge densities are chosen to represent the systems from the weak to strong coupling regimes. Our goal is to determine the dependence of the degree of charge inversion on increasing concentration of both mono- and trivalent salts and to provide a systematic study on this peculiar effect between short-range and electrostatic correlations. The numerical results show that addition of monovalent salt diminishes the condensation of trivalent counterions due to either the favorable solvation energy or the available space constraints. As the concentration of trivalent salt increases, on the other hand, the inclusion of the ionic size and size asymmetry results in a damped oscillatory charge inversion at low enough surface charge and another counterintuitive surface charge amplification. It is proposed that both of the anomalous events in the weak coupling regime are thought to be entropic in origin which is completely different from the electrostatic driven charge inversion in the strong coupling regime. In addition, the electrostatic images arising from the dielectric mismatch lead to a decaying depletion effect on the structure of double layer with growing salt concentration in the case of low charged interface but have no effect at high surface charge values. The microscopic information obtained here points to the need for a more quantitative theoretical treatment in describing the charge inversion phenomenon of real colloidal systems.

No abstract