Insights from Monte Carlo simulations on charge inversion of planar electric double layers in mixtures of asymmetric electrolytes.

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.