Testing one component plasma models on colloidal overcharging phenomena.

In this paper, the mechanisms of overcharging of a colloidal macroion in the presence of multivalent counterions are investigated by means of Monte Carlo simulations. This computational technique appears as a powerful tool for probing the validity of semianalytical models developed for this issue. In particular, the simulations performed are compared with the predictions of two different models based on the one component plasma (OCP) theory. Therein, the multivalent ionic atmosphere confined at the macroion surface is approximated by a two-dimensional Wigner crystal. These kinds of models are largely used in the literature since (in some cases) they present quite simple equations to describe the electric double layer (EDL) of macroions with different geometries in the presence of much smaller (but still multivalent) ions. In this sense, charge inversion phenomena of membranes, polyelectrolytes, DNA molecules, etc., are straightforwardly predicted in terms of these expressions. Unfortunately, comparisons between these predictions and experimental results are scarce, mostly due to the difficulty to reproduce the experimental conditions in the laboratory. Accordingly, the goal of the present paper is to simulate EDLs under real conditions (in which overcharging phenomena are expected to happen) and use the results obtained in this way for comparing with those obtained from OCP models.