Long-range forces and charge inversions in model charged colloidal dispersions at finite concentration

In charged colloidal dispersion systems the interest is in finding their stability conditions, phase transitions, and transport properties, either in bulk or confinement, among other physicochemical quantities, for which the knowledge of the dispersions' molecular structure and the associated macroion-macroion forces is crucial. To investigate these phenomena simple models have been proposed. Most of the theoretical and simulation studies on charged particles suspensions are at infinite dilution conditions. Hence, these studies have been focused on the electrolyte structure around one or two isolated central particle(s), where phenomena as charge reversal, charge inversion and surface charge amplification have been shown to be relevant. However, experimental studies at finite volume fraction exhibit interesting phenomenology which imply very long-range correlations. A simple, yet useful, model is the Colloidal Primitive Model, in which the colloidal dispersion is modeled as a mixture of size (and charge) asymmetrical hard spheres, at finite volume fraction. In this paper we review recent integral equations solutions for this model, where very long-range attractive-repulsive forces, as well as new long-range, giant charge inversions are reported. The calculated macroions radial distribution functions, charge distributions, and macroion-macroion forces are qualitatively consistent with existing experimental results, and Monte Carlo and molecular dynamics simulations.