A new correlation effect in the Helmholtz and surface potentials of the electrical double layer

The restricted primitive model of an electrical double layer around a spherical macroparticle is studied by using integral equation theories and Monte Carlo simulations. The resulting theoretical curves for the Helmholtz and surface potentials versus the macroparticle charge show an unexpected positive curvature when the ionic size of uni- and divalent electrolyte species is increased. This is a novel effect that is confirmed here by computer experiments. An explanation of this phenomenon is advanced in terms of the adsorption and layering of the electrolytic species and of the compactness of the diffuse double layer. It is claimed that the interplay between electrostatic and ionic size correlation effects, absent in the classical Poisson-Boltzmann view, is responsible for this singularity.