How to polarise an interface with ions: the discrete Helmholtz model

Abstract

The distribution of electrolytes in an electric field usually relies on theories based on the Poisson–Boltzmann formalism. These models predict that, in the case of a metallic electrode, ionic charges screen the electrode potential, leading to concentration-dependent ion distributions. This theoretical framework was first applied at solid–liquid interfaces and then transposed to soft interfaces. However, in this latter case, the potential in which the electrolytes evolve is not homogeneous, which is less amenable to a mean-field description. In this report, we show that at polarised soft interfaces the potential difference takes place between two closely interacting ionic monolayers. In this configuration, ions of opposite charges directly neutralise each other leading to an absence of diffuse layers and charge screening by surrounding ions. Thus, independently of the electrolyte concentrations, the surface charge density is a linear function of the potential difference, which results in a constant capacitance.