Heterogeneous surface charge confining an electrolyte solution.

The structure of dilute electrolyte solutions close to a surface carrying a spatially inhomogeneous surface charge distribution is investigated by means of classical density functional theory within the approach of fundamental measure theory. For electrolyte solutions, the influence of these inhomogeneities is particularly strong because the corresponding characteristic length scale is the Debye length, which is large compared to molecular sizes. Here, a fully three-dimensional investigation is performed, which accounts explicitly for the solvent particles, and thus provides insight into effects caused by ion-solvent coupling. The present study introduces a versatile framework to analyze a broad range of types of surface charge heterogeneities even beyond the linear response regime. This reveals a sensitive dependence of the number density profiles of the fluid components and of the electrostatic potential on the magnitude of the charge as well as on the details of the surface charge patterns at small scales.