Structure of electric double layers: A simple weighted density functional approach

Abstract

A simple weighted density functional approach is developed for inhomogeneous ionic fluids and applied to the structure of the electric double layer using the restricted primitive model where the ions are considered to be charged hard spheres of equal diameter. The formalism is nonperturbative with both hard-sphere and electrical contributions to the one-particle correlation function evaluated through a suitably averaged weighted density, the only input being the second-order direct correlation functions of the corresponding uniform system. The approach is designed in such a way, that the calculation of the weight function is decoupled from the weighted density. Numerical results on the ionic density profile and the mean electrostatic potential near a hard wall at several surface charge densities are shown to compare well with available simulation results. The corresponding results for the nonprimitive molecular solvent model provide insight into the layering effect and the charge inversion phenomena.