Fluctuation and correlation effects in a charged surface immersed in an electrolyte solution

Abstract

We explore correlation and fluctuation effects in an overall neutral system consisting of a single homogeneously charged planar surface with both the counterions and coions distributed on both sides of the surface. Using a field-theoretic formulation, we compute the one-loop correction to the electrostatic potential, to the ion densities, to the surface tension, and to the surface free energy. From the asymptotic behavior of the electrostatic potential, we obtain an exact expression for the effective surface charge density, which can become negative, indicating charge inversion. Furthermore, we find that the ion distributions can be substantially different from the mean-field ion densities. In particular, the counterion density, at high couplings, develops a minimum at some intermediate distances, larger than the Gouy-Chapman length, away from the charged surface, whereas the coion density develops a maximum, whose values can be greater than the counterion density. Therefore, the coions develop a second layer. Moreover, the one-loop correction always lowers the electrostatic contributions to the surface tension and at high couplings, the surface tension may become negative.