Classical charged fluids at equilibrium near an interface: Exact analytical density profiles and surface tension

Abstract

The structure of equilibrium density profiles in an electrolyte in the vicinity of an interface with an insulating or conductive medium is of crucial importance in chemical physics and colloidal science. The Coulomb interaction is responsible for screening effects, and in dilute solutions the latter effects give rise to universal leading corrections to nonideality, which distinguish electrolyte from nonelectrolyte solutions. An example is provided by the excess surface tension for an air-water interface, which is determined by the excess particle density, and which was first calculated by Onsager and Samaras. Because of the discrepancy between the dielectric constants on both sides of the interface, every charge in the electrolyte interacts with an electrostatic image, and the Boltzmann factor associated with the corresponding self-energy has an essential singularity over the length scalel from the wall. Besides Coulomb interactions, short-range repulsions must be taken into account in order to prevent the collapse between charges with opposite signs or between each charge and its image when the solvent dielectric constant is lower than that of the continuous medium on the other side of the interface. For a dilute and weaklycoupled electrolyte,l is negligible with respect to the bulk Debye screening length ξD. In the framework of the grand-canonical ensemble, systematic partial resummations in Mayer diagrammatics allow one to exhibit that, in this regime, the exact density profiles at leading order are the same as if they were calculated in a partially-linearized mean-field theory, where the screened pair interaction obeys an inhomogeneous Debye equation. In the latter equation the effective screening length depends on the distancex from the interface: it varies very fast over the lengthl and tends to its bulk value over a few ξDs. The equation can be solved iteratively at any distancex, and the exact density profiles are calculated analytically up to first order in the coupling parameter l/ξD. They show the interplay between three effects: (1) the geometric repulsion from the interface associated with the deformation of screening clouds, (2) the polarization effects described by the images on the other side of the interface, (3) the interaction between each charge and the potential drop created by the electric layer which appears as soon as the fluid has not a charge-symmetric composition. Moreover, the expressions allow us to go beyond Onsager-Samaras theory: the surface tension is calculated for charge-asymmetric electrolytes and for any value of the ratio between the dielectric constants on both sides of the interface. Similar diagrammatic techniques also allow one to investigate the charge renormalization in the dipolar effective pair interaction along the interface with an insulating medium.