Toward Modeling the Structure of Electrolytes at Charged Mineral Interfaces using Classical Density Functional Theory (2312.04976v2)

Abstract: The organization of water molecules and ions between charged mineral surfaces determines the stability of colloidal suspensions and the strength of phase-separated particulate gels. In this article we assemble a density functional that measures the free energy due to the interaction of water molecules and ions near electric double layers. The model accounts for the finite size of the particles using fundamental measure theory, hydrogen-bonding between water molecules using Wertheim's statistical association theory, long-range dispersion interactions using Barker and Henderson's high temperature expansion, electrostatic correlations using a functionalized mean-spherical approximation, and Coulomb forces through the Poisson equation. These contributions are shown to produce highly correlated structures, aptly rendering the layering of counter-ions and co-ions at highly charged surfaces, and permitting the solvation of ions and surfaces to be measured by a combination of short-ranged association and long-ranged attraction. The model is tested in a planar geometry near soft, charged surfaces to reproduce the structure of water near graphene and mica. For mica surfaces, explicitly representing the density of the outer oxygen layer of the exposed silica tetrahedra in the domain permits water molecules to hydrogen-bind to the surface. When electrostatic interactions are included, water molecules assume a hybrid character, being accounted for implicitly in the dielectric constant but explicitly otherwise. The disjoining pressure between approaching like-charged surfaces is calculated, demonstrating the model's ability to probe pressure oscillations that arise during the expulsion of ions and water layers from the interfacial gap, and predict the strong inter-attractive stresses that form at narrow interfacial spacing when the surface charge is overscreened.