PNNL

Abstract

Understanding the electrochemical properties of mineral–water interfaces tends to rely upon electrical double layer (EDL) models, but these models are based on the assumption that electrostatic equilibrium is constantly maintained. In reality, interfacial reactions, ion diffusion, and their electrochemical signatures are based in nonequilibrium conditions of locally or globally imbalanced electrical fields where current EDL models have limited purview. Here we performed molecular dynamics (MD) simulations of the orthoclase (001) surface in contact with a 1 M NaCl aqueous solution under various electric fields, to explore the interplay between EDL structure and dynamics when perturbed by electric fields of different direction and strength, by confinement, and by different distributions of structural surface charge. The simulations showed that confinement between two opposing (001) surfaces led to the development of an induced field when the applied field was perpendicular to the surfaces and, as a result, to ionic diffusion coefficients that were independent of electric field strength. In contrast, when the applied field was parallel to the surfaces, confinement resulted in ionic diffusion coefficients that were more strongly dependent on the magnitude of the electric field than in bulk water. Differences in the density and distribution of aluminol groups on the two surfaces had a significant impact on how the interfacial structure and dynamics varied in the presence of an electric field. Notably, these differences resulted in an electro-osmotic flow with opposite directions at the two surfaces under parallel applied electric field. Overall, the MD simulations highlighted the importance of considering atomic-level structure and heterogeneities when developing models of the electrochemical properties of mineral–water interfaces.