Behavior of mixtures of symmetric and asymmetric electrolytes near discretely charged planar surfaces: a Monte Carlo study.

Canonical Monte Carlo (CMC) simulations are employed in this work in order to study the structure of the electrical double layer (EDL) near discretely charged planar surfaces in the presence of symmetric and asymmetric indifferent electrolytes within the framework of a primitive model. The effects of discreteness and strength of surface charge, charge asymmetry, and size asymmetry are specific focuses of this work. The CMC simulation protocol is initially tested against the classical theory, the modified Gouy-Chapman (GC) theory, in order to assess the reliability of the simulation results. The CMC simulation results and the predictions of the classical theory show good agreement for 1:1 electrolytes and low surface charge, at which conditions the GC theory is valid. Simulations with symmetric and asymmetric electrolytes and mixtures of the two demonstrate that size plays an important role in determining the species present in the EDL and how the surface charge is screened. A size-exclusion effect could be consistently detected. Although it is energetically favorable that higher-valence ions screen the surface charge, their larger size prevents them from getting close to the surface. Smaller ions with lower valences perform the screening of the charge, resulting in higher local concentrations of small ions close to the surface. The simulations also showed that the strength of the surface charge enhances the size-exclusion effect. This effect will definitely affect the magnitude of the forces between interacting charged surfaces.