Influence of anisotropic ion shape, asymmetric valency, and electrolyte concentration on structural and thermodynamic properties of an electric double layer

TL;DR

This study uses grand canonical Monte Carlo simulations to explore how ion shape, valency asymmetry, and electrolyte concentration influence the structure and thermodynamics of electric double layers near charged surfaces.

Contribution

It introduces a detailed simulation model accounting for anisotropic ion shapes and valency asymmetry, revealing their effects on electric double layer properties.

Findings

Differential capacitance curves change shape with electrolyte concentration.

Valency asymmetry shifts the capacitance maximum position.

Ion shape and valency influence the electrode-ion distribution profiles.

Abstract

Grand canonical Monte Carlo simulation results are reported for an electric double layer modelled by a planar charged hard wall, anisotropic shape cations, and spherical anions at different electrolyte concentrations and asymmetric valencies. The cations consist of two tangentially tethered hard spheres of the same diameter, $d$. One sphere is charged while the other is neutral. Spherical anions are charged hard spheres of diameter $d$. The ion valency asymmetry 1:2 and 2:1 is considered, with the ions being immersed in a solvent mimicked by a continuum dielectric medium at standard temperature. The simulations are carried out for the following electrolyte concentrations: 0.1, 1.0 and 2.0 M. Profiles of the electrode-ion, electrode-neutral sphere singlet distributions, the average orientation of dimers, and the mean electrostatic potential are calculated for a given electrode surface charge, $\sigma$, while the contact electrode potential and the differential capacitance are presented for varying electrode charge. With an increasing electrolyte concentration, the shape of differential capacitance curve changes from that with a minimum surrounded by maxima into that of a distorted single maximum. For a 2:1 electrolyte, the maximum is located at a small negative $\sigma$ value while for 1:2, at a small positive value.