Monte Carlo Study of a Planar Electric Double Layer Formed by Ions with Off-Center Charge

Abstract

Grand canonical Monte Carlo simulation results are reported for an electric double layer (EDL) modeled by a planar charged hard wall, hard sphere cations with an off-center charge, and spherical anions with a charge at the center of the sphere. The ion charge numbers are Z = +1 and Z = -1, and the diameter, d, of a hard sphere is the same for anions and cations. The ions are immersed in a solvent mimicked by a continuum dielectric medium at standard temperature. The results are obtained for three values of charge displacement, s = d/16, d/4, 7d/16 from the center of the sphere and the following electrolyte concentrations: 0.5, 1.0, 2.0, and 3.0 M. The profiles of electrode-ion singlet distributions, cation reduced charge density, angular function, and mean electrostatic potential are reported for an electrode surface charge density σ = -0.30 C m, whereas the electrode potential and the differential capacitance of EDL are shown as functions of the electrode charge density varying from -1.00 to +1.00 C m. At negative electrode charges and with increasing values of the charge separation, the differential capacitance curve rises. As the electrolyte concentration increases, the shape of the differential capacitance curve changes from that of a minimum surrounded by two maxima into that of a distorted single maximum.

Asymmetric Finite Size of Ions and Orientational Ordering of Water in Electric Double Layer Theory Within Lattice Model

“…5). Asymmetric camel-like shape of the voltage dependence of the differential capacitance was also predicted by Monte-Carlo simulations [69][70][71] and by molecular dynamic simulations [69]. The asymmetric camel-like double layer differential capacitance can be theoretically predicted also within a simple Stern model by taking into account the decrease of permittivity in Stern layer (Fig.…”