5 research outputs found
Influence of anisotropic ion shape, asymmetric valency, and electrolyte concentration on structural and thermodynamic properties of an electric double layer
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, . One sphere is charged while the other is neutral. Spherical
anions are charged hard spheres of diameter . 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, , 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 value while for 1:2, at a small
positive value.Comment: 10 pages, 6 figure
Double layer for hard spheres with an off-center charge
Simulations for the density and potential profiles of the ions in the planar
electrical double layer of a model electrolyte or an ionic liquid are reported.
The ions of a real electrolyte or an ionic liquid are usually not spheres; in
ionic liquids, the cations are molecular ions. In the past, this asymmetry has
been modelled by considering spheres that are asymmetric in size and/or valence
(viz., the primitive model) or by dimer cations that are formed by tangentially
touching spheres. In this paper we consider spherical ions that are asymmetric
in size and mimic the asymmetrical shape through an off-center charge that is
located away from the center of the cation spheres, while the anion charge is
at the center of anion spheres. The various singlet density and potential
profiles are compared to (i) the dimer situation, that is, the constituent
spheres of the dimer cation are tangentially tethered, and (ii) the standard
primitive model. The results reveal the double layer structure to be
substantially impacted especially when the cation is the counterion. As well as
being of intrinsic interest, this off-center charge model may be useful for
theories that consider spherical models and introduce the off-center charge as
a perturbation.Comment: 11 pages, 7 figure