Title: Influence of anisotropic ion shape, asymmetric valency, and electrolyte concentration on structural and thermodynamic properties of an electric double layer
Author(s):

	M. Kaja ( Department of Physical Chemistry, Adam Mickiewicz University of Poznan, Umultowska 89b, 61-614 Poznan, Poland ) ,
	S. Lamperski ( Department of Physical Chemistry, Adam Mickiewicz University of Poznan, Umultowska 89b, 61-614 Poznan, Poland ) ,
	W. Silvestre-Alcantara ( Laboratory of Theoretical Physics, Department of Physics, University of Puerto Rico, San Juan, 00931-3343, Puerto Rico ) ,
	L.B. Bhuiyan ( Laboratory of Theoretical Physics, Department of Physics, University of Puerto Rico, San Juan, 00931-3343, Puerto Rico ) ,
	D. Henderson ( Department of Chemistry and Biochemistry, Brigham Young University, Provo UT 84602-5700, USA )

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, σ, 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 σ value while for 1:2, at a small positive value.

Key words: charged dimers, valency asymmetry, electrical double layer, grand-canonical Monte Carlo simulation
PACS: 82.45.Fk, 61.20.Qg, 73.30.+y, 82.45.Mp, 61.20.Ja

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