  Monte Carlo simulations of a spherical macroion, surrounded by a
size-asymmetric electrolyte in the primitive model, were performed. We
considered 1:1 and 2:2 salts with a size ratio of 2 (i.e., with coions twice
the size of counterions), for several surface charge densities of the
macrosphere. The radial distribution functions, electrostatic potential at the
Helmholtz surfaces, and integrated charge are reported. We compare these
simulational data with original results obtained from the Ornstein-Zernike
integral equation, supplemented by the hypernetted chain/hypernetted chain
(HNC/HNC) and hypernetted chain/mean spherical approximation (HNC/MSA)
closures, and with the corresponding calculations using the modified
Gouy-Chapman and unequal-radius modified Gouy-Chapman theories. The HNC/HNC and
HNC/MSA integral equations formalisms show good concordance with Monte Carlo
"experiments", whereas the notable limitations of point-ion approaches are
evidenced. Most importantly, the simulations confirm our previous theoretical
predictions of the non-dominance of the counterions in the size-asymmetric
spherical electrical double layer [J. Chem. Phys. 123, 034703 (2005)], the
appearance of anomalous curvatures at the outer Helmholtz plane and the
enhancement of charge reversal and screening at high colloidal surface charge
densities due to the ionic size asymmetry.
