The electrical double layer for a fully asymmetric electrolyte around a spherical colloid: an integral equation study.

The hypernetted chain/mean spherical approximation (HNC/MSA) integral equation for a totally asymmetric primitive model electrolyte around a spherical macroparticle is obtained and solved numerically in the case of size-asymmetric systems. The ensuing radial distribution functions show a very good agreement when compared to our Monte Carlo and molecular-dynamics simulations for spherical geometry and with respect to previous anisotropic reference HNC calculations in the planar limit. We report an analysis of the potential versus charge relationship, radial distribution functions, mean electrostatic potential, and cumulative reduced charge for representative examples of 1:1 and 2:2 salts with a size-asymmetry ratio of 2. Our results are collated with those of the modified Gouy-Chapman (MGC) and unequal radius modified Gouy-Chapman (URMGC) theories and with those of HNC/MSA in the restricted primitive model (RPM) to assess the importance of size-asymmetry effects. One of the most striking characteristics found is that, contrary to the general belief, away from the point of zero charge the properties of an asymmetric electrical double layer (EDL) are not those corresponding to a symmetric electrolyte with the size and charge of the counterion, i.e., counterions do not always dominate. This behavior suggests the existence of a new phenomenology in the EDL that genuinely belongs to a more realistic size-asymmetric model where steric correlations are taken into account consistently. Such novel features cannot be described by traditional mean-field theories such as MGC, URMGC, or even by enhanced formalisms, such as HNC/MSA, if they are based on the RPM.