Looking deeper into the structure of mixed electric double layers near the point of zero charge

Molecular simulations have been carried out using the Metropolis Monte Carlo approach to investigate the structure of planar electric double layers containing counterion mixture within the framework of the unrestricted primitive model. The results reveal that near the point of zero charge, the rise of monovalent salt drastically elevates the collapse of ions regardless of their polarity. In particular, we fail to observe the formation of a strongly correlated liquid in the first counterion layer due to favorable entropic effects, in contrast to the early data from molecular dynamics simulations [corrected] for a spherical electric double layer [R. Messina, E. González-Tovar, M. Lozada-Cassou, and C. Holm, Europhys. Lett. 60, 383 (2002)]. Moreover, the large size of coions is found to be a pivotal factor in determining the reversal of electrophoretic mobility. On the other hand, the repulsive image charge forces thoroughly annihilate this peculiar reversal of mobility within the investigated scope of concentrations, but exert no effect on the emergence of charge reversal. These findings highlight potential applications of coion's characteristics to control gene delivery and colloidal stability as well as to design viral packing and polyelectrolyte self-assembly.