Effects of asymmetric salt and a cylindrical macroion on charge inversion: electrophoresis by molecular dynamics simulations.

Abstract

The charge inversion phenomenon is studied by molecular dynamics simulations, focusing on size and valence asymmetric salts, and a threshold of surface charge density for charge inversion. The charge inversion criteria by the electrophoretic mobility and the radial distribution functions of ions coincide except around the charge inversion threshold. The reversed electrophoretic mobility increases with the ratio of coion to counterion radii, a(-)/a(+), while it decreases with the ratio of coion to counterion valences, Z(-)/Z(+). The monovalent salt enhances charge inversion of a strongly charged macroion at small salt ionic strength, while it reduces reversed mobility otherwise. A cylindrical macroion is more persistent to monovalent salt than a spherical macroion of the same radius and surface charge density.