Nonlinear electrophoresis of a highly charged particle by incorporating electrostatic correlations and ion steric interactions for a finite Debye length

Most of the existing theories on electrophoresis are based on the consideration of a weak applied electric field and ions as point charges, which create a mean electric potential and neglect ion–solvent interactions. These theories cannot demonstrate the dependence of electrophoretic mobility on the applied electric field (nonlinear electrophoresis), reversal in mobility with increasing ion concentration and/or surface charge density or counterion saturation in the electric double layer. In this study we consider a modified electrokinetic model to analyse nonlinear electrophoresis by taking into account the finite ion size effects and ion–ion electrostatic correlations. In this approach, the mean-field-based model is extended to capture the many-body phenomena by considering the non-local electrostatic contribution in the ion free energy functional and the ion–ion hydrodynamic steric interactions are incorporated through the volume exclusion effect in the electrochemical potential. The viscosity of the medium is considered to vary with the local ionic volume fraction. Stronger correlations for multivalent counterions create ion layering, charge density oscillation and mobility reversal. Such phenomena are captured by the present continuum model. The ion crowding attenuates the growth of the electrophoretic mobility with the electric field. At a higher range of the imposed electric field, the ion concentration in the electric double layer enhances, which modifies both the overscreening and ion crowding processes.