Diffusive-convective transition in the non-equilibrium charging of an electric double layer

We study the non-equilibrium electrolyte kinetics in a planar nanocapacitor that is driven by periodically switching surfaces charges using simulations, theory and scaling analysis. The combined effects of inter-ionic charge correlations and hydrodynamic interactions lead to correlated convective behavior for weakly charged ions. These dynamic correlations, signaling the breakdown of the Poisson-Nernst-Planck theory, are distinct from static correlations that are manifested by the crossover from Poisson-Boltzmann to strong-coupling theory that occurs as the ion valency increases. Copyright (C) EPLA, 2016