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Effects Of Electrostatic Correlations On Electrokinetic Phenomena, Brian Storey, Martin Bazant
Effects Of Electrostatic Correlations On Electrokinetic Phenomena, Brian Storey, Martin Bazant
Brian Storey
The classical theory of electrokinetic phenomena is based on the mean-field approximation that the electric field acting on an individual ion is self-consistently determined by the local mean charge density. This paper considers situations, such as concentrated electrolytes, multivalent electrolytes, or solvent-free ionic liquids, where the mean-field approximation breaks down. A fourth-order modified Poisson equation is developed that captures the essential features in a simple continuum framework. The model is derived as a gradient approximation for nonlocal electrostatics of interacting effective charges, where the permittivity becomes a differential operator, scaled by a correlation length. The theory is able to capture …