Ion‐ion correlations and effective charges in electrolyte and macroion systems

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Abstract
Various ion‐ion correlation mechanisms that affect double layer interactions between charged macroparticles in electrolyte solutions are reviewed and discussed. Such effects give rise to quantitative and sometimes qualitative deviation from the prediction of the Poisson‐Boltzmann theory. Special attention is given to the attractive double layer interactions that can appear between equally charged surfaces at short surface separations for aqueous systems with divalent counterions. The long‐range behaviour of the double layer interaction is also treated. It is efficiently described in terms of effective surface charge densities, which summarizes how the inner parts of the diffuse double layer affects the distant parts. The magnitude as well as the sign of the effective charge depends on the state of the system. Charge reversal can occur for aqueous systems with divalent counterions. A major objective of the paper is to describe and illustrate the mechanisms in a simple and graphical manner.