The study of the electrical double
layer lies at the
heart of colloidal
and interfacial science. The standard mean-field Poisson–Boltzmann
(PB) theory is incapable of modeling many phenomena originating from
ion correlation. An important example is charge inversion or overcharging
of electrical double layers in multivalent electrolyte solutions.
Existing theories aiming to include correlations cannot capture the
non-monotonic dependence of charge inversion on salt concentration
because they have not systematically accounted for the inhomogeneous
nature of correlations from surface to the bulk and the excluded volume
effect of ions and solvent molecules. In this work, we modify the
Gaussian renormalized fluctuation theory by including the excluded
volume effect to study ion condensation and charge inversion. A boundary
layer approach is developed to accurately model the giant difference
in ion correlations between the condensed layer near the surface and
the diffuse layer outside. The theory is used to study charge inversion
in multivalent electrolytes and their mixtures. We predict a surface
charge induced formation of a three-dimensional condensed layer, which
is necessary but not sufficient for charge inversion. The value of
the effective surface potential is found to depend non-monotonically
on the bulk salt concentration. Our results also show a non-monotonic
reduction in charge inversion in monovalent and multivalent electrolyte
mixtures. Our work is the first to qualitatively reproduce experimental
and simulation observations and explains the underlying physics.
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