Counterion-only electrical double layers: An application of density functional theory.

Abstract

Within the framework of density functional theory, a self-consistent approach of weighted correlation approximation is developed to give an accurate account of the cross correlations between the Coulombic interaction and the hard-sphere exclusion in the counterion-only electrical double layers. Application of the approach to the cases of practical interest, against the Monte Carlo simulations, shows that it is excellent in describing the structural properties and the pressures of the confined solutions involving both mono- and divalent counterions between two planar charged walls. In particular, the study suggests that the relative importance of electrostatic correlations in comparison to the effects of ionic excluded volume and direct Coulomb interactions depends on the valency of the counterions and the surface charge density. In a clay system with mixed counterions, the competition between the mono- and divalent ions results in a large swelling when the fraction of surface charge compensated by monovalent counterions is greater than 30%. In the opposite situation involving mostly divalent counterions, a limited swelling is found and the attraction between the clay particles favors the formation of stacks incorporating a water layer of about 1.0 nm. These findings are consistent with experimental observations, giving insight into some mechanisms governing the stability of colloidal clay in salt-free or dilute solutions.