Three component model of cylindrical electric double layers containing mixed electrolytes: A systematic study by Monte Carlo simulations and density functional theory.
ABSTRACT The structure of electric double layer around a hard rigid impenetrable cylindrical polyion is studied using density functional theory as well as Monte Carlo simulations. The three component model, presented here, is an extension of solvent primitive model where the solvent molecules are treated as the neutral hard spheres, counterions and coions as the charged hard spheres, all of equal diameters, and in addition the mixture of mono- and multivalent counterions are also considered. The theory is partially perturbative where the hard sphere interactions are treated within the weighted density approach and the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The theoretical predictions in terms of the density profiles and the mean electrostatic potential profiles are found to be in good agreement with the simulation results. The presence of neutral hard spheres incorporate the effects of exclude volume interactions (ionic size correlations) while the mixture of mono- and multivalent counterions enhance the ionic charge correlation effects. Thus, this model study shows clear manipulations of ionic size and charge correlations in dictating the ionic density profiles as well as mean electrostatic potential profiles of the diffuse layer. The behavior of diffused double layer has been characterized at varying ionic concentrations, at different concentration ratios of mono- and multivalent counterions of mixed electrolytes, at different diameters of hard spheres, and at varying polyion surface charge density.
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ABSTRACT: A computationally practical density-functional theory of nonuniform fluid mixtures ‘‘designed primarily for the study of interfacial phenomena’’ is presented and applied to the structure of a binary hard-sphere mixture near a hard wall. The theory is based on a weighted-density approximation for the one-particle direct correlation functions of the nonuniform system, and requires as input only the one- and two-particle direct correlation functions of the corresponding uniform system. Numerical results for density and concentration profiles are presented and compared with available simulation data.Physical Review A 01/1992; 44(12):8242-8248. · 3.04 Impact Factor