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Size and charge correlations in spherical electric double layers: a case study with fully asymmetric mixed electrolytes within the solvent primitive model
RSC Advances Pub Date : 10/23/2020 00:00:00 , DOI:10.1039/D0RA06145J
Abstract

Size and charge correlations in spherical electric double layers are investigated through Monte Carlo simulations and density functional theory, through a solvent primitive model representation. A fully asymmetric mixed electrolyte is used for the small ions, whereas the solvent, apart from being a continuum dielectric, is also treated as an individual component. A partially perturbative density functional theory is adopted here, and for comparison, a standard canonical ensemble Monte Carlo simulation is used. The hard-sphere free energy is treated within a weighted density approach and the residual ionic contribution is estimated through perturbation around the uniform density. The results from both methods corroborate each other quantitatively over a wide range of physical parameters. The importance of structural correlations is envisaged through the size and charge asymmetry of the supporting electrolytes that includes the solvent as a component.

Graphical abstract: Size and charge correlations in spherical electric double layers: a case study with fully asymmetric mixed electrolytes within the solvent primitive model
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