American Chemical Society, Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry), 44(115), p. 12911-12914, 2011
DOI: 10.1021/jp2078105
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We use a classical density functional theory (DFT) to study the electric double layer formed by charged hard spheres near a planar charged surface. The DFT predictions are found to be in good agreement with recent computer simulation results. We study the capacitance of the charged hard-sphere system at a range of densities and surface charges and find that the capacitance exhibits a local minimum at low ionic densities and small electrode charge. Although this charging behavior is typical for an aqueous electrolyte solution, the local minimum gradually turns into a maximum as the density of the hard spheres increases. Charged hard spheres at high density provide a reasonable first approximation for ionic liquids. In agreement with experiment, the capacitance of this model ionic liquid double layer has a maximum at small electrode charge density.