Abstract
A recently proposed local second contact value theorem [Henderson D., Boda D., J. Electroanal. Chem., 2005, 582, 16] for the charge profile of an electric double layer is used in conjunction with the existing Monte Carlo data from the literature to assess the contact behavior of the electrode-ion distributions predicted by the density functional theory. The results for the contact values of the co- and counterion distributions and their product are obtained for the symmetric valency, restricted primitive model planar double layer for a range of electrolyte concentrations and temperatures. Overall, the theoretical results satisfy the second contact value theorem reasonably well, the agreement with the simulations being semi-quantitative or better. The product of the co- and counterion contact values as a function of the electrode surface charge density is qualitative with the simulations with increasing deviations at higher concentrations.
Highlights
One of the more interesting recent developments in the electric double layer research has been the advancement of contact value theorems involving the charge profile in a primitive model (PM) planar double layer
It is a condition on the contact value of the total density profile in a planar double layer, and for a symmetric valency restricted primitive model (RPM) planar double layer – the model system of interest in this paper, the HBL relation reads b2 gsum(d/2) = [gco(d/2) + gctr(d/2)]/2 = a + 2
In this study we propose to utilize the Henderson and Boda (HB) second contact value theorem and the existing Monte Carlo (MC) simulation results from the literature for f to assess the density functional theory (DFT) of the planar double layer
Summary
One of the more interesting recent developments in the electric double layer research has been the advancement of contact value theorems involving the charge profile in a primitive model (PM) planar double layer (charged hard spheres moving in a dielectric continuum next to a planar electrode) (see, for example, references [1,2,3,4]). We will call equation (1) the first contact value theorem, while equations (3) and (5) represent two versions of the second contact value theorem Another interesting recent result that concerns us in this paper is the behavior of the product of the co- and counterion contact values f = gco(d /2)gctr(d /2) in the RPM planar double layer. In this study we propose to utilize the HB second contact value theorem and the existing MC simulation results from the literature for f to assess the density functional theory (DFT) of the planar double layer.
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