We report Monte Carlo simulation results for double layers of 1:1 and 2:1 electrolytes near an electrode with an inner layer that has a dielectric constant, ε(2), smaller than that of the electrolyte, ε(3). The electrolyte is modeled in the implicit solvent framework (primitive model), while the electrode is a metal electrode in this study (ε(1) → ∞). The charged hard sphere ions are not allowed to enter into the inner layer. We show that the capacitance of the inner layer is C(δ) = ε(0)(ε(2) + ε(3))/2δ, where δ is the thickness of the inner layer. This result is different from that obtained from solutions of the Poisson-Boltzmann equation (ε(0)ε(2)/δ), indicating that interpretation of experimental data with a fitted ε(2) dielectric constant of the inner layer must be done using a different equation. We also show that the properties of the diffuse layer are not independent of the value of ε(2), which is a usual assumption of the Poisson-Boltzmann theory. This is mainly because the repulsive image charges repel both the counterions and the co-ions, while the electrode charge attracts the counterions and repels the co-ions.
© 2011 American Chemical Society