Articles you may be interested inThe tail effect on the shape of an electrical double layer differential capacitance curve Temperature dependence of the double-layer capacitance for the restricted primitive model: The effect of chemical association between unlike ions J. Chem. Phys. 123, 016101 (2005); 10.1063/1.1949209 Self-affine and mound roughness effects on the double-layer charge capacitance J. Appl. Phys. 92, 7175 (2002); 10.1063/1.1519952Nonlinear Poisson-Boltzmann theory of a double layer at a rough metal/electrolyte interface: A new look at the capacitance data on solid electrodesIn this paper we investigate the influence of self-affine roughness on the charge density and capacitance of electrical double layers within the nonlinear regime. The roughness influence is significant for small roughness exponents (HϽ0.5) and/or large long wavelength roughness ratios w/, as well as small Debye lengths D ͑Ͻ͒. With increasing electrode voltage, the apparent charge density increases fast in an exponential manner for relatively high voltages. On the other hand, the charge capacitance increases up to a maximum after which it approaches an asymptotic value, which is determined by the roughness ratio of the actual to apparent flat interface area. The roughness influence is amplified within the nonlinear regime if the interface becomes rougher at any lateral roughness wavelength ͑smaller exponent H and/or larger ratio w/). Finally, the total charge capacitance, which is obtained by considering the contribution from the thin Helmholtz layer, is also shown to be highly sensitive to interface roughness details within the nonlinear regime.
The influence of random self-affine and mound substrate roughness on the wetting scenario of adsorbed van der Waals films is investigated as a function of characteristic roughness parameters. The roughness influence, which leads to triple-point wetting, is calculated by the bending free energy penalty of a solid film picking up the substrate morphology. For self-affine roughness, an increment of the roughness exponent H and/or a decrement of the roughness ratio w/ ͑with w being the rms roughness amplitude and the in-plane correlation length͒ leads to a noticeable increment of the thickness of adsorbed solid films. Similarly for mound roughness the thickness dependence of the solid wetting layer on the average mound separation and system correlation length follow the general scenario that smoother substrates ͑w/Ӷ1 and/or w/Ӷ1͒ lead to thicker solid films. Nevertheless, in this case the thickness increment is a highly nonmonotonic function of and for р.
In this paper we investigate the dependence of Parsons-Zobel plots on characteristic self-affine roughness parameters of the metal electrode in electrical double layers. Among the roughness amplitude w, the correlation length , and roughness exponent H, the latter appears to have the most prominent effect especially for values in the range H Ͻ 0.5. In addition, with decreasing compact layer thickness the influence of roughness leads to stronger nonlinear behavior of the plots for relatively large electrode potentials. Finally, it is shown that dynamic changes of the electrode roughness (for example by growth on metal films) should be carefully quantified with respect to their influence on the Parson-Zobel plots and related double-layer systems.
In this article, we investigate the influence of self-affine and mound roughness on the charge capacitance of double layers. The influence of self-affine roughness is more significant for small roughness exponents (H<0.5) and/or large roughness ratios w/ξ, as well as small charge and counter charge separations in electrolyte plasma as described by the Debye length λD(<ξ). On the other hand, mound roughness has a more complex influence on the charge capacitance, when the system correlation length ζ is larger than the average mound separation λ. In this case, the charge capacitance oscillates as a function of the parameters λ and ζ before it approaches the Gouy–Chapman [G. Gouy, J. Phys. (Paris) 9, 457 (1910); D. L. Chapman, Philos. Mag. 25, 475 (1913)] asymptotic limit for smooth interfaces. Furthermore, the oscillation magnitude is larger for relatively small Debye lengths λD(<ζ,λ).
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