Electrocapillary coupling at rough surfaces.

We investigate the impact of the surface roughness on the experimental value of the electrocapillary coupling coefficient, ς. This quantity relates the response of electrode potential, E, to tangential elastic strain, e, and also measures the variation of the surface stress, f, with the superficial charge density, q. We combine experiments measuring the apparent coupling coefficient ςeff for gold thin film electrodes in weakly adsorbing electrolyte with data for the surface roughness determined by atomic force microscopy and by the capacitance ratio method. We find that even moderate roughness has a strong impact on the value of ςeff. Analyzing the mechanics of corrugated surfaces affords a correction scheme yielding values of ς that are invariant with roughness and that agree with expectations for the true coupling coefficient on ideal, planar surfaces. The correction is simple and readily applied to experiments measuring ςeff from surface stress changes in cantilever bending studies or from the potential variation in dynamic electro-chemo-mechanical analysis.