Adsorbate Isotherm Analysis by Reflection Anisotropy Spectroscopy on Copper (110) in Hydrochloric Acid

Reflectance anisotropy spectroscopy (RAS) is a powerful optical probe that works on a polarization contrast basis. It can be operated in any environment, ranging from ultrahigh vacuum to vapor phases and liquids. The measured optical anisotropies are caused by several symmetry breaking effects and are exclusively assigned to the surface for otherwise bulk isotropic materials. In this work, we present a systematic study comprising in situ RAS-transient to assess the surface thermodynamics of the chloride adsorption on Cu(110) upon systematic variations of the applied electrode potentials in comparison to cyclic voltammetry (CV). Numerical time-derivatives of the measured RAS-transients are shown to be exclusively associated with electrical currents of those electrochemical reactions, which change the properties of the electrode surface. The recorded transient line-shapes track the Frumkin type isotherm properties related to chloride coverage. Both connections are theoretically discussed. Owing to the surface and interface specificity, RAS is shown to exhibit a high surface sensitivity. In particular, processes taking place in parallel, namely, the hydrogen evolution reaction (HER) as well as the copper dissolution as Cu⁺ and Cu²⁺, do not contribute to the RAS response.