Sulfate adsorption at Au(111) electrodes: an optical second harmonic generation study

Second harmonic generation (SHG) generation was employed to study adsorption of sulfate at the Au(111) electrode surface. The experiments were carried out using both pp and ss polarisations for the input and output photons. The amplitudes of the isotropic, one-fold and three-fold symmetry elements of the electrode susceptibility were determined. The isotropic term is a complex number. Its real part displays this same linear dependence on the electrode charge density in the absence and presence of adsorbed sulfate. The phase angle of the complex number is also not changed by sulfate adsorption. These features indicate that adsorbed sulfate changes the static electric field at the interface, however it does not affect the electronic structure of the metal. The one-fold symmetry amplitude changes with potential. This change displays lifting of the surface reconstruction. We observed similar effect of sulfate on the structure of the electrode surface to that reported earlier by Magnussen et al. [Faraday Discuss. 94 (1992) 329].