A noval in situ study of adsorption processes at Au(111) electrodes by second harmonic generation

Abstract Second harmonic generation (SHG) is an in situ spectroscopic tool par excellence for an electrode surface. Since the SHG response is determined by the nonlinear susceptibility tensor of third rank, χ (2) , an understanding of the quite complex and different SHG-anisotropy patterns requires the evaluation of the important χ ijk tensor elements and their distinct dependences on both electrode potential and adsorption of ions or neutral molecules. The Fourier analysis of the azimuthal SHG data reveals that the observed SHG potential dependences arise mainly from two distinct sources: (i) The surface reconstruction, here denoted as Au(111)−(1 × 23) ↔ Au(111)−(1 × 1); it is controlled by potential and ad/desorption of ions or molecules and leads, via the SHG anisotropy, to an observable change in surface symmetry such as C 3v ↔ C s . (ii) The change of charge density of the electrode surface which is caused by potential shifts and/or adsorption processes; it alters mainly the a x term, e.g. the perpendicular part of the nonlinear polarizability of the metal surface.