Abstract
Vibrational sum-frequency-generation (SFG) spectroscopy experiments at electrified interfaces involve incident laser radiation at frequencies in the IR and near-IR/visible regions as well as a static electric field on the surface. Here we show that mixing the three fields present on the surface can result in third-order effects in resonant SFG signals. This was achieved for closed packed self-assembled monolayers (SAMs) with molecular groups of high optical nonlinearity and surface potentials similar to those typically applied in cyclic voltammograms. Broadband SFG spectroscopy was applied to study a hydrophobic well-ordered araliphatic SAM on a Au(111) surface using a thin-layer analysis cell for spectro-electrochemical investigations in a 100 mM NaOH electrolyte solution. Resonant contributions were experimentally separated from non-resonant contributions of the Au substrate and theoretically analyzed using a fitting function including third-order terms. The resulting ratio of third-order to second-order susceptibilities was estimated to be [Formula: see text](10(-10)) m/V.