Sum-frequency generation from thiophenol on silver in the mid and far-IR

Sum-frequency (SF) spectra of a monolayer of thiophenol on silver are reported in the mid and far-IR (infrared). The free-electron laser FELIX was used to reach wavelengths up to 54 mu m. Molecular vibrations of thiophenol are observed at wavelengths near 10 mm (three modes), 14 mu m (1 mode), and 24 mu m (1 mode). The appearance of the different vibrational modes in the spectra varies dramatically due to interference between the resonant sum-frequency signal and the nonresonant sum-frequency signal from silver. The standard model used to describe line shapes in SF spectra is shown to be insufficient to explain the different line shapes for the various vibrational modes of thiophenol on silver. (C) 1999 American Institute of Physics. [S0021-9606(99)70709-9].