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 μm. Molecular vibrations of thiophenol are observed at wavelengths near 10 μm (three modes), 14 μm (1 mode), and 24 μm (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.
Sum-frequency generation from thiophenol on silver in the mid and far-IR
R. Braun, B. D. Casson, C. D. Bain, E. W. M. van der Ham, Q. H. F. Vrehen, E. R. Eliel, A. M. Briggs, P. B. Davies; Sum-frequency generation from thiophenol on silver in the mid and far-IR. J. Chem. Phys. 1 March 1999; 110 (9): 4634–4640. https://doi.org/10.1063/1.478345
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