With the enhanced sensitivity of Photothermal Deflection Spectroscopy (PDS), vibrational overtone spectra have been obtained in organic thin films for the first time, covering the range from the near IR to the visible (0.4 - 2 eV). The absorption spectra of polycarbonate, for instance, exhibits C-I1 stretch modes for Δn> I where n is the vibrational quantum level. Previous measurements were constrained to either long fibers, which pose the problem of various scattering losses not related to absorption, or to a restricted wavelength region in the visible accessible by dye laser sources. The unparalleled sensitivity of PDS allows precise determination of frequency, lineshape and intensity of the various modes, even for films ≈10µm thick over a broad energy range. The overtone spectra can be used as a probe of various basic molecular properties. In a manner similar to NMR spectroscopy, it is possible to study specific atomic bonds.
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Skumanich, A., Moylan, C. Vibrational Overtone Spectra in Polymeric Thin Films. MRS Online Proceedings Library 228, 91–94 (1991). https://doi.org/10.1557/PROC-228-91