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  • Title: Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: resolving interfacial inhomogeneities of "identical" molecular groups.
    Author: Velarde L, Zhang XY, Lu Z, Joly AG, Wang Z, Wang HF.
    Journal: J Chem Phys; 2011 Dec 28; 135(24):241102. PubMed ID: 22225136.
    Abstract:
    The ability to achieve sub-wavenumber resolution (0.6 cm(-1)) and a large signal-to-noise ratio in high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) allows for the detailed SFG spectral lineshapes to be used in the unambiguous determination of fine spectral features. Changes in the structural spectroscopic phase in SFG-VS as a function of beam polarization and experimental geometry proved to be instrumental in the identification of an unexpected 2.78 ± 0.07 cm(-1) spectral splitting for the two methyl groups at the vapor/dimethyl sulfoxide (DMSO, (CH(3))(2)SO) liquid interface as well as in the determination of their orientational angles.
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