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Title: Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS)

The emergence of sub-wavenumber high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BBSFG-VS) [Velarde et al., J. Chem. Phys., 2011, 135, 241102] has offered new opportunities in obtaining and understanding the spectral lineshape and temporal effects on the surface vibrational spectroscopy. Particularly, the high accuracy in the HR-BBSFG-VS spectral lineshape measurement provides detailed information on the complex coherent vibrational dynamics through spectral measurement. Here we present a unified formalism of the theoretical and experimental approaches for obtaining the accurate lineshape of the SFG response, and then present a analysis on the higher and lower spectral resolution SFG spectra as well as their temporal effects of the cholesterol molecules at the air/water interface. With the high spectral resolution and accurate lineshape, it is shown that the parameters from the sub-wavenumber resolution SFG spectra can be used not only to understand but also to quantitatively reproduce the temporal effects in the lower resolution SFG measurement. These not only provide a unified picture in understanding both the frequency-domain and the time-domain SFG response of the complex molecular interface, but also provide novel experimental approaches that can directly measure them.
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Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Chemistry Chemical Physics. PCCP, 15(46):19970-19984
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
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Country of Publication:
United States
Spectral; sum-frequency generation vibational spectroscopy; lineshape; vibrational dynamics; Environmental Molecular Sciences Laboratory