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        Experimental Determinations of Coherent Multidimensional Vibrational Spectroscopy

        Besemann, Daniel,Condon, Nicholas,Meyer, Kent,Zhao, Wei,Wright, John C. Korean Chemical Society 2003 Bulletin of the Korean Chemical Society Vol.24 No.8

        Coherent multidimensional vibrational spectroscopy is a new technique for establishing correlations between features in vibrational spectra that are caused by intra- and intermolecular interactions. These interactions cause cross-peaks between vibrational transitions that reflect the coupling. In this paper, we use Doubly Vibrationally Enhanced Infrared Spectroscopy (DOVE-IR) and DOVE-Raman processes to obtain coherent two dimensional vibrational spectra. The spectra are fitted to obtain the dephasing rates and third order susceptibilities $(χ^{(3)})$ for the nonlinear processes. We show that the DOVE $χ^{(3)}$ values are directly related to the molar absorptivities and Raman $χ^{(3)}$. We then use these relationships to obtain estimates for the $χ^{(3)}$ of the stimulated photon echo and $χ^{(5)}$ of the six wave mixing spectroscopies, respectively. We also predict the ratio of the cascaded four wave mixing signal to the six wave mixing signal.

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