David W. McCamant Department of Chemistry, University of Rochester

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Presentation transcript:

David W. McCamant Department of Chemistry, University of Rochester Two-Dimensional Raman Spectroscopy of Metallocenes: Probing the Dynamics of Organometallic Bonds (b) David W. McCamant Department of Chemistry, University of Rochester Vibrational coupling in aromatic hydrocarbons and metallocenes will be probed using femtosecond stimulated Raman spectroscopy (FSRS). FSRS has a unique ability to introduce and probe vibrational coherence in order to elucidate the anharmonic vibrational couplings that drive energy flow through molecules. (a) Schematic of 2D-FSRS experiment. (b) The detected spectrum of the probe measures the interaction between the impulsively driven vibrations and the vibrations probed by FSRS. In the presence of anharmonic coupling between the driven (wlow) and probed (whi) vibrations or via a coherent cascade, sidebands are observed in the stimulated Raman spectrum at Raman shifts of w=w(+)=whi+wlow and w=w(-)=whi-wlow. The shape of the sideband peak varies with changes in time delay, Dt, and produces a time dependent lineshape. C D Cl C D Cl Coupling between low and high frequency modes is facilitated by the 3rd order force constant C-Cl Bend C-D Stretch