Ensemble dephasing in vibrationally excited jet-cooled tetrazine and its complexes with Ar, Kr, and Xe

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Abstract
A time delayed, fully resonant, version of coherent anti-Stokes Raman spectroscopy (CARS) has been used to study intramolecular and intermolecular dephasing in vibrationally excited jet-cooled tetrazine and its van der Waals complexes with argon, krypton, and xenon. When there is 1200 to 2200 cm−1 of vibrational energy in the ground electronic state manifold, the dephasing of all species is dominated by the macroscopic interference associated with the heterogeneous structure of the Q-branch transitions. The observed macroscopic dephasing times are about 300 ps to 2 ns, which implies that the lower limit for the intramolecular dephasing times falls in the same range. The influence of excited state resonances on the dephasing characteristics of these molecules is qualitatively accounted for by formulas derived from the wave packet theory of Tannor, Rice, and Weber.