Rovibrational state mixing in the aldehyde C–H stretch fundamental region of acetaldehyde | CU Experts

We have studied rovibrational state mixing in acetaldehyde using infrared laser induced fluorescence. Molecules are isolated and cooled in supersonic molecular beams, and irradiated in the C–H stretch fundamental region with an infrared optical parametric oscillator. Spectral resolution is provided with either a circular variable filter machine or a cryogenic Michelson interferometer. We have found evidence of several strong Fermi resonances between the aldehyde C–H stretch and a few overtones and combinations of lower frequency modes. In addition, there is substantial random state mixing in this region as evidenced by the average experimental dilution factor of 0.2. The dependence of the dilution factor on the average J excited by the laser shows that the extent of state mixing scales linearly with J. We have observed from dispersed fluorescence spectra that random rotational coupling occurs between different Kp states. Our previous statistical coupling model has been applied to the interpretation of the data, and its applicability is discussed. For the model calculation, the methyl torsion is specially treated as a very anharmonic mode in the eumeration of the zeroth order bath states. The average coupling width derived from the model calculation is 0.35 cm−1. The relative energy content apportioned among vibrational modes in the molecule following excitation is measured and is successfully explained with the model.

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