State-to-state dissociation dynamics in CF3NO

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Abstract
The state‐to‐state dissociation dynamics of CF3NO have been investigated by exciting the parent compound in a supersonic jet expansion with one tunable laser and monitoring the state distribution of the NO fragment by one‐ or two‐photon laser‐induced fluorescence using a second tunable laser. At the lowest levels of excitation, CF3NO dissociates to give an NO distribution which is consistent with a statistical distribution of energy in the products. As more highly excited vibronic states of S1 are selected, the product distribution begins to show signs of nonstatistical behavior, although the deviations are small. The appearance time of the NO decreases nearly monotonically with increasing energy above the S1 origin and is equal to the fluorescence lifetime of the CF3NO* to within experimental error. It is likely that both the appearance time of the NO and the fluorescence lifetime of the CF3NO* measure the rate of internal conversion from S1 to highly excited vibrational levels of S0, which then dissociate in a nearly statistical fashion on the S0 surface. The barrier to dissociation of the CF3–NO bond is 39.61±0.23 kcal/mol.

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