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State-to-state theory of vibrational kinetics and dissociation in three-atomic gases AIP Conf. Proc. 585, 620 (2001); 10.1063/1.1407618State-to-state unimolecular reaction dynamics of HOCl near the dissociation threshold: The role of vibrations, rotations, and IVR probed by time-and eigenstate-resolved spectroscopyThe state-to-state dissociation dynamics of CF 3 NO 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. CF 3 NO 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 S I 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 S I origin and is equal to the fluorescence lifetime of the CF 3 NO· to within experimental error. It is likely that both the appearance time of the NO and the fluorescence lifetime of the CF 3NO· measure the rate of internal conversion from S I to highly excited vibrational levels of So, which then dissociate in a nearly statistical fashion on the So surface. The barrier to dissociation ofthe CF 3 -NO bond is 39.61 ±0.23 kcaVmol.