The near ultraviolet dissociation dynamics of azomethane:: Correlated V-T energy disposal and product appearance times
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abstract
We have measured the translational energy release for methyl radical photofragments with zero and one quantum of umbrella vibration, which were produced by the ultraviolet dissociation of azomethane. Translational energy distributions exhibit bimodal structure and are similar for both methyl radical vibrational states and for two dissociation wavelengths (355 and 330 nm). Compared to earlier non-state-selective measurements, these distributions exhibit a stronger preference for high kinetic energies. We have also observed that the appearance times for both methyl radical vibrational states are fast compared to the experimental time resolution, thus resolving an outstanding mechanistic disagreement. These observations are consistent with a previously proposed mechanism in which a concerted three-body dissociation follows randomization of parent internal energy.
