Unimolecular Processes IV: Product State Distributions after Dissociation

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Abstract
The statistical adiabatic channel model is used to calculate the distribution of internal states and center of mass translational energies of fragments in unimolecular dissociation. The reactions ClNO → Cl + NO and NO2 → NO + O are considered as examples. The influence of molecular parameters and dynamical constraints is illustrated. Mechanisms providing randomness in photodissociation and unimolecular decomposition are discussed as well as the relation between dissociation rates and statistical scattering. The statistical calculations for NO2 decomposition are in good agreement with the experimental center of mass translational energy distributions from photofragment spectroscopy.