THEORETICAL INVESTIGATION OF THE VIBRATIONAL PREDISSOCIATION OF N2O3

Classical trajectories are used to calculate vibrational predissociation rates of asymmetric N2O3 for initial conditions that include excitation of the nu-1 (NO stretch), the nu-2 (NO2 asymmetric stretch), the nu-3 (NO2 symmetric stretch), and the nu-4 (NO2 bend) vibrational modes, and combinations of these modes. The results show strong mode selectivity. This selectivity is in accord with the experimental results of Chewter, Smith and Yarwood which show that intramolecular energy flow from the nu-1 mode is relatively slow and that N2O3 exhibits "non-RRKM behavior". The mode selectivity corresponds to the extent of the projections of the various normal modes along the reaction coordinate.