A CLASSICAL TRAJECTORY STUDY OF IVR IN DIMETHYL PEROXIDE .2. DISSOCIATION LIFETIMES AND COMPARISON WITH STATISTICAL CALCULATIONS

Average vibrational predissociation lifetimes have been calculated for the dissociation of CH3OOCH3. Classical trajectories were used to simulate overtone-induced dissociation over the three potential surfaces described in an earlier paper [J. Phys. Chem. 1991, 95, 4213]. Comparisons are made with simple RRKM calculations, with parameters adjusted to fit the experimental bulb kinetic results. Qualitative agreement between the trajectory results and RRKM calculated lifetimes, as well as a general inspection of the trajectories, indicates the dissociation process may be described as statistical. A method to prevent the leakage of zero-point energy from the instantaneous normal modes of the molecule during the calculation of trajectories [J. Chem. Phys. 1989, 91, 2863] has been implemented, and the results are discussed.