Dynamicsof the O + ClO Reaction: Reactive and VibrationalRelaxation Processes.

Classical trajectories have beenintegrated to study the O + ClOreaction, both reactive and vibrational energy transfer processes,for the range of temperatures 100 ≤ T/K ≤500 using momentum Gaussian binning. The employed potential energysurface is the recently proposed single-sheeted double many-body expansionpotential energy surface for the 2A″ ground-stateof ClO2based on multireference ab initio data. A capture-typeregime with a room-temperature rate constant of (17.8 ± 0.5)× 10–12cm3s–1and temperature dependence of k(T/K)/cm3s–1= 22.4 × 10–12× T–0.81exp(−39.2/T) has been found. Although the value reported here is halfof the experimental and recommended one, tentative explanations aregiven. Other dynamical attributes are also examined for the titlereaction, with state-to-all and state-to-state vibrational relaxationand excitation rate constants reported for temperatures of relevancein stratospheric chemistry. [ABSTRACT FROM AUTHOR]