Dynamics of CO formation in the reaction O(3P)+C2H3 Original Research Article

The internal state distributions of CO(ν, J) formed in the reaction of oxygen atoms with vinyl radicals were measured using an arrested relaxation FTIR apparatus. In spite of the deep potential energy minimum corresponding to vinoxy radical, the expected intermediate in the reaction, the CO is born with a strongly non-statistical vibrational distribution. Ab initio calculations on the important stationary points of the C2H3O potential energy hypersurface provide some insight into the reaction dynamics. In particular, the barrier for H-atom migration in the process: vinoxy → acetyl, is calculated to be 42 kcal mol−1 above the vinoxy potential minimum; this lies some 80 kcal mol−1 below the reagent energy. Since this is the only substantial barrier on the reactive potential surface, the dynamics of the reaction are better described as following a direct, rather than a complex-forming mechanism.