Dynamics of the reaction of oxygen atoms with carbon suboxide

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Abstract
The dynamics of the O(3P)+C3O2→3CO reaction (ΔH° =−115 kcal/mole) has been investigated by means of a CO laser resonance absorption technique. The reaction mixtures consisted of NO2 and C3O2, with He or SF6 dilution. The O(3P) atom was generated by the flash photolysis of the NO2 above 300 nm. The three CO’s formed in the reaction were found to carry vibrationally about 19% of the total available energy, with an apparent near statistical population distribution. The results of an 18O‐labeled experiment, however, indicate that the two CO’s originating from the parent C3O2 molecule are vibrationally much colder (〈Ev〉? 4.2 kcal/mole) than that from the reaction of the O atom with the center C atom (〈Ev〉?15 kcal/mole). This result is attributed to the incomplete randomization of the reaction energy in the dissociating C3O3 complex. Possible reaction mechanisms are presented.

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