INTERNAL ENERGY-DISTRIBUTIONS OF THE SO(X(3)SIGMA(-)) PRODUCT FROM THE O(P-3)+OCS REACTION

The SO(X(3) Sigma(-)) product vibrational and rotational state distrib utions following the title reaction have been studied by laser induced fluorescence on the (B-3 Sigma(-)-X(3) Sigma(-)) transition. The O(P- 3) atom was generated by 351 nm photolysis of NO2. The SO(X(3) Sigma(- )) product is highly vibrationally excited and the vibrational state d istribution is inverted at nu ''=5 with detectable population up to nu ''=9. The observed vibrational state distribution has been modelled e ffectively by a Franck-Condon/Golden Rule treatment. The nascent rotat ional state distribution of nu ''=4 and 6 can be characterized by rota tional temperatures, T-R=2288 +/- 357 K and T-R=2227 +/- 297 K, respec tively. The rotational state populations are nearly equilibrated with the ambient gas within 10 hard sphere collisions. A surprisal analysis reveals that the observed rotational state distribution is colder tha n would be predicted on the basis of a purely statistical energy dispo sal model. The observed SO(X(3) Sigma(-)) internal energy accounts for approximate to 34% of the total energy available to products. The non -statistical energy disposal results are consistent with a direct S at om abstraction mechanism.