Dynamics of the reaction O(P-3)+H2S -> OH+SH. 2. State-resolved differential cross sections and angular momentum correlations

Measurements are reported of Doppler resolved polarized laser-induced fluor escence of the OH product of the O(P-3) + H2S reaction, leading to estimate s of the differential cross sections and angular momentum correlations in t he system. O(P-3) was produced with translational energy above the barrier to reaction by the polarized 355 nm photolysis of NO2. Three quantum states were studied in detail. For the most populated OH level, v" = 1, N" = 6, t he scattering for the A" Lambda doublet was found to be largely sideways/ba ckward, with the remaining energy appearing as product translation, and mea surements of average Lambda doubler scattering showed similar behavior for the A' Lambda doubler. The same scattering dynamics were observed for the v " = 0, N" = 13 state. For the rotationless v" = 1, N" = 1 state the results were more ambiguous, but if the same distribution of available energy appe ared in the SH fragment as deduced for the measurements on rotationally exc ited OH, then the scattering was seen to be clearly backward. Polarization measurements of the two OH levels with N" > 1 showed that the angular momen tum vector J' was directed perpendicular to the plane containing the relati ve velocity vectors of reactants and products. A model of the scattering is proposed through a planar transition state and is able to account qualitat ively for these observations of the vector characteristics of the reaction, together with the scalar attributes (quantum state populations) reported i n the previous paper. The model predicts that the SH coproduct will be scat tered largely forward with respect to the O(P-3) atom velocity, with low in ternal energy, and dominantly in the A" Lambda doubler.