Rotational, spin-orbit, and A doublet populations have been measured in the OH(ν″ = 1) product of the O(3P) + H2S reaction. Ground-state O atoms with kinetic energies above the barrier to reaction were formed by photolysis of NO2 at 355 nm. Rotational populations were found to be hotter than statistically predicted, with excitation up to the energetic limit in a distribution that suggests efficient conversion of reagent kinetic energy into OH product rotation. Spin-orbit ratios show approximately equal populations in the 2∏3/2 and 2∏1/2 states of OH, but A doublets favor the symmetric A′ level for all measured values of N″. A model of the dynamics involving a planar transition state is invoked to explain the observations and predicts the SH cofragment to be formed in the A″ A doublet with little rotational energy.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry