RRKM and direct MP2/6-31G(d,p) quasiclassical trajectory study of the H2 elimination in the photodissociation of vinyl chloride at 193 nm

RRKM calculations and MP2/6-31G(d,p) quasiclassical trajectories (QCT) were performed to investigate the H2 elimination in the photodissociation of vinyl chloride at 193 nm. The kinetic study involved nine elementary steps and the QCT investigation was made for the relevant reaction channels. The trajectories were initiated at the transition states using a microcanonical, quasiclassical normal-mode sampling. Comparison between the calculated product energy distributions and the available experimental data is discussed. Overall, the present results (RRKM and QCT) suggest that the direct three-center elimination, which may occur via two similar transition states, is the dominant mechanism for H2 production.