Internal Energy Distributions of OH Products in the Reaction of O(<SUP>3</SUP>PJ) with HSiCl3

초록

The OH,(X-2 Pi, upsilon ''=0, 1) internal state distributions from the reaction of electronically ground state oxygen atoms with HSiCl3 were measured using laser-induced fluorescence. The ground-state O(P-3(J)) atoms with kinetic energies above the reaction barrier were produced by photolysis of NO2 at 355 run. The OH product revealed strong vibrational Population inversion, P(upsilon ''=1)/P(upsilon ''=0) = 4.0 +/- 0.6, and rotational distributions in both vibrational states exhibit Substantial rotational excitations to the limit of total available energy. However, no preferential populations in either of the two A doublet states were observed from the micropopulations, which supports a mechanism involving a direct abstraction of hydrogen by the atomic oxygen. It was also found that the collision energy between O and HSiCl3 is effectively Coupled into the excitation of the internal degrees of freedom of the OH product (<f(vib)> = 0.62, and <f(rot)> = 0.20). The dynamics appear consistent with expectations for the kinematically constrained reaction which Supports the reaction type, heavy + light-heavy -> heavy-light + heavy (H + LH' -> HL + H'). The dynamics of oxygen atom collision with HSiCl3 are discussed in comparison to those with SiH4.

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