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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 30, Number 2
BKCSDE 30(2)
February 20, 2009 

Internal Energy Distributions of OH Products in the Reaction of O(3PJ) with HSiCl3
Hyon Tae Kwak, Seung Chul Ha, Sungwoo Jang, Hong Lae Kim, Chan Ryang Park*
Trichlorosilane, O(3PJ), LIF, OH, Internal energy distribution
The OH(X2Π, υ"=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(3PJ) atoms with kinetic energies above the reaction barrier were produced by photolysis of NO2 at 355 nm. The OH product revealed strong vibrational population inversion, P(υ"=1)/P(υ"=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 Λ 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 (<fvib> = 0.62, and <frot> = 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.
429 - 434
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