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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

Title	Internal Energy Distributions of OH Products in the Reaction of O(³P_J) with HSiCl₃
Author	Hyon Tae Kwak, Seung Chul Ha, Sungwoo Jang, Hong Lae Kim, Chan Ryang Park*
Keywords	Trichlorosilane, O(³P_J), LIF, OH, Internal energy distribution
Abstract	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(³P_J) 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 (<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.
Page	429 - 434
Full Text	PDF

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