Multidimensional steric effect for the XeBr* (B, C) formation in the oriented Xe*((3)P2, M(J) = 2) + oriented CF3Br reaction.
Steric effect for the XeBr(*) (B, C) formation in the oriented Xe(*)((3)P(2), M(J) = 2) + oriented CF(3)Br reaction has been observed as a function of the mutual configuration between the molecular orientation and the atomic orientation in the collision frame. Molecular steric opacity function has been determined as a function of the atomic orbital alignment (L(Z)(')) in the collision frame. The L(Z)(') selectivity in the molecular steric opacity function is different between the XeBr(*) (B, C) channels: For the XeBr(*) (C) channel, the L(Z)(') = 0 alignment is favorable at the molecular axis direction and the absolute value(L(Z)(')) = 1 alignment is favorable at the sideway direction, whereas for the XeBr(*) (B) channel, the L(Z)(') = 0 alignment is favorable at the sideway direction and the absolute value(L(Z)(')) = 1 alignment is favorable at the molecular axis direction. However, the shape of the steric opacity function for the XeBr(*) (B) channel at the L(Z)(') = 0 (and absolute value(L(Z)(')) = 1) alignment is similar to that for the XeBr(*) (C) channel at the absolute value(L(Z)(')) = 1 (and L(Z)(') = 0) alignment, respectively: A large molecular orientation dependence (i.e., the largest reactivity at the Br-end with the small molecular alignment dependence) is recognized for the XeBr(*) (B) channel at the L(Z)(') = 0 alignment and for the XeBr(*) (C) channel at the absolute value(L(Z)(')) = 1 alignment, whereas a large molecular alignment dependence (i.e., the largest reactivity at the Br-end with the poor reactivity at the sideway) is recognized for the XeBr(*) (B) channel at the absolute value(L(Z)(')) = 1 alignment and for the XeBr(*) (C) channel at the L(Z)(') = 0 alignment. We propose the indirect mechanism for the dark channels (Xe + Br + CF(3)) via the back-electron transfer from the CF(3) segment (or dissociating CF(3)...Br(-)) to Xe(+) as the origin of the significant molecular alignment dependence in the molecular steric opacity function.
Ohoyama
H
H
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. ohyama@chem.sci.osaka-u.ac.jp
Oda
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R
Kasai
T
T