Reaction Dynamics of Vibrationally Excited CH_3D Molecules with Chlorine

Details Reaction Dynamics of Vibrationally Excited CH_3D Molecules with Chlorine Reaction Dynamics of Vibrationally Excited CH_3D Molecules with Chlorine

Jun 2009

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..confewf08a&link_type=abstract

"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec

Physics

Dynamics

Scientific paper

State-resolved reactions of CH_{3}D molecules with Cl atoms probe the consumption and disposal of vibrational and translational energy. Using state-resolved detection it is possible to determine the relative effects of these on the reaction and gain a better understanding of the reactivity differences between modes.
In one recent experiment, we explored the effect of exciting either the combination of the C-H symmetric stretch and the C-D stretch (ν_1 + ν_2), the combination of the C-D stretch and the C-H antisymmetric stretch (ν_{2} + ν_{4}), or the combination of the C-D stretch and the first overtone of the CH_3 bend (ν_{2} + 2ν_{5}). The reaction dynamics largely follow a spectator picture in which the surviving bond retains its initial vibrational excitation. In at least 80% of the reactive encounters of vibrationally excited CH_3D with Cl, cleavage of the C-H bond produces CH_2D radicals with an excited C-D stretch, and cleavage of the C-D bond produces CH_3 radicals with an excited C-H stretch. Deviations from the spectator picture seem to reflect mixing in the initially prepared eigenstates and, possibly, collisional coupling during the reaction.

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