TITLE

Reactive scattering dynamics in atom+polyatomic systems: F+C2H6→HF(v,J)+C2H5

AUTHOR(S)
Whitney, Erin S.; Zolot, Alexander M.; McCoy, Anne B.; Francisco, Joseph S.; Nesbitt, David J.
PUB. DATE
March 2005
SOURCE
Journal of Chemical Physics;3/22/2005, Vol. 122 Issue 12, p124310
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
State-to-state scattering dynamics of F+C2H6→HF(v,J)+C2H5 have been investigated at Ecom=3.2(6) kcal/mol under single-collision conditions, via detection of nascent rovibrationally resolved HF(v,J) product states with high-resolution infrared laser absorption methods. State-resolved Doppler absorption profiles are recorded for multiple HF(v,J) transitions originating in the v=0,1,2,3 manifold, analyzed to yield absolute column-integrated densities via known HF transition moments, and converted into nascent probabilities via density-to-flux analysis. The spectral resolution of the probe laser also permits Doppler study of translational energy release into quantum-state-resolved HF fragments, which reveals a remarkable linear correlation between (i) HF(v,J) translational recoil and (ii) the remaining energy available, Eavail=Etot-EHF(v,J). The dynamics are interpreted in the context of a simple impulsive model based on conservation of linear/angular momentum that yields predictions in good agreement with experiment. Deviations from the model indicate only minor excitation of ethyl vibrations, in contrast with a picture of extensive intramolecular vibrational energy flow but consistent with Franck–Condon excitation of the methylene CH2 bending mode. The results suggest a relatively simple dynamical picture for exothermic atom+polyatomic scattering, i.e., that of early barrier dynamics in atom+diatom systems but modified by impulsive recoil coupling at the transition state between translational/rotational degrees of freedom.
ACCESSION #
16669536

 

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