Reactive scattering of F+HD -> HF(v,J)+D: HF(v,J) nascent product state distributions and evidence for quantum transition state resonances
- BATTELLE (PACIFIC NW LAB)
- California Institute of Technology
- Colorado, University Of
Single collision reactive scattering dynamics of F+ HDHF(v,J)+ D have been investigated exploiting high-resolution (0.0001 cm?1) infrared laser absorption for quantum state resolved detection of nascent HF(v,J) product states. State resolved Doppler profiles are recorded for a series of HF rovibrational transitions and converted into state resolved fluxes via density-to-flux analysis, yielding cross-section data for relative formation of HF(v,J) at Ecom0.6(2), 1.0(3), 1.5(3), and 1.9(4) kcal/mol. State resolved HF(v,J) products at all but the lowest collision energy exhibit Boltzmann-type populations, characteristic of direct reactive scattering dynamics. At the lowest collision energy[Ecom0.6(2) kcal/mol], however, the HF(v= 2,J) populations behave quite anomalously, exhibiting a nearly''flat'' distribution out to J11 before dropping rapidly to zero at the energetic limit. These results provide strong experimental support for quantum transition state resonance dynamics near Ecom0.6 kcal /mol corresponding classically to H atom chattering between the F and D atoms, and prove to be in remarkably quantitative agreement with theoretical wave packet predictions by Skodje et al.[J. Chem. Phys. 112, 4536 (2000)]. These fully quantum state resolved studies therefore nicely complement the recent crossed beam studies of Dong et al.[J. Chem. Phys. 113, 3633 (2000)], which confirm the presence of this resonance via angle resolved differential cross-section measurements. The observed quantum state distributions near threshold also indicate several rotational states in the HF(v= 3) vibrational manifold energetically inaccessible to F(2P3/2) reagent, but which are consistent with a minor (5%) nonadiabatic contribution from spin?orbit excited F*(2P1/2).?2002 American Institute of Physics.
- Research Organization:
- Pacific Northwest National Lab., Richland, WA (US)
- Sponsoring Organization:
- US Department of Energy (US)
- DOE Contract Number:
- AC06-76RL01830
- OSTI ID:
- 15001010
- Report Number(s):
- PNNL-SA-36233; 830403000; TRN: US200401%%306
- Journal Information:
- Journal of Chemical Physics, Vol. 116, Issue 13; Other Information: PBD: 1 Dec 2001
- Country of Publication:
- United States
- Language:
- English
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