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Quantum state resolved scattering dynamics of F+HCl-->HF(v,J)+Cl
1JILA, National Institute of Standards and Technology and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Abstract:
State-to-state reaction dynamics of the reaction F+HCl-->HF(v,J)+Cl have been studied under single-collision conditions using an intense discharge F atom source in crossed supersonic molecular beams at Ecom=4.3(1.3) kcal/mol. Nascent HF product is monitored by shot-noise limited direct infrared laser absorption, providing quantum state distributions as well as additional information on kinetic energy release from high resolution Dopplerimetry. The vibrational distributions are highly inverted, with 34(4)%, 44(2)%, and 8(1)% of the total population in vHF=1, 2, and 3, respectively, consistent with predominant energy release into the newly formed bond. However, there is a small [14(1)%] but significant formation channel into the vHF=0 ground state, which is directly detectable for the first time via direct absorption methods. Of particular dynamical interest, both the HF(v=2,J) and HF(v=1,J) populations exhibit strongly bimodal J distributions. These results differ significantly from previous flow and arrested-relaxation studies and may signal the presence of microscopic branching in the reaction dynamics.
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