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 E-com=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 upsilon(HF)=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 upsilon(HF)=0 ground state, which is directly detectable for the first time via direct absorption methods. Of particular dynamical interest, both the HF(upsilon=2,J) and HF(upsilon=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. (c) 2007 American Institute of Physics.
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