Temperature dependence of the vibrational energy distributions in the reactions F + H2 and F + D2

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Abstract
Using chemical laser methods, the behavior of the product vibrational distributions in the reactions F+H2→ HF+H and F+D2→ DF+D has been studied as a function of reactant temperature. Both the equal-gain and zero-gain techniques were employed. In the F + H2 system, k3/k2 and k2/k1 increase as temperature decreases, k2/k1 showing a much stronger dependence than k3/k2. Both the k3/k2 and k2/k1 temperature dependences fit an Arrhenius-type form, k3/k2= 0.39 exp (+117/R T) and k2/k1= 2.14 exp (+254/R T). An opposite behavior is observed for the F + D2 system: k3/k2 rises with increasing temperature. These results provide the first quantitative evidence that reaction product vibrational distributions are temperature dependent and they demonstrate the applicability of chemical lasers to such measurements.