Abstract
The nascent product vibrational state distribution is obtained for the thermal energy associative detachment reaction H+F−→HF(v?5)+e−, ΔH = −57.0 kcal/mol. The relative vibrational populations are as follows: Nv = 10 = 0.00±0.06; Nv = 20 = 0.23±0.04; Nv = 30 = 0.27±0.03; Nv = 40 = 0.29±0.03; and Nv = 50 = 0.21±0.03. Arguments are presented that suggest that Nv = 00 = 0. The average fraction of the total energy deposited in product vibration is <fv≳ = 0.64±0.03. The release of the very light electron as one of the reaction products places severe angular momentum constraints on the reaction system. A simple kinematic model predicts a highly non-Boltzmann HF rotational state distribution which increases with increasing J up to some cutoff level. The high degree of vibrational excitation in the HF product has been accounted for by theoretical calculations of Gauyacq using the zero-range potential approximation.
Published Version
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