Non-statistical energy partitioning in the decomposition of chemically activated CF₃OH and CH₂FOH molecules

The vibrational energy distributions of the HF produced in the following two reactions: O(¹D) + CHF₃ → [CF₃OH†] → HF† + CF₂O, O(¹D) + [CH₃ → [CH₂FOH† + CH₂O have been determined by measuring the appearance times of laser pulses resulting from various vibration-rotation transitions in a grating-tuned laser cavity. This technique has been explicitly corroborated for the HF† produced by the O(¹D) + CHF₃ reaction using a Statz and deMars rate equation model The observed HF† vibrational energy distributions in both systems were found to be considerably hotter than those predicted by simple statistical models, indicating that the excited fluoromethanol intermediates are short-lived and the available energies in these reactions have not been completely randomized.