The dynamics and microscopic kinetics of the reactions of O(1D2) atoms with CHCl3 and CHF3

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Abstract
The energy disposal and branching ratios in the reactions of O(1D2) with CHCl3 and CHF3 have been measured using an implementation of time‐resolved Fourier transform spectroscopy in this laboratory. The infrared emission from the products of the reactions is measured as a function of time after the creation of the O(1D2) atom by UV photolysis of ozone. The reaction with CHCl3 produces OH, HCl, and CO as primary products. The OH vibrational excitation indicates simple abstraction dynamics. The HCl has much lower vibrational excitation, characteristic of a longer‐lived insertion‐elimination process, which also produces CO in the decomposition of the internally excited Cl2CO product. Only HF is observed in the reaction with CHF3. In this case the vibrational distribution is nonmonotonic, indicating contributions from two microscopic channels, possibly associated with the formation of F2CO in both the ground (X̃ 1A1) and first excited (Ã 1A2) states.

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