Abstract

Abstract The kinetics of the recombination reaction of FC(O)O radicals has been experimentally and theoretically investigated. The FC(O)O radicals were generated by excimer laser flash photolysis of mixtures of (FCO) 2 and O 2 in excess of CO at 297 K and monitored by absorption spectroscopy at 545 nm. In agreement with the predictions from unimolecular rate theory, no appreciable falloff effects were observed for total pressures ranging from 117 to 727 Torr. The measured limiting high pressure rate coefficient, k rec, ∞ = (7.0 ± 1.1) × 10 −13 cm 3 molecule −1 s −1 , agrees very well with that predicted by a simplified version of the statistical adiabatic channel model. The influence of the dominant potential energy surface features on k rec, ∞ was examined between 200 and 600 K.

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