The falloff curves of the unimolecular dissociation CFI (+Ar) → CF + I (+Ar) are modelled by combining quantum-chemical characterizations of the potential energy surface for the reaction, standard unimolecular rate theory, and experimental information on the average energy transferred per collision between excited CFI and Ar. The (essentially) parameter-free theoretical modelling gives results in satisfactory agreement with data deduced from earlier shock wave experiments employing a variety of reactant concentrations (between a few ppm and a few percent in the bath gas Ar). New experiments recording absorption-time signals of CFI, I, CF and (possibly) IF at 450-500 and 200-300 nm are reported. By analysing the decomposition mechanism, besides the unimolecular dissociation of CFI, these provide insight into the influence of secondary reactions on the experimental observations.
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