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Abstract:
The thermal dissociation/recombination reactions of the perfluoromethyl halides CF4↔CF3+F, CF3Cl↔CF3+Cl, CF3Br↔CF3+Br, and CF3I↔CF3+I are analyzed with respect to their transition (for increasing pressures) from second-order to first-order dissociation (or from third-order to second-order recombination). The dependence of this transition on the temperature is documented. Practical aspects of the modelling of falloff curves are discussed.