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The thermal dissociation data for SF6 has been re-evaluated using RRKM unimolecular reaction rate theory and was found to be consistent with a higher value for the sulfur–fluorine bond strength (92 kcal/mole). A model based on a rate equation formalism has been developed that includes unimolecular dissociation, collisional energy transfer (V–T processes), and absorption and emission of laser radiation. The model was designed to test theories of absorption of laser radiation for laser-induced chemical reaction in SF6 that are amenable to a rate equation formalism. It was found that the thermal reaction and vibrational relaxation data could be adequately reproduced. Sample calculations of laser-induced chemical reactions are performed.