Computational studies of the reaction of the hydroxyl radical with hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs)

The reaction rate constants of a hydroxyl radical with some hydrofluorocarbons and hydrofluoroethers have been calculated using "transition state theory". A new computational method has been developed for transferring along the reaction coordinate the very high accuracy corrections, obtained at G2 level of theory, from small models (CH₄ and CF₃H) to larger molecules (halogenated ethanes and methyl ethers). The substituent effects on the C-H bond strengths and on the reaction rate constants have been examined, as well as the geometrical and electronic features of the transition states.