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 hydrofluorocarb ons and hydrofluoroethers have been calculated using "transition state theo ry". A new computational method has been developed for transferring along t he reaction coordinate the very high accuracy corrections, obtained at G2 l evel of theory, from small models (CH4 and CF3H) to larger molecules (halog enated 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. (C) 2001 Elsevier Science B.V. All rights reserved.