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Theoretical studies of monofluorination reactions for hydrofluorocarbons (HFCs) over CoF 3 have been performed by semi-empirical molecular orbital calculations. Heats of formation of intermediates such as cations or radicals have been calculated. The results are consistent with the experimental regioselectivity for the monofluorination of HFCs (C 2 -C 4 ) over CoF 3 .