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Theoretical study of the reactions M(+)+CH(3)F (M=Ge, As, Se, Sb).

CASSCF-MRMP2 calculations have been carried out to analyze the reactions of the methyl fluoride molecule with the atomic ions Ge(+), As(+), Se(+) and Sb(+). For these interactions, potential energy curves for the low-lying electronic states were calculated for different approaching modes of the fragments. Particularly, those channels leading to C-H and C--F oxidative addition products, H(2)FC-M-H(+) and H(3)C-M-F(+), respectively were explored, as well as the paths which evolve to the abstraction (M-F(+)+CH(3)) and the elimination (CH(2)M(+)+HF) asymptotes. For the reaction Ge(+)+CH(3)F the only favorable channel leads to fluorine abstraction by the ion. As(+) and Sb(+) can react with CH(3)F along pathways yielding stable addition products. However, a viable path joining the oxidative addition product H(3)C-M-F(+) with the elimination asymptote CH(2)M(+)+HF was found for the reaction of the fluorocarbon compound with As(+). No favorable channels were detected for the interaction of fluoromethane with Se(+). The results discussed herein allow rationalizing some of the experimental data found for these interactions through gas-phase mass spectrometry.