DENSITY-FUNCTIONAL STUDIES OF THE POTENTIAL-ENERGY SURFACE OF THE NI+(CF3) COMPLEX

The potential energy surface (PES) of [Ni,C,F-3](+) has been examined by density functional calculations. The global minimum of Ni+(CF3) is found to be a FNi+... F2C ion-dipole structure with a calculated bond dissociation energy D-0(FNi+-F2C) = 52.5 +/- 5.0 kcal/mol. The intact trifluoromethyl isomer, Ni+-CF3, and the inserted difluorocarbene isom er, F2C-Ni+-F, are located at higher energies on the PES. The transiti on state structures connecting these minima are optimized and the larg est barrier of the system, 13.6 kcal/mol, involves C-F activation. (C) 1998 Elsevier Science B.V.