Translational excitation functions have been determined for production of several MnF* states-b(5) Pi, c(5) Sigma(+), d(5) Pi, and (most probably) e(5) Sigma(+)-in the reaction of a laser-ablated beam of Mn atoms with gaseous CF4. Although all observed channels show high initial thresholds, similar to 200-300 kJ mol(-1), reaction appears to be due to excited Mn atoms rather than the ground state, a(6)S. The reagent species appears to be either the first or third metastable level, a(6)D(J) or a(4)D(J). Analysis of the energy dependences, in terms of a multiple line-of-centers model [Levy, Res. Chern. Kinet. 1993, I, 163], indicates that at relatively low energies, a common process is responsible for b(5) Pi and c(5) Sigma(+) formation, involving a similar to 14% forward shift in reaction transition state as collision energy increases. Quite separate processes, without transition state shifts, lead to production of MnF*(d(5) Pi) and of MnF*(e(5) Sigma(+))/"blue" emission at relatively low energies and to enhanced c(5) Sigma(+) production at high energies. It is possible that enhanced production of MnF*(e(5) Sigma(+)) and perhaps the d(5) Pi state from similar to 650-700 kJ mol(-1) derives from the depletion of MnF*(b(5) Pi, c(5) Sigma(+)). Despite the undoubted negative CF4 electron affinity, it seems likely that avoided ionic-covalent curve crossings at least play a role in the b(5) Pi/c(5) Sigma(+) production channel.