MULTIPLE CHEMILUMINESCENT CHANNELS IN THE REACTION MN-]MNF+SF5(SF6)

Five different MnF emitting states-A(7)II, e(5) Sigma(+), d(5)II, c(5 ) Sigma(+), and b(5)II-have been observed from collisions between SF6 molecules and a pulsed, laser-ablated beam of Mn atoms. The various ex citation functions, measured up to nominal collision energy E(T)(0) = 2000 kJ mol(-1), have been modeled by the multiple line-of-centers app roach. The analysis indicates that MnF(A(7) Sigma(+)) is predominantl y formed on a single potential surface, with probable progenitor Mn(z (8)P(J)); the e(5) Sigma(+), d(5)II, and c(5) Sigma(+) states are form ed via three common potential surfaces, with likely reagent state Mn( a(6)D(J)), while the a(6)D(J) state is also likely to be the progenito r of MnF(b(5)II). Partial depletion of the b(5)II state at high energ y seems to be accompanied by enhanced yield of the other emitters. All reactions seem to be characterized by a shift forward in transition s tate location with increasing collision energy. The results suggest an electron jump barrier at short internuclear distances, forced outward at higher collision energies due to lack of time for the SF6 to disto rt to the equilibrium geometry of SF6-.