Ma. Spence et Mr. Levy, ROTATIONAL ALIGNMENT IN MNO-ASTERISK(A(6)SIGMA(-2()) FROM THE REACTION MN+O), The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(41), 1997, pp. 7490-7498
The collision energy dependence of chemiluminescence, and its polariza
tion relative to the initial velocity vector k, has been determined fo
r MnO(A(6) Sigma(+)) product from the Mn + O-2 reaction in the range
0-1500 kJ mol(-1). Analysis of the excitation function by the multiple
line-of-centers approach indicates that three parallel processes, att
ributed to a(4)D(J), z(8)P(J) (perhaps), and a(6)D(J) atoms, contribut
e. All seem to involve a significant excess barrier and a forward tran
sition state shift with increasing collision energy, suggesting that r
eaction proceeds via inner ionic-covalent curve crossings at short int
ernuclear distances. The measured alignments are relatively modest, in
dicating a predominant contribution to MnO rotation from O-O recoil in
a nonlinear Mn-O-O configuration.