ROTATIONAL AND SPIN-ORBIT EFFECTS IN THE DYNAMICS OF O(P-3(J))-ORBIT PROPENSITIES(HYDROCARBON REACTIONS .2. MODELS FOR SPIN)

The spin-orbit states of OH have been found in part I to be unequally populated in reactions of O(P-3(j)) with saturated hydrocarbons. We cl arify the correlations in these systems within an adiabatic, Omega-con serving approximation, and show that the observed OH spin-orbit distri butions are not well reproduced in this adiabatic limit. However, the inclusion of strong nonadiabatic coupling between surfaces of the same Omega and parity results in a much improved prediction. The necessary mixing is demonstrated to be compatible with a previous independent c haracterization of the entrance channel surfaces in O(P-3(j)) + CH4 co llisions, and with the known propensities for inelastic, j-changing co llisions of O(P-3(j)) with closed shell partners. The nonadiabatic mod el which agrees best with the observed OH spin-orbit ratios suggests t hat the O(P-3(j)) reactivity should vary only moderately with j. (C) 1 997 American Institute of Physics.