Quantum stereodynamics of the F+OH(v, j) reactive collision on the 1(3) A'' state

Abstract

The reactivity dependence on the k, j vector correlation for the title reaction is studied for j=1, 2, 3 by a quantum wavepacket method in a large range of translational energy on a recently obtained 3A'' adiabatic potential energy surface. It is found that the reaction is extraordinarily enhanced when initially k and j are perpendicular, or equivalently, when the OH internuclear vector is parallel to the initial relative velocity in the rotating body-fixed plane. Such a result is interpreted in terms of the kinematic constraints imposed by the small skew angle in heavy-light + heavy reactions, being a general situation in this kind of HL + H → H + LH reactions. The total reaction cross-sections obtained are in rather good agreement with quasiclassical results, especially as j increases. Finally, the rate constants obtained are compared with available experimental data at nearly room temperature.