On the reaction Na(2P)+H2→Na(2S)+H2 nonadiabatic effects

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Abstract
This work reports the first ab initio treatment of nonadiabatic coupling strengths for the quenching reaction, Na(2P)+H2→Na(2S)+H2. In particular, guided by the ab initio SCF‐CEPA calculation of Botschwina et al. [J. Chem. Phys. 7 5, 5438 (1981)], the C2v allowed crossing seam of conical intersections of the 1 2A’ and 2 2A’ potential energy surfaces is located at the state averaged MCSCF/CI level. These crossings provide the path or funnel for channeling the Na(2P) nonradiatively to Na(2S). In order to determine the efficacy of this feature in inducing this transition, nonadiabatic coupling matrix elements arising from three internal coordinates are determined using a recently developed algorithm based on analytic gradient techniques.