Nonadiabatic State-to-State Reactive Collisions among Open Shell Reactants with Conical Intersections: The OH(2Π) + F(2P) Example

Accurate wave packet calculations on the OH((2)Pi) + F(P-2) --> O(P-3) + HF((1)Sigma(+)) reactive collisions are performed using a recently proposed coupled diabatic states. Adiabatic and nonadiabatic dynamics are compared in detail, analyzing the final state distribution of products. It is found that with the new surfaces a significant increase of the rate constant is obtained, with noticeable nonadiabatic effects. The inclusion of the spin-orbit splittings for the calculation of the electronic partition function produces an important increase of the reaction rate constants, yielding a rather good agreement with the experimental results. It is also concluded that spin-orbit couplings are also necessary in the entrance channel to describe this reaction.