Nonadiabatic state-to-state reactive collisions among open shell reactants with conical intersections: the OH((2)Pi) + F((2)P) example.
Accurate wave packet calculations on the OH((2)Pi) + F((2)P) → O((3)P) + 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.
Zanchet
Alexandre
A
Unidad Asociada UAM-CSIC, Instituto de Física Fundamental, CSIC, Serrano 123, 28006 Madrid, Spain.
González-Lezana
Tomás
T
Aguado
Alfredo
A
Gómez-Carrasco
Susana
S
Roncero
Octavio
O