Time-dependent wavepacket investigation of state-to-state reactive scattering of Cl with para-H(2) including the open-shell character of the Cl atom.
We describe a time-dependent wavepacket based method for the calculation of the state-to-state cross sections for the Cl+H(2) reaction including all couplings arising from the nonzero spin and electronic orbital angular momenta of the Cl atom. Reactant-product decoupling allows us to use a physically correct basis in both the reactant and the product arrangements. Our calculated results agree well with the experimental results of Yang and co-workers. We also describe a model with two coupled potential energy surfaces, which includes the spin-orbit coupling, which is responsible for the largest non-Born-Oppenheimer effects in the Cl+H(2) reaction but neglects the off-diagonal electronically diabatic coupling and all Coriolis couplings due to the electronic spin and orbital angular momenta. The comparison of the results of the full six-state and two-state models with an electronically adiabatic (one-state) description reveals that the latter describes well the reaction out of the ground spin-orbit state, while the two-state model, which is computationally much faster than the full six-state model, describes well the reaction from both the ground and excited spin-orbit states.
Sun
Zhigang
Z
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
Zhang
Dong H
DH
Alexander
Millard H
MH