Time-dependent wavepacket investigation of state-to-state reactive scattering of Cl with para-H2 including the open-shell character of the Cl atom

Abstract

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-state͒ 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.

Influence of rovibrational excitation on the non-diabatic state-to-state dynamics for the Li(2p) + H2 → LiH + H reaction

“…The TDWP method employed in this study is developed by Sun et al ., which only requires the wave-packet propagate in reactant Jacobi coordinates to extract the S -matrix information. This method is fairly effective in dealing with the reaction, which takes place over two coupled PESs, such as the Cl + H 2 reaction 32 . In the body fixed representation, the Hamiltonian of the Li(2p) + H 2 system can be written aswhere Here, is the diatom reference potential.…”

Quasiclassical trajectory study of the postquenching dynamics of OH AΣ2+ by H2/D2 on a global potential energy surface

“…The development of electronic structure theory combined with the rise in computational power has stimulated theoretical advances in simulating nonadiabatic effects in various chemical reactions. 1-3 A number of different approaches have been developed to treat these effects, including the multiconfiguration time-dependent Hartree methods, 4 the full multiple spawning method, 5 full quantum dynamical calculations, 6,7 etc.…”

Extraction of state-to-state reactive scattering attributes from wave packet in reactant Jacobi coordinates

“…77,66 However, the recent focus has been on the disagreement between theory and experiment for the Cl͑ 2 P 1 2 / 3 2 ͒ +H 2 reaction including spin-orbit effects. 64,72,[78][79][80][81] In the following numerical calculations, the benchmark BW PES 68 is used.…”