Buren Bayaer, Yang Zijiang, Chen Maodu
Key Laboratory of Materials Modification by Laser, Electron, and Ion Beams (Ministry of Education), School of Physics, Dalian University of Technology, Dalian 116024, P. R. China.
Phys Chem Chem Phys. 2020 Feb 14;22(6):3633-3642. doi: 10.1039/c9cp06026j. Epub 2020 Jan 30.
Time-dependent wave packet calculations are carried out for two reaction channels of the non-adiabatic Na(3p) + HD → NaH/NaD + D/H reaction. The potential well on the excited state potential energy surface makes the reaction preferable to proceed through the insertion reaction path. The dominance of the NaD + H reaction channel and product rotational state distributions are found to be in agreement with the characteristics of typical adiabatic insertion reactions. However, significant forward scattering peaks in the differential cross sections (DCS) are found to be inconsistent with the forward-backward symmetric scattering characteristic of typical adiabatic insertion reactions, which indicate that the Na(3p) + HD reaction is dominated by a direct reaction mechanism. The comparison between adiabatic and non-adiabatic calculated DCSs reveals that the non-adiabatic couplings in the reaction could reduce the lifetime of the intermediate complex. Finally, the insertion-abstraction mechanism is put forward for the non-adiabatic Na(3p) + HD reaction.
