Xie Changjian, Jiang Bin, Yang Minghui, Guo Hua
Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
Department of Chemical Physics, University of Science and Technology of China , Hefei 230026, China.
J Phys Chem A. 2016 Aug 25;120(33):6521-8. doi: 10.1021/acs.jpca.6b06450. Epub 2016 Aug 15.
The F + CHD3 → HF/DF + CD3/CHD2 reaction is studied using a state-to-state quasi-classical trajectory method on a recently developed ab initio based full-dimensional potential energy surface. Consistent with sudden vector projection model predictions, the HF/DF products are highly excited in both vibrational and rotational modes, while the CD3/CHD2 product internal excitation is mostly in the umbrella/out-of-plane mode. Furthermore, the C-H stretching vibration in the CHD3 reactant is found to behave as an active mode for the HF + CD3 channel, leading to additional excitation in the HF product but having almost no impact on CD3 vibrational state distributions. On the other hand, this mode acts as a spectator for the DF + CHD2 channel, exerting little influence on the DF and other CHD2 vibrational modes except an extra quantum excitation in the C-H stretching mode. The calculated vibrational state resolved differential cross sections are in good agreement with available experimental results at Ec = 9.00 kcal/mol.
采用态-态准经典轨迹方法，在最近开发的基于从头算的全维势能面上研究了F + CHD3 → HF/DF + CD3/CHD2反应。与突然矢量投影模型的预测一致，HF/DF产物在振动和转动模式上都高度激发，而CD3/CHD2产物的内部激发主要在伞形/面外模式。此外，发现CHD3反应物中的C-H伸缩振动对于HF + CD3通道是一种活性模式，导致HF产物有额外的激发，但对CD3振动状态分布几乎没有影响。另一方面，对于DF + CHD2通道，该模式是一个旁观者，除了在C-H伸缩模式中有额外的量子激发外，对DF和其他CHD2振动模式几乎没有影响。在Ec = 9.00 kcal/mol时，计算得到的振动状态分辨的微分截面与现有实验结果吻合良好。
