State-to-State Mode Specificity in F + CHD3 → HF/DF + CD3/CHD2 Reaction

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• 作者：Changjian Xie ; Bin Jiang ; Minghui Yang ; Hua Guo
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：August 25, 2016
• 年：2016
• 卷：120
• 期：33
• 页码：6521-6528
• 全文大小：598K
• 年卷期：0
• ISSN：1520-5215

文摘

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 E_c = 9.00 kcal/mol.