Toward a Comprehensive Understanding of Mode-Specific Dynamics of Polyatomic Reactions: A Full-Dimensional Quantum Dynamics Study of the H + NH3 Reaction
Toward a Comprehensive Understanding of Mode-Specific Dynamics of Polyatomic Reactions: A Full-Dimensional Quantum Dynamics Study of the H + NH3 Reaction
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全面了解多原子反应的模式特异性动力学：H NH3 反应的全维量子动力学研究
DOI：
10.1021/acs.jpca.1c08399
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Minghui Yang
中科院分区：
文献类型：
--
作者：
Hongwei Song;Weiyu Xie;Chaoyang Zhang;Minghui Yang
Mode specificity not only sheds light on reaction dynamics but also opens the door for chemical reaction control. This work reports a state-of-the-art full-dimensional quantum dynamics study on the prototypical hydrogen abstraction reaction of hydrogen with ammonia, which serves as a benchmark for advancing our fundamental understanding of polyatomic reaction dynamics. By taking advantage of the (3 + 1) Radau–Jacobi coordinates, the bond-specific probabilities are resolved with the reactant NH3initiated from either a non-degenerate or degenerate stretching vibrational state. The observed different atom-specific abstraction probabilities from individual states of the degenerate pair are rationalized in the local mode representation according to the different vibrational energy deposited in each N–H bond. It is verified that the three H atoms in NH3have the same abstraction probability as that from the degenerate pair and the linear combination of the degenerate pair gives the same reaction probability. In addition, the symmetric and asymmetric stretching modes of the reactant NH3have comparable efficacies on driving the reaction.
