Control of Mode/Bond Selectivity and Product Energy Disposal by the Transition State: X + H2O (X = H, F, O(3P), and Cl) Reactions
Control of Mode/Bond Selectivity and Product Energy Disposal by the Transition State: X + H2O (X = H, F, O(3P), and Cl) Reactions
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DOI：
10.1021/ja408422y
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发表时间：
2013-10-09
影响因子：
15
通讯作者：
Guo, Hua
中科院分区：
文献类型：
--
作者：
Jiang, Bin;Guo, Hua
预测模式/键选择性和能量处理的能力对于控制化学反应是至关重要的。我们认为过渡态在状态到状态的反应性中起着至关重要的作用，并提出了一个基于与过渡态反应坐标耦合的简单的突变模型。这种所谓的突然向量投影（SVP）模型的适用性检验了几个原型原子-三原子，即X + H2O （X = H， F， O（P-3）和Cl）反应。结果表明，SVP模型能够定性地预测这些多原子反应的实验和全维量子动力学结果，包括本工作中报道的结果。这些结果以及其他反应的结果表明，SVP模型为理解双分子反应中的量子态分解反应性提供了一个通用范例。
The ability to predict mode/bond selectivity and energy disposal is of central importance for controlling chemical reactions. We argue that the transition state plays a critical role in state-to-state reactivity and propose a simple sudden model based on coupling with the reaction coordinate at the transition state. The applicability of this so-called sudden vector projection (SVP) model is examined for several prototypical atom-triatom, namely, X + H2O (X = H, F, O(P-3), and Cl) reactions. It is shown that the SVP model is capable of qualitatively predicting experimental and full-dimensional quantum dynamical results, including those reported in this work, for these polyatomic reactions. These results, and those for other reactions, suggest that the SVP model offers a general paradigm for understanding quantum state resolved reactivity in bimolecular reactions.