Understanding mode-specific dynamics in the local mode representation
Understanding mode-specific dynamics in the local mode representation
复制标题
了解局部模式表示中特定于模式的动态
DOI：
10.1039/c8cp03240h
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发表时间：
2018
影响因子：
3.3
通讯作者：
Yang Minghui
中科院分区：
文献类型：
--
作者：
Song Hongwei;Yang Minghui
模式特异性是反应动力学过渡态控制的一个重要特征。简正模表象已被广泛用于描述基元化学反应的模式特异性。然而，光谱学家已经证明，本地模式表示在分析泛音和组合带谱方面具有优势。本文采用（2 + 1）Radau-Jacobi坐标系下的全维量子散射模型，研究了氢原子与H2S和H2O分子之间的特定模式反应动力学。在正常模式表征中违反我们的物理直觉的反应中的模式特异性在局部模式表征中得到了很好的合理化。揭示了分子内和/或分子间相互作用引起的不同XH键之间的能量流动及其对提取和交换反应动力学的影响。
Mode specificity is a main characteristic of transition state control of reaction dynamics. The normal mode representation has been widely employed to describe the mode specificity in elementary chemical reactions. However, spectroscopists have demonstrated that the local mode representation has advantages in analyzing the overtone and combination band spectra. In this work, the mode-specific reaction dynamics between the hydrogen atom and the molecules H2S and H2O is studied using a full-dimensional quantum scattering model in the (2 + 1) Radau–Jacobi coordinates. The mode specificities in the reactions that violates our physical intuition in the normal mode representation are well rationalized in the local mode representation. The energy flow between different XH bonds resulting from the intramolecular interaction and/or intermolecular interaction is unveiled, together with its impacts on dynamics of the abstraction and exchange reactions.