From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ⇆ HX plus OH [X = F, Cl, and O(3P)] Reactions
From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ⇆ HX plus OH [X = F, Cl, and O(3P)] Reactions
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DOI：
10.1021/acs.jpca.5b02510
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发表时间：
2015-05-21
影响因子：
2.9
通讯作者：
Guo, Hua
中科院分区：
文献类型：
--
作者：
Li, Jun;Jiang, Bin;Guo, Hua
本文以反应为例，综述了量子态分辨动力学理论研究的最新进展。它表明，取得进展是可能的两个领域的重大事态发展。首先，现在可以以高保真度和必要的排列对称性对大构型空间上的许多高水平从头算点进行精确的解析表示。由此产生的全维全球势能面，使动力学计算使用准经典轨迹或更重要的量子力学方法。第二个进步是发展了精确和有效的量子动力学方法，这对于提供可靠的处理反应动力学中的量子效应，如隧穿，共振和零点能量是必要的。这两个进步的有力结合使我们能够实现反应动力学的定量准确表征，揭示了丰富的动力学特征，如空间转向，强模式特异性和键选择性。最近提出的突然矢量投影模型可以合理化反应模式的反应性的依赖性，该模型将模式特异性和键选择性归因于反应模式与反应坐标在相关过渡态的耦合。这些理论研究所提供的更深刻的见解使我们对反应动力学的理解达到了一个新的水平。
We survey the recent advances in theoretical understanding of quantum state resolved dynamics, using the title reactions as examples. It is shown that the progress was made possible by major developments in two areas. First, an accurate analytical representation of many high-level ab initio points over a large configurations space can now be made with high fidelity and the necessary permutation symmetry. The resulting full-dimensional global potential energy surfaces enable dynamical calculations using either quasi-classical trajectory or more importantly quantum mechanical methods. The second advance is the development of accurate and efficient quantum dynamical methods, which are necessary for providing a reliable treatment of quantum effects in reaction dynamics such as tunneling, resonances, and zero-point energy. The powerful combination of the two advances has allowed us to achieve a quantitatively accurate characterization of the reaction dynamics, which unveiled rich dynamical features such as steric steering, strong mode specificity, and bond selectivity. The dependence of reactivity on reactant modes can be rationalized by the recently proposed sudden vector projection model, which attributes the mode specificity and bond selectivity to the coupling of reactant modes with the reaction coordinate at the relevant transition state. The deeper insights provided by these theoretical studies have advanced our understanding of reaction dynamics to a new level.