Quantum interference in H plus HD → H2 + D between direct abstraction and roaming insertion pathways
Quantum interference in H plus HD → H2 + D between direct abstraction and roaming insertion pathways
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H HD – H2 D 中直接抽象和漫游插入路径之间的量子干扰
DOI：
10.1126/science.abb1564
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发表时间：
2020-05-15
期刊：
影响因子：
56.9
通讯作者：
Yang, Xueming
中科院分区：
文献类型：
--
作者：
Xie, Yurun;Zhao, Hailin;Yang, Xueming
量子干涉（QI）效应在化学反应动力学中起着重要作用。Xie等人在原型基元反应H + HD → H2 + D的反冲散射方向上测量的微分截面中发现了不寻常的QI振荡（参见奥伊兹的观点）。拓扑分析表明，这种模式起源于QI之间的直接抽象和以前未知的反弹插入路径，这是受几何相位的能量远低于圆锥形交叉。在三原子系统中，在这两个不同的路径之间观察到的QI是化学反应性的量子性质的一个明显例子。《科学》，本期第767页;另见第706页在圆锥交叉点下方的反冲方向上观察到受几何相位影响的量子干涉。理解量子干涉对化学反应动力学的研究至关重要。在这里，我们提供了一个有趣的情况下，在H + HD → H2 + D反应中，在1.94和2.21 eV之间的碰撞能量范围内，两个拓扑不同的路径之间的量子干涉，表现为H2微分截面的能量依赖性的振荡。（v′ = 2，j′ = 3）乘积（其中v′是振动量子数，j′是转动量子数）。观察到的显着的振荡模式归因于强的量子直接提取途径和一个不寻常的漫游插入途径之间的干扰。更有趣的是，观察到的干涉图样还提供了一个灵敏的探测几何相位效应的能量远低于圆锥交叉在这个反应中，这类似于物理学中的Aharonov-Bohm效应，清楚地表明了化学反应的量子性质。
Intriguing interference mechanism Quantum interference (QI) effects play a fundamental role in the dynamics of chemical reactions. Xie et al. detected unusual QI oscillations in the differential cross section measured in the recoil scattering direction of the prototypical elementary reaction H + HD → H2 + D (see the Perspective by Aoiz). Topological analysis showed that this pattern originates from the QI between a direct abstraction and previously unknown rebounding insertion pathways, which are affected by the geometric phase at energies far below the conical intersection. The QI observed between these two distinctive pathways in the three-atom system is a clear example of the quantum nature of chemical reactivity. Science, this issue p. 767; see also p. 706 Quantum interference affected by the geometric phase is observed in the recoil direction well below the conical intersection. Understanding quantum interferences is essential to the study of chemical reaction dynamics. Here, we provide an interesting case of quantum interference between two topologically distinct pathways in the H + HD → H2 + D reaction in the collision energy range between 1.94 and 2.21 eV, manifested as oscillations in the energy dependence of the differential cross section for the H2 (v′ = 2, j′ = 3) product (where v′ is the vibrational quantum number and j′ is the rotational quantum number) in the backward scattering direction. The notable oscillation patterns observed are attributed to the strong quantum interference between the direct abstraction pathway and an unusual roaming insertion pathway. More interestingly, the observed interference pattern also provides a sensitive probe of the geometric phase effect at an energy far below the conical intersection in this reaction, which resembles the Aharonov–Bohm effect in physics, clearly demonstrating the quantum nature of chemical reactivity.