State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
School of Physical Science and Technology, ShanghaiTech University, 100 Haike Road, Shanghai 201210, China.
Science. 2020 May 15;368(6492):767-771. doi: 10.1126/science.abb1564.
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 → H + 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 H (' = 2, ' = 3) product (where ' is the vibrational quantum number and ' 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.
理解量子干涉对于研究化学反应动力学至关重要。在这里,我们提供了一个有趣的案例,即在 1.94 到 2.21 eV 的碰撞能范围内,H + HD → H + D 反应中两种拓扑上不同途径之间的量子干涉,表现为向后散射方向上 H('=2,'=3)产物微分截面的能量依赖性中的振荡(其中'是振动量子数,'是转动量子数)。观察到的明显的振荡模式归因于直接提取途径和不寻常的漫游插入途径之间的强烈量子干涉。更有趣的是,观察到的干涉模式还提供了在反应中远远低于锥形交叉点的能量下几何相位效应的敏感探针,这类似于物理学中的 Aharonov-Bohm 效应,清楚地表明了化学反应性的量子性质。