State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, Liaoning, People's Republic of China. International Center for Quantum Materials (ICQM) and School of Physics, Peking University, Beijing 100871, People's Republic of China. Collaborative Innovation Center of Quantum Matter, Beijing 100871, People's Republic of China.
Rep Prog Phys. 2017 Feb;80(2):026401. doi: 10.1088/1361-6633/80/2/026401. Epub 2016 Dec 23.
The concept of the transition state has played an important role in the field of chemical kinetics and reaction dynamics. Reactive resonances in the transition-state region can dramatically enhance the reaction probability; thus investigation of the reactive resonances has attracted great attention from chemical physicists for many decades. In this review, we mainly focus on the recent progress made in probing the elusive resonance phenomenon in the simple A + BC reaction and understanding its nature, especially in the benchmark F/Cl + H and their isotopic variants. The signatures of reactive resonances in the integral cross section, differential cross section (DCS), forward- and backward-scattered DCS, and anion photodetachment spectroscopy are comprehensively presented in individual prototype reactions. The dynamical origins of reactive resonances are also discussed in this review, based on information on the wave function in the transition-state region obtained by time-dependent quantum wave-packet calculations.
过渡态的概念在化学动力学和反应动力学领域发挥了重要作用。过渡态区域的反应共振可以显著提高反应概率;因此,几十年来,化学物理学家一直对反应共振的研究非常关注。在这篇综述中,我们主要关注在探测简单 A + B C 反应中难以捉摸的共振现象方面取得的最新进展,并理解其本质,特别是在基准 F/Cl + H 及其同位素变体中。在单个原型反应中,全面呈现了积分截面、微分截面(DCS)、前向和后向 DCS 以及阴离子光电子能谱中反应共振的特征。基于通过含时量子波包计算获得的过渡态区域波函数信息,本文还讨论了反应共振的动力学起源。