State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, Liaoning 116023, China.
Chem Soc Rev. 2018 Aug 28;47(17):6744-6763. doi: 10.1039/c8cs00041g.
The transition state is a key concept in the field of chemistry and is important in the study of chemical kinetics and reaction dynamics. Chemical reactions in the gas phase are essentially molecular scattering processes, which are quantum mechanical in nature. Thus probing and understanding detailed quantum structure in the transition state region of chemical reactions, such as reactive resonances, is a central topic in this field. In this article, we focus on recent progress in the study of resonances in elementary bimolecular reactions using state-of-the-art transition state spectroscopy methods: high-resolution photoelectron spectroscopy and quantum state specific backward scattering spectroscopy. The experimental results are compared with high-level quantum dynamics calculations based on highly accurate potential energy surfaces. The dynamics of reactive resonances are also interpreted based on scattering wavefunctions obtained by time-dependent wavepacket calculations. Here, we review many systems that illustrate how reactive resonances can strongly influence the dynamics of elementary chemical reactions.
过渡态是化学领域的一个关键概念，在研究化学动力学和反应动力学中非常重要。气相中的化学反应本质上是分子散射过程，具有量子力学性质。因此，探测和理解化学反应过渡态区域的详细量子结构，如反应共振，是该领域的一个核心课题。在本文中，我们重点介绍了使用最先进的过渡态光谱方法——高分辨率光电子能谱和量子态特异后向散射光谱——研究基本双分子反应中共振的最新进展。实验结果与基于高精度势能面的高精度量子动力学计算进行了比较。基于通过时变波包计算获得的散射波函数，对反应共振的动力学进行了解释。在这里，我们回顾了许多系统，这些系统说明了反应共振如何强烈影响基本化学反应的动力学。
