Liu Kopin
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan; email:
Annu Rev Phys Chem. 2016 May 27;67:91-111. doi: 10.1146/annurev-physchem-040215-112522. Epub 2016 Feb 25.
Vibrational motions of a polyatomic molecule are multifold and can be as simple as stretches or bends or as complex as concerted motions of many atoms. Different modes of excitation often possess different capacities in driving a bimolecular chemical reaction, with distinct dynamic outcomes. Reactions with vibrationally excited methane and its isotopologs serve as a benchmark for advancing our fundamental understanding of polyatomic reaction dynamics. Here, some recent progress in this area is briefly reviewed. Particular emphasis is placed on the key concepts developed from those studies. The interconnections among mode and bond selectivity, Polanyi's rules, and newly introduced vibrational-induced steric phenomena are highlighted.
多原子分子的振动运动是多样的，可能简单如拉伸或弯曲，也可能复杂如许多原子的协同运动。不同的激发模式在驱动双分子化学反应时往往具有不同的能力，会产生不同的动力学结果。涉及振动激发的甲烷及其同位素变体的反应是推动我们对多原子反应动力学基本理解的基准。在此，简要回顾该领域的一些最新进展。特别强调了从这些研究中发展出的关键概念。突出了模式和键选择性、波兰尼规则以及新引入的振动诱导空间现象之间的相互联系。
