Czakó Gábor, Gruber Balázs, Papp Dóra, Tajti Viktor, Tasi Domonkos A, Yin Cangtao
MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary.
Phys Chem Chem Phys. 2024 Jun 6;26(22):15818-15830. doi: 10.1039/d4cp00417e.
Controlling the outcome of chemical reactions by exciting specific vibrational and/or rotational modes of the reactants is one of the major goals of modern reaction dynamics studies. In the present Perspective, we focus on first-principles vibrational and rotational mode-specific dynamics computations on reactions of neutral and anionic systems beyond six atoms such as X + CH [X = F, Cl, OH], HX + CH [X = Br, I], OH + CHI, and F + CHCHCl. The dynamics simulations utilize high-level analytical potential energy surfaces and the quasi-classical trajectory method. Besides initial state specificity and the validity of the Polanyi rules, mode-specific vibrational-state assignment for polyatomic product species using normal-mode analysis and Gaussian binning is also discussed and compared with experiment.
通过激发反应物的特定振动和/或转动模式来控制化学反应的结果是现代反应动力学研究的主要目标之一。在本综述中，我们专注于对六个以上原子的中性和阴离子体系反应进行第一性原理振动和转动模式特异性动力学计算，例如X + CH [X = F、Cl、OH]、HX + CH [X = Br、I]、OH + CHI和F + CHCHCl。动力学模拟使用高水平的分析势能面和准经典轨迹方法。除了初始态特异性和波兰尼规则的有效性外，还讨论了使用简正模式分析和高斯分箱法对多原子产物物种进行模式特异性振动态分配，并与实验进行了比较。
