Ellerbrock Roman, Zhao Bin, Manthe Uwe
Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld, Germany.
Department of Chemistry and The PULSE Institute, Stanford University, Stanford, CA 94305, USA.
Sci Adv. 2022 Apr;8(13):eabm9820. doi: 10.1126/sciadv.abm9820. Epub 2022 Mar 30.
An accurate full-dimensional quantum state-to-state simulation of the six-atom title reaction based on first-principles theory is reported. Counterintuitive effects are found: Increasing the energy in the reactant's CD umbrella vibration reduces the energy in the corresponding product vibration. An in-depth analysis reveals the crucial role of the effective dynamical transition state: Its geometry is controlled by the vibrational states of the reactants and subsequently controls the quantum state distribution of the products. This finding enables generalizing the concept of transition state control of chemical reactions to the quantum state-specific level.
报道了基于第一性原理理论对六原子标题反应进行的精确全维态-态量子模拟。发现了违反直觉的效应：增加反应物CD伞形振动的能量会降低相应产物振动的能量。深入分析揭示了有效动力学过渡态的关键作用：其几何结构由反应物的振动态控制，进而控制产物的量子态分布。这一发现使得将化学反应过渡态控制的概念推广到量子态特定水平成为可能。
