Kling Nora G, Díaz-Tendero S, Obaid R, Disla M R, Xiong H, Sundberg M, Khosravi S D, Davino M, Drach P, Carroll A M, Osipov T, Martín F, Berrah N
Department of Physics, University of Connecticut, Storrs, CT, 06269, USA.
Departamento de Química, Módulo 13, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
Nat Commun. 2019 Jun 27;10(1):2813. doi: 10.1038/s41467-019-10571-9.
Being the lightest, most mobile atom that exists, hydrogen plays an important role in the chemistry of hydrocarbons, proteins and peptides and most biomolecules. Hydrogen can undergo transfer, exchange and migration processes, having considerable impact on the chemical behavior of these molecules. Although much has been learned about reaction dynamics involving one hydrogen atom, less is known about those processes where two or more hydrogen atoms participate. Here we show that single and double hydrogen migrations occurring in ethanol cations and dications take place within a few hundred fs to ps, using a 3D imaging and laser pump-probe technique. For double hydrogen migration, the hydrogens are not correlated, with the second hydrogen migration promoting the breakup of the C-O bond. The probability of double hydrogen migration is quite significant, suggesting that double hydrogen migration plays a more important role than generally assumed. The conclusions are supported by state-of-the-art molecular dynamics calculations.
作为现存最轻、最易移动的原子，氢在碳氢化合物、蛋白质、肽以及大多数生物分子的化学过程中发挥着重要作用。氢能够经历转移、交换和迁移过程，对这些分子的化学行为产生重大影响。尽管人们已经对涉及单个氢原子的反应动力学有了很多了解，但对于两个或更多氢原子参与的过程却知之甚少。在这里，我们使用三维成像和激光泵浦 - 探测技术表明，乙醇阳离子和二价阳离子中发生的单氢和双氢迁移在几百飞秒到皮秒的时间内完成。对于双氢迁移，两个氢原子不相关，第二个氢原子的迁移促进了C - O键的断裂。双氢迁移的概率相当可观，这表明双氢迁移所起的作用比通常认为的更为重要。这些结论得到了最先进的分子动力学计算的支持。
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