Jia Dongming, Manz Jörn, Yang Yonggang
State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy , Shanxi University , Taiyuan 030006 , China.
International Center for Chemical Theory , University of Science and Technology of China , Hefei 230026 , China.
J Phys Chem Lett. 2019 Aug 1;10(15):4273-4277. doi: 10.1021/acs.jpclett.9b01687. Epub 2019 Jul 17.
During charge migration, electrons flow rapidly from one site of a molecule to another, perhaps inducing subsequent processes (e.g., selective breaking of chemical bonds). The first joint experimental and theoretical preparation and measurement of the initial state and subsequent quantum dynamics simulation of charge migration for fixed nuclei was demonstrated recently for oriented, ionized iodoacetylene. Here, we present new quantum dynamics simulations for the same system with moving nuclei. They reveal the decisive role of the nuclei, i.e. they switch charge migration off (decoherence) and on (recoherence). This is a new finding in attosecond-to-femtosecond chemistry and physics which opens new prospects for laser control over electronic dynamics via nuclear motions.
在电荷迁移过程中，电子会迅速从分子的一个位点流向另一个位点，这可能会引发后续过程（例如，化学键的选择性断裂）。最近，针对取向的、电离的碘代乙炔，首次实现了固定原子核电荷迁移初始态的联合实验与理论制备及测量，以及后续的量子动力学模拟。在此，我们展示了针对同一系统、原子核运动情况下的新量子动力学模拟。这些模拟揭示了原子核的决定性作用，即它们会开启（再相干）和关闭（退相干）电荷迁移。这是阿秒到飞秒化学与物理领域的一项新发现，为通过核运动对电子动力学进行激光控制开辟了新前景。
