Wang Zhenzhen, Hu Xiaoqing, Xue Xiaorui, Zhou Shengpeng, Li Xiaokai, Yang Yizhang, Zhou Jiaqi, Shu Zheng, Zhao Banchi, Yu Xitao, Gong Maomao, Wang Zhenpeng, Ma Pan, Wu Yong, Chen Xiangjun, Wang Jianguo, Ren Xueguang, Wang Chuncheng, Ding Dajun
Institute of Atomic and Molecular Physics and Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, 130012, Changchun, China.
Key Laboratory of Computational Physics, Institute of Applied Physics and Computational Mathematics, 100088, Beijing, China.
Nat Commun. 2023 Sep 5;14(1):5420. doi: 10.1038/s41467-023-41204-x.
Real-time imaging of transient structure of the electronic excited state is fundamentally critical to understand and control ultrafast molecular dynamics. The ejection of electrons from the inner-shell and valence level can lead to the population of different excited states, which trigger manifold ultrafast relaxation processes, however, the accurate imaging of such electronic state-dependent structural evolutions is still lacking. Here, by developing the laser-induced electron recollision-assisted Coulomb explosion imaging approach and molecular dynamics simulations, snapshots of the vibrational wave-packets of the excited (A) and ground states (X) of DO are captured simultaneously with sub-10 picometre and few-femtosecond precision. We visualise that θ and R are significantly increased by around 50 and 10 pm, respectively, within approximately 8 fs after initial ionisation for the A state, and the R further extends 9 pm within 2 fs along the ground state of the dication in the present condition. Moreover, the R can stretch more than 50 pm within 5 fs along autoionisation state of dication. The accuracies of the results are limited by the simulations. These results provide comprehensive structural information for studying the fascinating molecular dynamics of water, and pave the way towards to make a movie of excited state-resolved ultrafast molecular dynamics and light-induced chemical reaction.
对电子激发态的瞬态结构进行实时成像对于理解和控制超快分子动力学至关重要。内壳层和价层电子的 ejection 会导致不同激发态的占据，进而引发多种超快弛豫过程，然而，目前仍缺乏对这种依赖于电子态的结构演化的精确成像。在此，通过开发激光诱导电子再碰撞辅助库仑爆炸成像方法和分子动力学模拟，以亚 10 皮米和飞秒级的精度同时捕捉到了 DO 的激发态（A）和基态（X）的振动波包的快照。我们观察到，对于 A 态，在初始电离后的约 8 飞秒内，θ 和 R 分别显著增加了约 50 皮米和 10 皮米，并且在当前条件下，R 在沿着双离子基态的 2 飞秒内进一步扩展了 9 皮米。此外，R 在沿着双离子自电离态的 5 飞秒内可以伸展超过 50 皮米。结果的准确性受模拟限制。这些结果为研究水迷人的分子动力学提供了全面的结构信息，并为制作激发态分辨的超快分子动力学和光致化学反应的动态影像铺平了道路。 （注：“ejection”原词有误，可能是“ejection”，推测意为“射出”“弹出”等，这里暂按此翻译）
