Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom
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DOI：
10.1103/physreva.97.043429
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发表时间：
2018-04-27
影响因子：
2.9
通讯作者：
Rolles, Daniel
中科院分区：
文献类型：
--
作者：
Brasse, Felix;Goldsztejn, Gildas;Rolles, Daniel
内壳光电子能谱由于其元素和位点的特异性，是一种广泛应用于探测物质化学结构的技术。本研究表明，时间分辨内壳光电子能谱可以高灵敏度地观察超快化学反应和核运动的电子响应。利用时间分辨内壳光电子和光离子能谱研究了碘甲烷（CH3I）在碘四维边以上电离的紫外解离。在光电子能谱中观察到的动力学比在碘碎片中观察到的动力学出现得更早、更快。利用晶体场和自旋轨道组态相互作用计算对实验结果进行了解释，并证明了时间分辨内壳光电子能谱是直接跟踪气相分子超快结构和电子转变的有力工具。
Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.