March Anne Marie, Assefa Tadesse A, Bressler Christian, Doumy Gilles, Galler Andreas, Gawelda Wojciech, Kanter Elliot P, Németh Zoltán, Pápai Mátyás, Southworth Stephen H, Young Linda, Vankó György
X-ray Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
European XFEL , Albert-Einstein-Ring 19, 22761 Hamburg, Germany.
J Phys Chem C Nanomater Interfaces. 2015 Jul 2;119(26):14571-14578. doi: 10.1021/jp511838q. Epub 2015 Feb 9.
X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES for time-resolved experiments. We discuss technical improvements that will make valence-to-core XES a practical pump-probe technique.
当X射线光谱学与激光泵浦、X射线探测测量方案相结合时，它可以成为追踪光引发化学反应过程中发生的电子和几何结构变化的强大工具。X射线吸收光谱（XAS）被认为是用于此类测量的成熟技术，目前正在使用最强的芯到芯发射线（Kα和Kβ）的X射线发射光谱（XES）。通量要求高的价到芯XES有望成为时间分辨光谱工具包的重要补充。在本文中，我们展示了对激光激发的溶液相亚铁氰化物的测量和密度泛函理论计算，证明了价到芯XES用于时间分辨实验的可行性。我们讨论了将使价到芯XES成为实用泵浦探测技术的技术改进。
