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 (K alpha and K beta) 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.
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March, A. M., Assefa, T. A., Bressler, C., Doumy, G., Galler, A., Gawelda, W., Kanter, E. P., Nemeth, Z., Pápai, M. I.
, Southworth, S. H., Young, L., & Vanko, G. (2015). Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species
. Journal of Physical Chemistry C
(26), 14571-14578. https://doi.org/10.1021/jp511838q