Condensed-Matter Physics & Materials Science Seminar
"Tracking chemical reactions with time-resolved x-ray spectroscopic techniques"
Presented by Tadese Abebaw Assefa, European XFEL Laboratory, Germany
Monday, November 21, 2016, 1:30 pm — ISB Bldg. 734, Conf. Rm. 201 (upstairs)
Transition metal compounds play a significant role in many chemical and biologically relevant processes. Hereby charge transfer, ligand detachment and attachment processes are fundamental ingredients, which often determine the outcome of a given chemical reaction. We investigated aqueous ferrocyanide ([FeII(CN)6]4-) ions, which undergoes charge transfer and ultrafast ligand dissociation upon irradiation of 266 and 355 nm laser light. Time-resolved (TR) x-ray absorption and emission spectroscopies (XAS and XES) deliver information about structural and electronic changes in real-time implemented to follow the chemical reaction. Synchrotron-based studies are limited with 100ps time resolution enables us to disentangle simultaneous photoproducts formed after 266 nm laser excitation. Furthermore, we investigated the ultrafast ligand dissociation of aqueous ferrocyanide ions upon irradiation of 355 nm laser light at the x-ray Free Electron Laser facility (SACLA, Japan). Based on a comparison of the simulated pre-edge peaks of 1s→3d transition with the experimental data, we concluded that the reaction pathway commences via ligand detachment resulting pentacoordinated intermediate complex ([FeII(CN)5]3-), followed by the formation of the long-lived photoaquated complex ([FeII(CN)5(H2O)]3-). The ligand detachment and attachment process takes 12.43 ± 5.77 ps. TR XES results also reveal spin state change in the intermediate state. Combining these findings we interpret the consecutive steps of ligand exchange mechanism for ferrocyanide ions. Also, we characterise the molecular structure of photoexcited [FeII(terpy)2]2+ molecule via TR Extended X-ray absorption fine structure (EXAFS). The data analysis in energy space used two structural model expansions which are the representations of DFT predicted 5E and 5B2 quintet high spin states. After statistical evaluation of the two models, the 5E high spin state model is in better agreement with experimental data. The ener
Hosted by: Ian Robinson
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