Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode

Roberto Alonso-Mori, Jan Kern, Richard J. Gildea, Dimosthenis Sokaras, Tsu Chien Weng, Benedikt Lassalle-Kaiser, Rosalie Tran, Johan Hattne, Hartawan Laksmono, Julia Hellmich, Carina Glöckner, Nathaniel Echols, Raymond G. Sierra, Donald W. Schafer, Jonas Sellberg, Christopher Kenney, Ryan Herbst, Jack Pines, Philip Hart, Sven HerrmannRalf W. Grosse-Kunstleve, Matthew J. Latimer, Alan R. Fry, Marc M. Messerschmidt, Alan Miahnahri, M. Marvin Seibert, Petrus H. Zwart, William E. White, Paul D. Adams, Michael J. Bogan, Sébastien Boutet, Garth J. Williams, Athina Zouni, Johannes Messinger, Pieter Glatzel, Nicholas K. Sauter, Vittal K. Yachandra, Junko Yano, Uwe Bergmann

Research output: Contribution to journalArticle

80 Scopus citations

Abstract

The ultrabright femtosecond X-ray pulses provided by X-ray free-electron lasers open capabilities for studying the structure and dynamics of a wide variety of systems beyond what is possible with synchrotron sources. Recently, this "probe-before-destroy"approach has been demonstrated for atomic structure determination by serial X-ray diffraction of microcrystals. There has been the question whether a similar approach can be extended to probe the local electronic structure by X-ray spectroscopy. To address this, we have carried out femtosecond X-ray emission spectroscopy (XES) at the Linac Coherent Light Source using redox-active Mn complexes. XES probes the charge and spin states as well as the ligand environment, critical for understanding the functional role of redox-active metal sites. Kβ1,3 XES spectra of Mn II and Mn2III,IVcomplexes at room temperature were collected using a wavelength dispersive spectrometer and femtosecond X-ray pulses with an individual dose of up to >100 MGy. The spectra were found in agreement with undamaged spectra collected at low dose using synchrotron radiation. Our results demonstrate that the intact electronic structure of redox active transition metal compounds in different oxidation states can be characterized with this shotby-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites by following reactions under functional conditions. The technique can be combined with X-ray diffraction to simultaneously obtain the geometric structure of the overall protein and the local chemistry of active metal sites and is expected to prove valuable for understanding the mechanism of important metalloproteins, such as photosystem II.

Original languageEnglish (US)
Pages (from-to)19103-19107
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume109
Issue number47
DOIs
StatePublished - Nov 20 2012

Keywords

  • Energy-dispersive XES
  • Femtosecond x-ray spectroscopy
  • Kβ emission lines

ASJC Scopus subject areas

  • General

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    Alonso-Mori, R., Kern, J., Gildea, R. J., Sokaras, D., Weng, T. C., Lassalle-Kaiser, B., Tran, R., Hattne, J., Laksmono, H., Hellmich, J., Glöckner, C., Echols, N., Sierra, R. G., Schafer, D. W., Sellberg, J., Kenney, C., Herbst, R., Pines, J., Hart, P., ... Bergmann, U. (2012). Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode. Proceedings of the National Academy of Sciences of the United States of America, 109(47), 19103-19107. https://doi.org/10.1073/pnas.1211384109