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

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 MnII and Mn2III,IV complexes 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 shot-by-shot method. This opens the door for studying the chemical dynamics of metal catalytic sites bymore » following reactions under functional conditions. Furthermore, 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.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [1] ;  [3] ;  [3] ;  [3] ;  [1] ;  [4] ;  [4] ;  [3] ;  [1] ;  [1] ;  [5] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] more »;  [3] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [3] ;  [1] ;  [3] ;  [6] ;  [1] ;  [1] ;  [4] ;  [7] ;  [8] ;  [3] ;  [3] ;  [3] ;  [1] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Technische Univ. Berlin (Germany)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stockholm Univ., Stockholm (Sweden)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technische Univ. Berlin (Germany)
  7. Umea Univ., Umea (Sweden)
  8. European Synchrotron Radiation Facility, Grenoble Cedex (France)
Publication Date:
OSTI Identifier:
1132324
Report Number(s):
SLAC-REPRINT-2014-130
Journal ID: ISSN 0027-8424
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 109; Journal Issue: 47; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; energy-dispersive XES; Kβ emission lines; femtosecond x-ray spectroscopy