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Title: X-ray-induced sample damage at the Mn L-edge: a case study for soft X-ray spectroscopy of transition metal complexes in solution

X-ray induced sample damage can impede electronic and structural investigations of radiation-sensitive samples studied with X-rays. Here we quantify dose-dependent sample damage to the prototypical Mn III(acac) 3 complex in solution and at room temperature for the soft X-ray range, using X-ray absorption spectroscopy at the Mn L-edge. We observe the appearance of a reduced Mn II species as the X-ray dose is increased. We find a half-damage dose of 1.6 MGy and quantify a spectroscopically tolerable dose on the order of 0.3 MGy (1 Gy = 1 J kg -1), where 90% of Mn III(acac) 3 are intact. Our dose-limit is around one order of magnitude lower than the Henderson limit (half-damage dose of 20 MGy) which is commonly employed for protein crystallography with hard X-rays. It is comparable, however, to the dose-limits obtained for collecting un-damaged Mn K-edge spectra of the photosystem II protein, using hard X-rays. The dose-dependent reduction of Mn III observed here for solution samples occurs at a dose limit that is two to four orders of magnitude smaller than the dose limits previously reported for soft X-ray spectroscopy of iron samples in the solid phase. We compare our measured to calculated spectra from abmore » initio restricted active space (RAS) theory and discuss possible mechanisms for the observed dose-dependent damage of Mn III(acac) 3 in solution. Lastly, on the basis of our results, we assess the influence of sample damage in other experimental studies with soft X-rays from storage-ring synchrotron radiation sources and X-ray free-electron lasers.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [3] ;  [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Helmholtz-Zentrum Berlin (HZB), (Germany). Inst. for Methods and Instrumentation for Synchrotron Radiation Research
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
  3. Uppsala Univ. (Sweden). Ångström Lab., Dept. of Chemistry
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 24; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1476594

Kubin, Markus, Kern, Jan, Guo, Meiyuan, Källman, Erik, Mitzner, Rolf, Yachandra, Vittal K., Lundberg, Marcus, Yano, Junko, and Wernet, Philippe. X-ray-induced sample damage at the Mn L-edge: a case study for soft X-ray spectroscopy of transition metal complexes in solution. United States: N. p., Web. doi:10.1039/c8cp03094d.
Kubin, Markus, Kern, Jan, Guo, Meiyuan, Källman, Erik, Mitzner, Rolf, Yachandra, Vittal K., Lundberg, Marcus, Yano, Junko, & Wernet, Philippe. X-ray-induced sample damage at the Mn L-edge: a case study for soft X-ray spectroscopy of transition metal complexes in solution. United States. doi:10.1039/c8cp03094d.
Kubin, Markus, Kern, Jan, Guo, Meiyuan, Källman, Erik, Mitzner, Rolf, Yachandra, Vittal K., Lundberg, Marcus, Yano, Junko, and Wernet, Philippe. 2018. "X-ray-induced sample damage at the Mn L-edge: a case study for soft X-ray spectroscopy of transition metal complexes in solution". United States. doi:10.1039/c8cp03094d. https://www.osti.gov/servlets/purl/1476594.
@article{osti_1476594,
title = {X-ray-induced sample damage at the Mn L-edge: a case study for soft X-ray spectroscopy of transition metal complexes in solution},
author = {Kubin, Markus and Kern, Jan and Guo, Meiyuan and Källman, Erik and Mitzner, Rolf and Yachandra, Vittal K. and Lundberg, Marcus and Yano, Junko and Wernet, Philippe},
abstractNote = {X-ray induced sample damage can impede electronic and structural investigations of radiation-sensitive samples studied with X-rays. Here we quantify dose-dependent sample damage to the prototypical MnIII(acac)3 complex in solution and at room temperature for the soft X-ray range, using X-ray absorption spectroscopy at the Mn L-edge. We observe the appearance of a reduced MnII species as the X-ray dose is increased. We find a half-damage dose of 1.6 MGy and quantify a spectroscopically tolerable dose on the order of 0.3 MGy (1 Gy = 1 J kg-1), where 90% of MnIII(acac)3 are intact. Our dose-limit is around one order of magnitude lower than the Henderson limit (half-damage dose of 20 MGy) which is commonly employed for protein crystallography with hard X-rays. It is comparable, however, to the dose-limits obtained for collecting un-damaged Mn K-edge spectra of the photosystem II protein, using hard X-rays. The dose-dependent reduction of MnIII observed here for solution samples occurs at a dose limit that is two to four orders of magnitude smaller than the dose limits previously reported for soft X-ray spectroscopy of iron samples in the solid phase. We compare our measured to calculated spectra from ab initio restricted active space (RAS) theory and discuss possible mechanisms for the observed dose-dependent damage of MnIII(acac)3 in solution. Lastly, on the basis of our results, we assess the influence of sample damage in other experimental studies with soft X-rays from storage-ring synchrotron radiation sources and X-ray free-electron lasers.},
doi = {10.1039/c8cp03094d},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 24,
volume = 20,
place = {United States},
year = {2018},
month = {6}
}

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