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Title: Femtosecond response of polyatomic molecules to ultra-intense hard X-rays

Abstract

We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10 20 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, itmore » is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10 20 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.« less

Authors:
 [1];  [2];  [3];  [1];  [1];  [4];  [5];  [2];  [6];  [7];  [4];  [4];  [8];  [9];  [10];  [11];  [10];  [12];  [12];  [13] more »;  [14];  [15];  [16];  [14];  [14];  [14];  [17];  [18];  [14];  [19];  [20];  [2];  [21];  [22] « less
  1. Kansas State Univ., Manhattan, KS (United States). J. R. Macdonald Laboratory, Department of Physics
  2. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany)
  3. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); Tohoku University, Sendai (Japan). Department of Chemistry, Graduate School of Science
  4. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  5. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Max Planck Institute for Nuclear Physics, Heidelberg
  6. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); University of Science and Technology Beijing (China). Department of Physics
  7. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); Aarhus University (Denmark). Department of Physics and Astronomy
  8. Physikalisch-Technische Bundesanstalt (PTB), Braunschweig (Germany)
  9. Max Planck Institute for Medical Research, Heidelberg (Germany)
  10. Argonne National Lab. (ANL), Lemont, IL (United States)
  11. Argonne National Lab. (ANL), Lemont, IL (United States); Philipps-Universität Marburg, Marburg (Germany). Faculty of Chemistry
  12. Sorbonne Universites, UPMC Universite Paris 06, CNRS, LCP-MR (UMR 7614) (France)
  13. Tohoku University, Sendai (Japan). Institute of Multidisciplinary Research for Advanced Materials
  14. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  15. Argonne National Lab. (ANL), Lemont, IL (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
  16. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Institut fur Optik und Atomare Physik, Technische Universitat Berlin (Germany)
  17. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  18. SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  19. Argonne National Lab. (ANL), Lemont, IL (United States); Univ. of Chicago, IL (United States). Department of Physics
  20. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States). Department of Physics and Astronomy
  21. Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Hamburg (Germany); University of Hamburg (Germany). Department of Physics
  22. Kansas State Univ., Manhattan, KS (United States). J. R. Macdonald Laboratory, Department of Physics; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376141
Report Number(s):
BNL-114081-2017-JA
Journal ID: ISSN 0028-0836
Grant/Contract Number:  
SC0012704; FG02-86ER13491; AC02-06CH11357; AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Volume: 546; Journal Issue: 7656; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Rudenko, A., Inhester, L., Hanasaki, K., Li, X., Robatjazi, S. J., Erk, B., Boll, R., Toyota, K., Hao, Y., Vendrell, O., Bomme, C., Savelyev, E., Rudek, B., Foucar, L., Southworth, S. H., Lehmann, C. S., Kraessig, B., Marchenko, T., Simon, M., Ueda, K., Ferguson, K. R., Bucher, M., Gorkhover, T., Carron, S., Alonso-Mori, R., Koglin, J. E., Correa, J., Williams, G. J., Boutet, S., Young, L., Bostedt, C., Son, S. -K., Santra, R., and Rolles, D. Femtosecond response of polyatomic molecules to ultra-intense hard X-rays. United States: N. p., 2017. Web. doi:10.1038/nature22373.
Rudenko, A., Inhester, L., Hanasaki, K., Li, X., Robatjazi, S. J., Erk, B., Boll, R., Toyota, K., Hao, Y., Vendrell, O., Bomme, C., Savelyev, E., Rudek, B., Foucar, L., Southworth, S. H., Lehmann, C. S., Kraessig, B., Marchenko, T., Simon, M., Ueda, K., Ferguson, K. R., Bucher, M., Gorkhover, T., Carron, S., Alonso-Mori, R., Koglin, J. E., Correa, J., Williams, G. J., Boutet, S., Young, L., Bostedt, C., Son, S. -K., Santra, R., & Rolles, D. Femtosecond response of polyatomic molecules to ultra-intense hard X-rays. United States. doi:10.1038/nature22373.
Rudenko, A., Inhester, L., Hanasaki, K., Li, X., Robatjazi, S. J., Erk, B., Boll, R., Toyota, K., Hao, Y., Vendrell, O., Bomme, C., Savelyev, E., Rudek, B., Foucar, L., Southworth, S. H., Lehmann, C. S., Kraessig, B., Marchenko, T., Simon, M., Ueda, K., Ferguson, K. R., Bucher, M., Gorkhover, T., Carron, S., Alonso-Mori, R., Koglin, J. E., Correa, J., Williams, G. J., Boutet, S., Young, L., Bostedt, C., Son, S. -K., Santra, R., and Rolles, D. Wed . "Femtosecond response of polyatomic molecules to ultra-intense hard X-rays". United States. doi:10.1038/nature22373. https://www.osti.gov/servlets/purl/1376141.
@article{osti_1376141,
title = {Femtosecond response of polyatomic molecules to ultra-intense hard X-rays},
author = {Rudenko, A. and Inhester, L. and Hanasaki, K. and Li, X. and Robatjazi, S. J. and Erk, B. and Boll, R. and Toyota, K. and Hao, Y. and Vendrell, O. and Bomme, C. and Savelyev, E. and Rudek, B. and Foucar, L. and Southworth, S. H. and Lehmann, C. S. and Kraessig, B. and Marchenko, T. and Simon, M. and Ueda, K. and Ferguson, K. R. and Bucher, M. and Gorkhover, T. and Carron, S. and Alonso-Mori, R. and Koglin, J. E. and Correa, J. and Williams, G. J. and Boutet, S. and Young, L. and Bostedt, C. and Son, S. -K. and Santra, R. and Rolles, D.},
abstractNote = {We report x-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 1020 watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 1020 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Fnally, our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.},
doi = {10.1038/nature22373},
journal = {Nature (London)},
issn = {0028-0836},
number = 7656,
volume = 546,
place = {United States},
year = {2017},
month = {5}
}

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    Theoretical evidence for the sensitivity of charge-rearrangement-enhanced x-ray ionization to molecular size
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