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Title: Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species

Abstract

Here, we describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L3-edge RIXS in the ferricyanide complex Fe(CN)63-, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [6]; ORCiD logo [3]; ORCiD logo [7];  [4]; ORCiD logo [1]
  1. Department of Physics, AlbaNova University Center, Stockholm University, SE-106 91 Stockholm, Sweden
  2. Universität Potsdam, Institut für Physik und Astronomie, 14476 Potsdam, Germany
  3. Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Institute for Methods and Instrumentation for Synchrotron Radiation Research, 12489 Berlin, Germany
  4. Universität Potsdam, Institut für Physik und Astronomie, 14476 Potsdam, Germany, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH
  5. Department of Chemistry – Ångström Laboratory, Uppsala University, 75121 Uppsala, Sweden
  6. PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, USA
  7. Department of Chemistry – Ångström Laboratory, Uppsala University, 75121 Uppsala, Sweden, Department of Biotechnology
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1422840
Alternate Identifier(s):
OSTI ID: 1436985
Grant/Contract Number:  
AC02-76SF00515; 2015-03956; KAW- 2013.0020; VI 419; 669531
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics Journal Volume: 20 Journal Issue: 10; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Norell, Jesper, Jay, Raphael M., Hantschmann, Markus, Eckert, Sebastian, Guo, Meiyuan, Gaffney, Kelly J., Wernet, Philippe, Lundberg, Marcus, Föhlisch, Alexander, and Odelius, Michael. Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species. United Kingdom: N. p., 2018. Web. doi:10.1039/C7CP08326B.
Norell, Jesper, Jay, Raphael M., Hantschmann, Markus, Eckert, Sebastian, Guo, Meiyuan, Gaffney, Kelly J., Wernet, Philippe, Lundberg, Marcus, Föhlisch, Alexander, & Odelius, Michael. Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species. United Kingdom. doi:10.1039/C7CP08326B.
Norell, Jesper, Jay, Raphael M., Hantschmann, Markus, Eckert, Sebastian, Guo, Meiyuan, Gaffney, Kelly J., Wernet, Philippe, Lundberg, Marcus, Föhlisch, Alexander, and Odelius, Michael. Mon . "Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species". United Kingdom. doi:10.1039/C7CP08326B.
@article{osti_1422840,
title = {Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species},
author = {Norell, Jesper and Jay, Raphael M. and Hantschmann, Markus and Eckert, Sebastian and Guo, Meiyuan and Gaffney, Kelly J. and Wernet, Philippe and Lundberg, Marcus and Föhlisch, Alexander and Odelius, Michael},
abstractNote = {Here, we describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L3-edge RIXS in the ferricyanide complex Fe(CN)63-, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.},
doi = {10.1039/C7CP08326B},
journal = {Physical Chemistry Chemical Physics},
number = 10,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C7CP08326B

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