---
_id: '40986'
abstract:
- lang: eng
  text: Currently, chemistry and physics are strongly dependent on the concept of
    the oxidation state. While the formal oxidation state is easily evaluated, the
    real physical oxidation state value is often difficult to determine and significantly
    varies from the formal values. Determination of the ionization threshold in X-ray
    absorption spectroscopy (XANES) relies on the absorption edge position and sometimes
    poses limitations, mainly due to the edge resonances. Moreover, the lower energy
    states can be probed only within x-soft or XUV photons providing only surface
    state information of probed materials. Here, we employ high energy resolution
    off-resonant spectroscopy to determine both 1s and 3p binding energies of Fe-based
    materials and therefore correlate to their physical oxidation state. The results
    are compared to the ones obtained with classical X-ray absorption, X-ray emission,
    and photoelectron spectroscopies. The observed differences in binding energies
    are discussed in a frame of initial and final state interactions with the atom's
    electronic configurations. The presented methodology is discussed towards potential
    use to single-shot experiments and application at X-ray free-electron lasers.
    Alternatively, core level X-ray emission spectroscopy can be used, but the emission
    line positions are strongly affected by spin-orbit interaction. However, due to
    the energy transfer from the photon to the excited core electron, the same information
    as in XANES is probed in high energy resolution off-resonant spectroscopy (HEROS).
    Based on the Kramers–Heisenberg theory, we propose a new approach for ionization
    threshold determination which is free of the limitations encountered in XANES-based
    determination of the core state energy. Namely, the value of core state energy
    can be determined analytically using a few HEROS spectra recorded with significantly
    higher spectral resolution. This approach provides a basis for the universal physical
    oxidation state determination method.
author:
- first_name: Michał
  full_name: Nowakowski, Michał
  id: '78878'
  last_name: Nowakowski
  orcid: 0000-0002-3734-7011
- first_name: Aleksandr
  full_name: Kalinko, Aleksandr
  last_name: Kalinko
- first_name: Jakub
  full_name: Szlachetko, Jakub
  last_name: Szlachetko
- first_name: Rafał
  full_name: Fanselow, Rafał
  last_name: Fanselow
- first_name: Matthias
  full_name: Bauer, Matthias
  id: '47241'
  last_name: Bauer
  orcid: 0000-0002-9294-6076
citation:
  ama: Nowakowski M, Kalinko A, Szlachetko J, Fanselow R, Bauer M. High resolution
    off resonant spectroscopy as a probe of the oxidation state. <i>Journal of Analytical
    Atomic Spectrometry</i>. 2022;37(11):2383-2391. doi:<a href="https://doi.org/10.1039/d2ja00232a">10.1039/d2ja00232a</a>
  apa: Nowakowski, M., Kalinko, A., Szlachetko, J., Fanselow, R., &#38; Bauer, M.
    (2022). High resolution off resonant spectroscopy as a probe of the oxidation
    state. <i>Journal of Analytical Atomic Spectrometry</i>, <i>37</i>(11), 2383–2391.
    <a href="https://doi.org/10.1039/d2ja00232a">https://doi.org/10.1039/d2ja00232a</a>
  bibtex: '@article{Nowakowski_Kalinko_Szlachetko_Fanselow_Bauer_2022, title={High
    resolution off resonant spectroscopy as a probe of the oxidation state}, volume={37},
    DOI={<a href="https://doi.org/10.1039/d2ja00232a">10.1039/d2ja00232a</a>}, number={11},
    journal={Journal of Analytical Atomic Spectrometry}, publisher={Royal Society
    of Chemistry (RSC)}, author={Nowakowski, Michał and Kalinko, Aleksandr and Szlachetko,
    Jakub and Fanselow, Rafał and Bauer, Matthias}, year={2022}, pages={2383–2391}
    }'
  chicago: 'Nowakowski, Michał, Aleksandr Kalinko, Jakub Szlachetko, Rafał Fanselow,
    and Matthias Bauer. “High Resolution off Resonant Spectroscopy as a Probe of the
    Oxidation State.” <i>Journal of Analytical Atomic Spectrometry</i> 37, no. 11
    (2022): 2383–91. <a href="https://doi.org/10.1039/d2ja00232a">https://doi.org/10.1039/d2ja00232a</a>.'
  ieee: 'M. Nowakowski, A. Kalinko, J. Szlachetko, R. Fanselow, and M. Bauer, “High
    resolution off resonant spectroscopy as a probe of the oxidation state,” <i>Journal
    of Analytical Atomic Spectrometry</i>, vol. 37, no. 11, pp. 2383–2391, 2022, doi:
    <a href="https://doi.org/10.1039/d2ja00232a">10.1039/d2ja00232a</a>.'
  mla: Nowakowski, Michał, et al. “High Resolution off Resonant Spectroscopy as a
    Probe of the Oxidation State.” <i>Journal of Analytical Atomic Spectrometry</i>,
    vol. 37, no. 11, Royal Society of Chemistry (RSC), 2022, pp. 2383–91, doi:<a href="https://doi.org/10.1039/d2ja00232a">10.1039/d2ja00232a</a>.
  short: M. Nowakowski, A. Kalinko, J. Szlachetko, R. Fanselow, M. Bauer, Journal
    of Analytical Atomic Spectrometry 37 (2022) 2383–2391.
date_created: 2023-01-30T16:24:06Z
date_updated: 2024-05-07T11:43:54Z
department:
- _id: '35'
- _id: '306'
doi: 10.1039/d2ja00232a
intvolume: '        37'
issue: '11'
keyword:
- Spectroscopy
- Analytical Chemistry
language:
- iso: eng
page: 2383-2391
publication: Journal of Analytical Atomic Spectrometry
publication_identifier:
  issn:
  - 0267-9477
  - 1364-5544
publication_status: published
publisher: Royal Society of Chemistry (RSC)
status: public
title: High resolution off resonant spectroscopy as a probe of the oxidation state
type: journal_article
user_id: '48467'
volume: 37
year: '2022'
...