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Radiation damage by extensive local water ionization from two-step electron-transfer-mediated decay of solvated ions

Gopakumar, G. ; Unger, I. ; Slavíček, P. ; Hergenhahn, U. ; Öhrwall, G. LU orcid ; Malerz, S. ; Céolin, D. ; Trinter, F. ; Winter, B. and Wilkinson, I. , et al. (2023) In Nature Chemistry 15(10). p.1408-1414
Abstract

Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger–Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al3+ ions, electronic relaxation involves two sequential solute–solvent electron transfer-mediated decay processes. The electron... (More)

Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger–Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al3+ ions, electronic relaxation involves two sequential solute–solvent electron transfer-mediated decay processes. The electron transfer-mediated decay steps correspond to sequential relaxation from Al5+ to Al3+ accompanied by formation of four ionized water molecules and two low-energy electrons. Such charge multiplication and the generated highly reactive species are expected to initiate cascades of radical reactions. [Figure not available: see fulltext.]

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Contribution to journal
publication status
published
subject
in
Nature Chemistry
volume
15
issue
10
pages
7 pages
publisher
Nature Publishing Group
external identifiers
  • pmid:37620544
  • scopus:85168658740
ISSN
1755-4330
DOI
10.1038/s41557-023-01302-1
language
English
LU publication?
yes
id
42be80c8-2528-4714-9709-32fd3584b053
date added to LUP
2023-12-22 15:13:41
date last changed
2024-04-21 00:28:56
@article{42be80c8-2528-4714-9709-32fd3584b053,
  abstract     = {{<p>Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger–Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al<sup>3+</sup> ions, electronic relaxation involves two sequential solute–solvent electron transfer-mediated decay processes. The electron transfer-mediated decay steps correspond to sequential relaxation from Al<sup>5+</sup> to Al<sup>3+</sup> accompanied by formation of four ionized water molecules and two low-energy electrons. Such charge multiplication and the generated highly reactive species are expected to initiate cascades of radical reactions. [Figure not available: see fulltext.]</p>}},
  author       = {{Gopakumar, G. and Unger, I. and Slavíček, P. and Hergenhahn, U. and Öhrwall, G. and Malerz, S. and Céolin, D. and Trinter, F. and Winter, B. and Wilkinson, I. and Caleman, C. and Muchová, E. and Björneholm, O.}},
  issn         = {{1755-4330}},
  language     = {{eng}},
  number       = {{10}},
  pages        = {{1408--1414}},
  publisher    = {{Nature Publishing Group}},
  series       = {{Nature Chemistry}},
  title        = {{Radiation damage by extensive local water ionization from two-step electron-transfer-mediated decay of solvated ions}},
  url          = {{http://dx.doi.org/10.1038/s41557-023-01302-1}},
  doi          = {{10.1038/s41557-023-01302-1}},
  volume       = {{15}},
  year         = {{2023}},
}