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Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique

Muchová, E. ; Gopakumar, G. ; Unger, I. ; Öhrwall, G. LU orcid ; Céolin, D. LU ; Trinter, F. ; Wilkinson, I. ; Chatzigeorgiou, E. ; Slavíček, P. and Hergenhahn, U. , et al. (2024) In Nature Communications 15(1).
Abstract

Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na+, Mg2+, and Al3+ ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger–Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of... (More)

Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na+, Mg2+, and Al3+ ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger–Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of hydrated electrons, which are determined to take place on a timescale ranging from several hundred attoseconds (as) below the 1s ionization threshold to only 20 as far above the 1s ionization threshold. The decrease in the delocalization times as a function of the photon energy is continuous. This indicates that the excited electrons remain in the vicinity of the studied ions even above the ionization threshold, i.e., metal-ion electronic resonances associated with the CTTS state manifolds are formed. The three studied isoelectronic ions exhibit quantitative differences in their electron energetics and delocalization times, which are linked to the character of the respective excited states.

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type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
15
issue
1
article number
8903
publisher
Nature Publishing Group
external identifiers
  • pmid:39406706
  • scopus:85206466547
ISSN
2041-1723
DOI
10.1038/s41467-024-52740-5
language
English
LU publication?
yes
id
4027e6d0-c6f6-4522-8075-df67e56397cd
date added to LUP
2024-11-27 10:58:56
date last changed
2025-07-10 05:42:19
@article{4027e6d0-c6f6-4522-8075-df67e56397cd,
  abstract     = {{<p>Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na<sup>+</sup>, Mg<sup>2+</sup>, and Al<sup>3+</sup> ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed. Using the core-hole-clock method, based on Auger–Meitner (AM) decay upon 1s excitation or ionization of the respective ions, upper limits are estimated for the metal-atom electron delocalization times to the neighboring water molecules. These delocalization processes represent the first steps in the formation of hydrated electrons, which are determined to take place on a timescale ranging from several hundred attoseconds (as) below the 1s ionization threshold to only 20 as far above the 1s ionization threshold. The decrease in the delocalization times as a function of the photon energy is continuous. This indicates that the excited electrons remain in the vicinity of the studied ions even above the ionization threshold, i.e., metal-ion electronic resonances associated with the CTTS state manifolds are formed. The three studied isoelectronic ions exhibit quantitative differences in their electron energetics and delocalization times, which are linked to the character of the respective excited states.</p>}},
  author       = {{Muchová, E. and Gopakumar, G. and Unger, I. and Öhrwall, G. and Céolin, D. and Trinter, F. and Wilkinson, I. and Chatzigeorgiou, E. and Slavíček, P. and Hergenhahn, U. and Winter, B. and Caleman, C. and Björneholm, O.}},
  issn         = {{2041-1723}},
  language     = {{eng}},
  number       = {{1}},
  publisher    = {{Nature Publishing Group}},
  series       = {{Nature Communications}},
  title        = {{Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique}},
  url          = {{http://dx.doi.org/10.1038/s41467-024-52740-5}},
  doi          = {{10.1038/s41467-024-52740-5}},
  volume       = {{15}},
  year         = {{2024}},
}