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Breakdown of the molecular orbital picture for X-ray emission of water

Cornetta, Lucas M. ; Carravetta, Vincenzo ; Tokushima, Takashi LU orcid ; Horikawa, Yuka ; Rubensson, Jan Erik ; Nordgren, Joseph and Ågren, Hans (2024) In Chemical Physics Letters 855.
Abstract

By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a1 peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a1 derived band.

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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
MO-breakdown, Water, X-ray emission
in
Chemical Physics Letters
volume
855
article number
141583
publisher
Elsevier
external identifiers
  • scopus:85202870246
ISSN
0009-2614
DOI
10.1016/j.cplett.2024.141583
language
English
LU publication?
yes
id
54d992aa-83e3-486f-8ca2-286a6197ce49
date added to LUP
2024-11-12 17:45:33
date last changed
2025-05-14 07:43:54
@article{54d992aa-83e3-486f-8ca2-286a6197ce49,
  abstract     = {{<p>By measuring X-ray emission of the water molecule in liquid phase we establish a first example of K-shell X-ray emission spectra with strong breakdown of the molecular orbital picture. A complete splitting of the 2a<sub>1</sub> peak into satellites is observed. A theoretical model with electronic configurations generated by coupled excitations/de-excitations, so-called semi-internal configuration interaction, captures the experimentally recorded features well. Differences with respect to the corresponding breakdown effect in ultraviolet photoelectron spectrum are highlighted. Molecular dynamics calculations indicate that solvent broadening can only make up for a small fraction of the width of the recorded 2a<sub>1</sub> derived band.</p>}},
  author       = {{Cornetta, Lucas M. and Carravetta, Vincenzo and Tokushima, Takashi and Horikawa, Yuka and Rubensson, Jan Erik and Nordgren, Joseph and Ågren, Hans}},
  issn         = {{0009-2614}},
  keywords     = {{MO-breakdown; Water; X-ray emission}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Chemical Physics Letters}},
  title        = {{Breakdown of the molecular orbital picture for X-ray emission of water}},
  url          = {{http://dx.doi.org/10.1016/j.cplett.2024.141583}},
  doi          = {{10.1016/j.cplett.2024.141583}},
  volume       = {{855}},
  year         = {{2024}},
}