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Fingerprint of Dipole Moment Orientation of Water Molecules in Cu2+ Aqueous Solution Probed by X-ray Photoelectron Spectroscopy

Mosaferi, Mohammadreza ; Céolin, Denis LU ; Rueff, Jean Pascal ; Selles, Patricia ; Odelius, Michael ; Björneholm, Olle LU ; Öhrwall, Gunnar LU orcid and Carniato, Stéphane (2023) In Journal of the American Chemical Society
Abstract

The electronic structure and geometrical organization of aqueous Cu2+ have been investigated by using X-ray photoelectron spectroscopy (XPS) at the Cu L-edge combined with state-of-the-art ab initio molecular dynamics and a quantum molecular approach designed to simulate the Cu 2p X-ray photoelectron spectrum. The calculations offer a comprehensive insight into the origin of the main peak and satellite features. It is illustrated how the energy drop of the Cu 3d levels (≈7 eV) following the creation of the Cu 2p core hole switches the nature of the highest singly occupied molecular orbitals (MOs) from the dominant metal to the dominant MO nature of water. It is particularly revealed how the repositioning of the Cu 3d levels... (More)

The electronic structure and geometrical organization of aqueous Cu2+ have been investigated by using X-ray photoelectron spectroscopy (XPS) at the Cu L-edge combined with state-of-the-art ab initio molecular dynamics and a quantum molecular approach designed to simulate the Cu 2p X-ray photoelectron spectrum. The calculations offer a comprehensive insight into the origin of the main peak and satellite features. It is illustrated how the energy drop of the Cu 3d levels (≈7 eV) following the creation of the Cu 2p core hole switches the nature of the highest singly occupied molecular orbitals (MOs) from the dominant metal to the dominant MO nature of water. It is particularly revealed how the repositioning of the Cu 3d levels induces the formation of new bonding (B) and antibonding (AB) orbitals, from which shakeup mechanisms toward the relaxed H-SOMO operate. As highlighted in this study, the appearance of the shoulder near the main peak corresponds to the characteristic signature of shakeup intraligand (1a1 → H-SOMO(1b1)) excitations in water, providing insights into the average dipole moment distribution (≈36°) of the first-shell water molecules surrounding the metal ion and its direct impact on the broadening of the satellite. It is also revealed that the main satellite at 8 eV from the main peak corresponds to (metal/1b2 → H-SOMO(1b1) of water) excitations due to a bonding/antibonding (B/AB) interaction of Cu 3d levels with the deepest valence O2p/H1s 1b2 orbitals of water. This finding underscores the sensitivity of XPS to the electronic structure and orientation of the nearest water molecules around the central ion.

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organization
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Contribution to journal
publication status
epub
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in
Journal of the American Chemical Society
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85189001892
  • pmid:38545903
ISSN
0002-7863
DOI
10.1021/jacs.3c14570
language
English
LU publication?
yes
id
d9311e24-3bd0-4f1f-960c-70919c248f59
date added to LUP
2024-04-11 12:17:23
date last changed
2024-06-20 20:22:14
@article{d9311e24-3bd0-4f1f-960c-70919c248f59,
  abstract     = {{<p>The electronic structure and geometrical organization of aqueous Cu<sup>2+</sup> have been investigated by using X-ray photoelectron spectroscopy (XPS) at the Cu L-edge combined with state-of-the-art ab initio molecular dynamics and a quantum molecular approach designed to simulate the Cu 2p X-ray photoelectron spectrum. The calculations offer a comprehensive insight into the origin of the main peak and satellite features. It is illustrated how the energy drop of the Cu 3d levels (≈7 eV) following the creation of the Cu 2p core hole switches the nature of the highest singly occupied molecular orbitals (MOs) from the dominant metal to the dominant MO nature of water. It is particularly revealed how the repositioning of the Cu 3d levels induces the formation of new bonding (B) and antibonding (AB) orbitals, from which shakeup mechanisms toward the relaxed H-SOMO operate. As highlighted in this study, the appearance of the shoulder near the main peak corresponds to the characteristic signature of shakeup intraligand (1a<sub>1</sub> → H-SOMO(1b<sub>1</sub>)) excitations in water, providing insights into the average dipole moment distribution (≈36°) of the first-shell water molecules surrounding the metal ion and its direct impact on the broadening of the satellite. It is also revealed that the main satellite at 8 eV from the main peak corresponds to (metal/1b<sub>2</sub> → H-SOMO(1b<sub>1</sub>) of water) excitations due to a bonding/antibonding (B/AB) interaction of Cu 3d levels with the deepest valence O2p/H1s 1b<sub>2</sub> orbitals of water. This finding underscores the sensitivity of XPS to the electronic structure and orientation of the nearest water molecules around the central ion.</p>}},
  author       = {{Mosaferi, Mohammadreza and Céolin, Denis and Rueff, Jean Pascal and Selles, Patricia and Odelius, Michael and Björneholm, Olle and Öhrwall, Gunnar and Carniato, Stéphane}},
  issn         = {{0002-7863}},
  language     = {{eng}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of the American Chemical Society}},
  title        = {{Fingerprint of Dipole Moment Orientation of Water Molecules in Cu<sup>2+</sup> Aqueous Solution Probed by X-ray Photoelectron Spectroscopy}},
  url          = {{http://dx.doi.org/10.1021/jacs.3c14570}},
  doi          = {{10.1021/jacs.3c14570}},
  year         = {{2023}},
}