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PreprintCC BYChemRxiv

Valence Delocalization in Trithorium Clusters Identified via Valence-to-Core Resonant Inelastic X-ray Scattering

  • Charles P. Moir1,2,3,4
  • Josef Tomeček1,2,4
  • Nathan M. Alcock1,2,3,4
  • John A. Seed1,2,4
  • Xinglan Deng1,2,4
  • Zhibo Qi1,2,3,4,5
  • Myron S. Huzan1,2,3,4
  • Shusaku Hayama5
  • Stephen T. Liddle1,2,4
  • Nikolas Kaltsoyannis1,2,4
  • Michael L. Baker1,2,3,4
5 affiliations
  1. 1Department of Chemistry
  2. 2University of Manchester
  3. 3University of Manchester at Harwell
  4. 4Centre for Radiochemistry Research, University of Manchester, Oxford Road, Manchester, UK, M13 9PL
  5. 5Harwell Science and Innovation Campus
Open at sourcePDFDOICite

Abstract

L 3 -edge valence-to-core resonant inelastic X-ray scattering (V2C-RIXS) is applied to thorium for the first time, demonstrating the technique’s sensitivity to actinide 6d-orbital participation in bonding. This sensitivity is exploited to identify states arising from delocalized valence molecular orbitals of predominantly 6d character in two trithorium clusters, [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 {K(DME) 2 } 2 ] 2b and [K(2.2.2-cryptand)] [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 ] 3 . Density functional theory based restricted open-shell configuration interaction with singles (DFT/ROCIS) accurately reproduces the V2C-RIXS spectra of 2b and 3 , enabling the quantitative assignment of inelastic intensity to the population of a delocalized three-center 6d z2 σ-bonding molecular orbital. In contrast, L 3 -edge high-energy-resolution fluorescence detection (HERFD) XANES spectra exhibit negligible sensitivity to 6d electron population in these compounds. This study, thus, establishes a clear distinction between the two techniques and identifies V2C-RIXS as a unique probe of 6d orbital contributions to bonding in actinide compounds.

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Cite

BibTeXRIS
BibTeX
@misc{moir2026valence,
  title = {{Valence Delocalization in Trithorium Clusters Identified via Valence-to-Core Resonant Inelastic X-ray Scattering}},
  author = {Charles P. Moir and Josef Tomeček and Nathan M. Alcock and John A. Seed and Xinglan Deng and Zhibo Qi and Myron S. Huzan and Shusaku Hayama and Stephen T. Liddle and Nikolas Kaltsoyannis and Michael L. Baker},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008222/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008222/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Valence Delocalization in Trithorium Clusters Identified via Valence-to-Core Resonant Inelastic X-ray Scattering
AU  - Charles P. Moir
AU  - Josef Tomeček
AU  - Nathan M. Alcock
AU  - John A. Seed
AU  - Xinglan Deng
AU  - Zhibo Qi
AU  - Myron S. Huzan
AU  - Shusaku Hayama
AU  - Stephen T. Liddle
AU  - Nikolas Kaltsoyannis
AU  - Michael L. Baker
PY  - 2026
DA  - 2026/09/02
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008222/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008222/v1
AB  - L 3 -edge valence-to-core resonant inelastic X-ray scattering (V2C-RIXS) is applied to thorium for the first time, demonstrating the technique’s sensitivity to actinide 6d-orbital participation in bonding. This sensitivity is exploited to identify states arising from delocalized valence molecular orbitals of predominantly 6d character in two trithorium clusters, [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 {K(DME) 2 } 2 ] 2b and [K(2.2.2-cryptand)] [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 ] 3 . Density functional theory based restricted open-shell configuration interaction with singles (DFT/ROCIS) accurately reproduces the V2C-RIXS spectra of 2b and 3 , enabling the quantitative assignment of inelastic intensity to the population of a delocalized three-center 6d z2 σ-bonding molecular orbital. In contrast, L 3 -edge high-energy-resolution fluorescence detection (HERFD) XANES spectra exhibit negligible sensitivity to 6d electron population in these compounds. This study, thus, establishes a clear distinction between the two techniques and identifies V2C-RIXS as a unique probe of 6d orbital contributions to bonding in actinide compounds.
ER  -