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Peer-reviewedCC BYInorganic chemistry

Disentangling Electronic Interactions in f7 Systems: A Comparative Study on GdIII, TbIV, CmIII, and BkIV.

  • Chad M Studvick1
  • Ivan A Popov2
  • Cristian Celis-Barros3
  1. 1Department of Chemistry, University of Akron, Akron, Ohio44325-3601, United States.
  2. 2Department of Chemistry, Washington State University, Pullman, Washington99164, United States.
  3. 3Radioisotope Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee37830, United States.
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Abstract

In this work, we demonstrate through computational spectroscopic analysis of four experimentally accessible f7 ions within complexes (GdIII, TbIV, CmIII, and BkIV) the extent to which electron-electron repulsion, spin-orbit coupling, and the identity of the ligand field influence the energy and intermediate coupling of an f7 ion's low-lying excited states. As expected, the energy of excited states is primarily governed by electron-electron repulsion in the lanthanides (GdIII and TbIV), whereas spin-orbit coupling and ligand field effects play an increasingly important role in the actinides (CmIII and BkIV). Additionally, the stabilization caused by a ligand field is significantly greater for ions in higher oxidation states, as evidenced by the decreased energy of the emissive state and the nephelauxetic reduction. Finally, mixing Russell-Saunders terms in an intermediate coupling scheme is shown to be more significant in actinides and at higher oxidation states, with TbIV exhibiting signs of behaving spectroscopically like an actinide. These results reveal a clear correlation between composition, excited-state energy, and covalency, which supports a direct correlation between f-orbital covalency and the f-f multiplet structure. Furthermore, these findings contribute to spectroscopic studies on high-valent f-element complexes.

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Cite

BibTeXRIS
BibTeX
@article{studvick2026disentangling,
  title = {{Disentangling Electronic Interactions in f7 Systems: A Comparative Study on GdIII, TbIV, CmIII, and BkIV.}},
  author = {Chad M Studvick and Ivan A Popov and Cristian Celis-Barros},
  journal = {Inorganic chemistry},
  year = {2026},
  month = sep,
  doi = {10.1021/acs.inorgchem.6c02332},
  url = {https://europepmc.org/article/MED/42916488},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Disentangling Electronic Interactions in f7 Systems: A Comparative Study on GdIII, TbIV, CmIII, and BkIV.
AU  - Chad M Studvick
AU  - Ivan A Popov
AU  - Cristian Celis-Barros
PY  - 2026
DA  - 2026/09/01
JO  - Inorganic chemistry
DO  - 10.1021/acs.inorgchem.6c02332
UR  - https://europepmc.org/article/MED/42916488
AB  - In this work, we demonstrate through computational spectroscopic analysis of four experimentally accessible f7 ions within complexes (GdIII, TbIV, CmIII, and BkIV) the extent to which electron-electron repulsion, spin-orbit coupling, and the identity of the ligand field influence the energy and intermediate coupling of an f7 ion's low-lying excited states. As expected, the energy of excited states is primarily governed by electron-electron repulsion in the lanthanides (GdIII and TbIV), whereas spin-orbit coupling and ligand field effects play an increasingly important role in the actinides (CmIII and BkIV). Additionally, the stabilization caused by a ligand field is significantly greater for ions in higher oxidation states, as evidenced by the decreased energy of the emissive state and the nephelauxetic reduction. Finally, mixing Russell-Saunders terms in an intermediate coupling scheme is shown to be more significant in actinides and at higher oxidation states, with TbIV exhibiting signs of behaving spectroscopically like an actinide. These results reveal a clear correlation between composition, excited-state energy, and covalency, which supports a direct correlation between f-orbital covalency and the f-f multiplet structure. Furthermore, these findings contribute to spectroscopic studies on high-valent f-element complexes.
SN  - 0020-1669
SN  - 1520-510X
ER  -