4f-Orbital Occupancy in Tetravalent Cerium Halide Complexes from X-ray Spectroscopy and Theory
Bibliographic record
Abstract
Recent studies of lanthanide bonding have shown that small amounts of metal–ligand covalency can impact bond energies and cause magnetic behavior to deviate from the free ion values. Quantifying covalent bonding parameters is necessary to support the rational tuning of these properties in applications for lanthanides in energy and quantum information science. Here, two measurements of f-electron occupancy in CeBr 6 2– are reported based on X-ray spectra at the Ce L 3 - and Br K-edges and compared to the corresponding results for CeF 6 2– and CeCl 6 2– . These values allow for the estimation of average metal–ligand overlap integrals and covalent bond stabilization energies. For this series of compounds, overlap integrals and bond covalency are found to have opposing trends as the halide is varied. Finally, correlations between Ce IV L 3 -edge doublet splittings, 4f-orbital occupancies ( n f ), and ligand-to-metal charge transfer (LMCT) energies are identified that may indicate significant mixing between the 4f and 5d orbitals in other, noncentrosymmetric Ce IV complexes.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.007 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".