X-ray photoelectron spectroscopy study of the skutterudites<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">La</mml:mi><mml:msub><mml:mi mathvariant="normal">Fe</mml:mi><mml:mn>4</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">Sb</mml:mi><mml:mn>12</mml:mn></mml:msub></mml:mrow></mml:math>,<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">Ce</mml:mi><mml:msub><mml:mi mathvariant="normal">Fe</mml:mi><mml:mn>4</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">Sb</mml:mi><mml:mn>12</mml:mn></mml:msub></mml:mrow></mml:math>,<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">Co</mml:mi><mml:msub><mml:mi mathvariant="normal">Sb</mml:mi><mml:mn>3</mml:mn></mml:msub></mml:mrow></mml:math>, and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:mi mathvariant="normal">Co</mml:mi><mml:msub><mml:mi mathvariant="normal">P</mml:mi><mml:mn>3</mml:mn></mml:msub></mml:mrow></mml:math>
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Bibliographic record
Abstract
The electronic structure of the skutterudites $\mathrm{Co}{\mathrm{Sb}}_{3}$, $\mathrm{Co}{\mathrm{P}}_{3}$, $\mathrm{La}{\mathrm{Fe}}_{4}{\mathrm{Sb}}_{12}$, and $\mathrm{Ce}{\mathrm{Fe}}_{4}{\mathrm{Sb}}_{12}$ has been investigated with x-ray photoelectron spectroscopy. The binding energies in the pnicogen and transition metal $2p$ spectra are shifted to reflect changes in the bonding character of these compounds. The asymmetric line shapes in the metal $2p$ spectra signal electronic delocalization. A plasmon loss satellite peak occurs in the Co $2p$ spectra of $\mathrm{Co}{\mathrm{Sb}}_{3}$ and $\mathrm{Co}{\mathrm{P}}_{3}$. The intensity of this peak in these and other Co-containing compounds increases with greater occupancy of the Co $3d$ band. The presence of trivalent rare earth was confirmed from the La and Ce $3d$ spectra, both of which contain shake-up satellite peaks. A second satellite peak, attributable to two-core-hole processes, also appears in the La $3d$ spectrum of $\mathrm{La}{\mathrm{Fe}}_{4}{\mathrm{Sb}}_{12}$ but not in $\mathrm{La}{\mathrm{Fe}}_{4}{\mathrm{P}}_{12}$, indicating the involvement of La-Sb covalent bonding and the population of La $4f$ conduction states in the former. This peak is absent in the Ce $3d$ spectrum of $\mathrm{Ce}{\mathrm{Fe}}_{4}{\mathrm{Sb}}_{12}$ because a $4{f}^{1}$ state is located below the Fermi edge. Fitting of the valence band spectra for all four compounds led to the formulations $({\mathrm{Co}}^{3+}){(P{n}^{1\ensuremath{-}})}_{3}$ and $({R}^{3+}){({\mathrm{Fe}}^{2+})}_{4}{({\mathrm{Sb}}^{1\ensuremath{-}})}_{12}$, with the electron deficiency in the rare-earth containing compounds being represented by a hole in the valence band.
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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 | 0.013 | 0.007 |
| Meta-epidemiology (narrow) | 0.007 | 0.014 |
| Meta-epidemiology (broad) | 0.003 | 0.013 |
| Bibliometrics | 0.004 | 0.009 |
| Science and technology studies | 0.012 | 0.010 |
| Scholarly communication | 0.012 | 0.012 |
| Open science | 0.016 | 0.014 |
| Research integrity | 0.013 | 0.013 |
| Insufficient payload (model declined to judge) | 0.653 | 0.015 |
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 it