A DFT study on the electronic and redox properties of [X <sub>8</sub> V <sub>14</sub> O <sub>50</sub> ] <sup> <i>n</i> – </sup> (X = Si <sup>IV</sup> , Ge <sup>IV</sup> , P <sup>V</sup> , and As <sup>V</sup> )
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Bibliographic record
Abstract
The electronic and redox properties of the title polyanions have been calculated by means of density functional theory (DFT). These were unrestricted open-shell systems with electronic configuration of d 1 of V. In this behalf, energies and compositions of α-LUMO, β-LUMO, α-HOMO, and β-HOMO were also analyzed. First of all, electronic and redox properties of vanadosilicate [Si 8 V 14 O 50 ] 12– (system 1) were calculated and then Si IV was substituted with Ge IV , P V , and As V for further investigations of systems 2, 3, and 4, respectively. The substitution greatly modifies the electronic properties as α-LUMOs are quite different in all the studied systems. The α-LUMO is mainly composed of V and O in system 1, V and Ge in system 2, V and O in system 3, and As, O, and V in system 4. The alpha HOMO–LUMO energy gaps are greatly reduced in systems 2, 3, and 4 as compared with system 1. The system 4 [As 8 V 14 O 50 ] 4– has minimal value of total bonding energy, whereas system 2 [Ge 8 V 14 O 50 ] 12– has maximal, so energetically system 4 is more favourable than the others. After the first reduction, α-LUMO in [Si 8 V 14 O 50 ] 14– is made up of V and Si, β-LUMO in [Ge 8 V 14 O 50 ] 13– is concentrated on V and Ge, β-LUMO in [P 8 V 14 O 50 ] 5– is composed of V only, whereas β-LUMO in [As 8 V 14 O 50 ] 5– is delocalized over V, O, and As with almost the same contribution of all three atoms.
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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 | 0.005 | 0.002 |
| Meta-epidemiology (narrow) | 0.003 | 0.002 |
| Meta-epidemiology (broad) | 0.003 | 0.001 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.002 | 0.003 |
| Scholarly communication | 0.002 | 0.002 |
| Open science | 0.004 | 0.001 |
| Research integrity | 0.001 | 0.004 |
| Insufficient payload (model declined to judge) | 0.001 | 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 it