Comparative Theoretical Investigation of the Vertical Excitation Energies and the Electronic Structure of [Mo<sup>V</sup>OCl<sub>4</sub>]<sup>-</sup>: Influence of Basis Set and Geometry
Bibliographic record
Abstract
The electronic structures, geometries, and vibration frequencies of the open-shell molybdenum(V) ion, [MoOCl(4)](-), have been calculated at the extended Hückel, semiempirical ZINDO/1, ZINDO/S, and PM3(tm), as well as ab initio and DFT theoretical levels. Electronic structure calculations suggest that the expected metal-fold orbital order can be satisfied only at the DFT level. The time-dependent density functional theory (TDDFT) approach has been used for the calculation of the vertical excitation energies in the UV-vis region with different basis sets, starting geometries, and exchange-correlation functionals. A good agreement between the predicted and the experimental electronic absorption and MCD spectra of the complex, [MoOCl(4)](-), was observed when the B3LYP and B3P86 exchange-correlation functionals were used with a full electron valence double-zeta with polarization basis set for the molybdenum and 6-311G(d) for all other atoms. Similar results were obtained when the LANL2DZ effective core potential for molybdenum atom and 6-31G(d) for all other atoms were used. The best absolute deviation of 0.13 and mean deviation of 0.01 eV were calculated for the bands in the UV-vis region by B3P86, while the results for the B3LYP exchange-correlation functional were less satisfactory. Compared to polarization functions, the inclusion of diffuse functions resulted in little improvement. The calculated excitations energies and charge-transfer band intensities are found to be sensitive to the Mo=O distance and O-Mo-Cl angle.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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 source (direct Gemma or distilled Codex), 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".