On the Origin of the Optical Activity in the d−d Transition Region of Tris-Bidentate Co(III) and Rh(III) Complexes
Bibliographic record
Abstract
Time-dependent density functional theory (TD-DFT) has been employed to calculate the rotatory strengths in the d-d transition region for various tris-bidentate Co(III) and Rh(III) complexes. Optimized structural parameters are also reported. Our results confirm a previously proposed relationship between the azimuthal distortion of a complex containing saturated tris(diamine) and its optical activity. Formally d-d transitions are forbidden and should not exhibit optical activity. However, it is shown here that the intensity of these bands originates from a coupling of even ligand combination (participating in the e(g) type LUMO) and an odd ligand combination (participating in the t(2)(g) HOMO). For complexes containing planar unsaturated ligands, the signs of the d-d bands observed from the single-crystal circular and linear dichroisms are in accordance with the TD-DFT predictions. It is shown that by using hypothetical Co(NH(3))(6)(3+) complexes it is possible to estimate the contribution from the azimuthal distortion to the total rotatory strengths of the saturated tris(diamine) complexes. A discussion is also provided of previous theoretical studies and the way in which these investigations rationalized the optical activity.
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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 | 0.000 | 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) | 0.001 | 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 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".