Raman intensity and conjugation with participation of ordinary σ‐bonds
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Bibliographic record
Abstract
Abstract This review covers Raman investigations over a wide range, but focused on the problem of conjugation with participation of ordinary σ‐bonds. The results show that σ–σ conjugation in a novel class of polymers, polydiakylmetallanes of the type [R 2 M] n , M = Si, Ge, Sn, studied recently, and σ–π conjugation in some organometallic compounds of Si, Ge and Sn, studied long ago, both manifest themselves in the Raman spectra qualitatively in a similar way to π–π conjugation in polyenes and lead to a significant increase in intensity of the lines, corresponding to stretching vibrations of the conjugated bonds, the effect being strongly dependent on mutual orientation of the latter. It was found that pre‐resonant enhancement of some lines in the Raman spectra of polymetallanes is exhibited only by macromolecules having a planar zig‐zag all‐ anti conformation of the backbone. Less ordered conformations do not show this effect, in spite of the proximity of the position of their lowest energy electronic absorption band ν e to the exciting line ν. Thus, proximity of ν e to ν in the resonance denominator is shown to be necessary but not sufficient for the pre‐resonant increase in Raman intensity to occur. These experimental findings are in good accord with Shorygin's general views on the conjugation phenomenon and with his semi‐classical treatment of the Raman intensity problem, confirming an important role of the derivative ∂ν e /∂ Q i that reflects the specificity of molecular electronic structure. Copyright © 2001 John Wiley & Sons, Ltd.
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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) | 0.001 | 0.000 |
Machine scores (provisional)
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Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
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