A general measure of conjugation in biphenyls and their radical cations
Bibliographic record
Abstract
Changes in the amount of conjugation in the biphenyl system upon torsion have been investigated with quantum chemistry computations. For the unsubstituted biphenyl and its radical cation, the change in the energy for the first electronic transition as determined from time-dependent density functional theory, specifically TD-B3LYP, upon an imposed change in torsion angle appears to provide a good general measure of the delocalization of the π-electrons. Upon substitution, though, a relationship could not be established between the excitation energy and the twist across the C–C bond connecting the two phenyl rings. In contrast, the π-interaction energy, i.e., the π–π interaction across the central C–C bond, determined from a natural bond orbital analysis, provides a uniform description of conjugation in the electronically different systems, for an imposed twist as well as upon substitution. Substituent effects are found to be larger and more varied for the biphenyl radical cations. Of particular interest is the introduction of the oxidizable substituents OCH 3 (methoxyl) and SCH 3 (methylthio), as this leads to the smallest changes in torsion angle in the biphenyl unit upon removal of an electron from the molecule. The findings of this work could ultimately prove useful for the rational design of conductive polymer materials.
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How this classification was reachedexpand
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 | 0.000 | 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) | 0.000 | 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 teacher head, 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".