Experimental and Theoretical Studies of the Benzylium<sup>+</sup>/Tropylium<sup>+</sup> Ratios after Charge Transfer to Ethylbenzene
Bibliographic record
Abstract
Benzylium versus tropylium ion yields from the fragmentation of ethylbenzene cations at various excitation energies are studied by forming excited ethylbenzene cations by charge transfer from a series of charge-transfer agents and by identifying the benzylium ion by its secondary reaction with neutral ethylbenzene. At lower excitation energies, the tropylium ion yield decreases with increasing energy from values near 16% (at an energy of 230 kJ mol -1 ) to 5% (at an energy of 500 kJ mol -1 ). At higher excitation energies, the tropylium ion yield increases again, which is attributed to secondary isomerization of the vibrationally highly excited benzylium ion arising from the primary fragmentation. It is suggested that this isomerization competes with radiative cooling of the excited benzylium ion. The experimental observations are rationalized in the framework of statistical unimolecular rate theory and electronic structure calculations.
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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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.009 | 0.001 |
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".