The Carbocation Rearrangement Mechanism, Clarified
Why this work is in the frame
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Bibliographic record
Abstract
The role of protonated cyclopropane (PCP(+)) structures in carbocation rearrangement is a decades-old topic that continues to confound. Here, quantum-chemical computations (PBE molecular dynamics, PBE and CCSD optimizations, CCSD(T) energies) are used to resolve the issue. PCP(+) intermediates are neither edge-protonated nor corner-protonated (normally) but possess "closed" structures mesomeric between these two. An updated mechanism for hexyl ion rearrangement is presented and shown to resolve past mysteries from isotope-labeling experiments. A new table of elementary-step barrier heights is provided. The mechanism and barrier heights should be useful in understanding and predicting product distributions in organic reactions, including petroleum modification.
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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 | 0.001 | 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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 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 it