A density functional theory study on the rearrangements of the 6-tricyclo[3.2.1.02,4]octyl cation and its isomers: a walk on the C8H11+ potential energy surface and a peek at molecular structures with AIM
Bibliographic record
Abstract
To fully rationalize the solvolytic results of five brosylates (exo,exo-, exo,endo-, and endo,exo-6tricyclo[3.2.1.02,4 ]octyl brosylates 1-OBs, 2-OBs, and 3-OBs, nortricyclyl-3-carbinyl brosylate (4-OBs), and 4-tricyclo[3.2.1.02,7 ]octyl brosylate (5-OBs)) we carried out a DFT (Becke3PW91/6-311G(d,p)) computational study on the C8 H11 + potential energy surface.Four key intermediate cations 9, 11, and 13 and their rearrangements are sufficient to account for the experimental results.It is not necessary to envoke so-called memory effects.A peek at the molecular structures of the cations with AIM (Atoms in Molecules) indicates that none of the intermediate cations have penta-coordinate carbons, so they are classical species.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| 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 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".