Gas Phase Pyrolysis Reaction of 1-pyrazoline: A Theoretical Kinetic Study
Bibliographic record
Abstract
We report kinetic and mechanistic studies of nitrogen elimination from 1-pyrazoline and its deuterated derivatives. This study was carried out for the gas phase employing 6-311 + G(d,p) basis sets with B3LYP, MPW1PW91 and PBEPBE methods. This reaction may proceed through two different mechanisms, molecular and radical. The molecular mechanism advances via two different paths and corresponding intermediates. There are either a four-centred cyclic or a six-centred cyclic intermediate as transition states in the molecular mechanism. The calculated kinetic parameters and isotope effects for the molecular mechanism are consistent with experimental results for cyclopropane formation. However, from the kinetic isotope effects point of view, the fit is better for the radical mechanism for propene formation. Considering activation energies, theoretical calculations suggest that the radical mechanism is the less suitable. The B3LYP method results are in a better agreement with the experimental results when considering only computational data.
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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) | 0.000 | 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) | 0.003 | 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".