Mechanisms for the Oxonolysis of Ethene and Propene: Reliability of Quantum Chemical Predictions
Bibliographic record
Abstract
Reactions of ozone with ethene and propene leading to primary ozonide (concerted and stepwise ozonolysis) or epoxide and singlet molecular oxygen (partial ozonolysis) are studied theoretically. The mechanism of concerted ozonolysis proceeds via a single transition structure which is a partial diradical. The transition structures and intermediates in the stepwise ozonolysis and partial ozonolysis mechanisms are singlet diradicals. Spin-restricted and unrestricted density functional methods are employed to calculate the structures of the closed-shell and diradical species. Although the partial diradicals exhibit moderate to pronounced instability in their RDFT and RHF solutions, RDFT is required to locate the transition structure for concerted ozonolysis. Spin projected fourth-order MøllerâPlesset theory (PMP4) was used to correct the DFT energies. The calculated pre-exponential factors and activation energies for the concerted ozonolysis of ethene and propene are in good agreement with experimental values. However, the PMP4//DFT procedure incorrectly predicts the stepwise mechanism as the favored channel. UCCSD(T) predicts the concerted mechanism as the favored channel but significantly overestimates the activation energies. RCCSD(T) is found to be more accurate than UCCSD(T) for the calculation of the concerted mechanism but is not applicable to the diradical intermediates. The major difficulty in accurate prediction of the rate constant data for these reactions is the wide range of spin contamination for the reference UHF wave functions and UDFT solutions across the potential energy surface. The possibility of the partial ozonolysis mechanism being the source of epoxide observed in some experiments is discussed.
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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".