H-atom abstraction from thiols by C-centered radicals. A theoretical and experimental study of reaction rates
Bibliographic record
Abstract
The Arrhenius parameters and rates of reaction of three hydroxyradicals, methyl radical, and the hindered primary C-centred radical from t-butyl alcohol with dithiothreitol were measured by pulse radiolysis in water. The bimolecular rate constants were found to be in the order: ˙C(CH3)2OH > ˙CH(CH3)OH > ˙CH2OH > ˙CH3 > ˙CH2C(CH3)2OH. The reaction of three of these, ˙C(CH3)2OH, ˙CH2OH, and ˙CH3, with methanethiol were examined at the ab initio B3LYP/6311+G(d,p) level, coupled with transition state theory, both in the gas phase and in solution. The solvent effects are evaluated by two different continuum models (SCIPCM, CPCM), coupled with a novel approach to the calculation of the solution phase entropy. The reaction is discussed in terms of the charge and spin polarization in the transition state, as determined by AIM analysis, and in terms of orbital interaction theory. Rate constants, calculated by transition state theory are in good agreement with the experimental data.
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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".