Entropy Changes in the Dissociation of Proton-Bound Complexes: A Variational RRKM Study
Bibliographic record
Abstract
Microcanonical variational transition state theory was employed to determine the entropy of activation, Δ S ⧧, for the dissociation of a series of acetonitrile−alcohol proton-bound pairs over an internal energy range corresponding to metastable ion decomposition observations on a magnetic sector mass spectrometer. It was found that Δ S ⧧ decreases with increasing size of the alcohol chain in the complex. These values ranged from 64 to 75 J K -1 mol -1 for (CH 3 CN)(CH 3 OH)H +, 34−43 J K -1 mol -1 for (CH 3 CN)(CH 3 CH 2 OH)H +, 6 J K -1 mol -1 for (CH 3 CN)(CH 3 CH 2 CH 2 OH)H +, and 11−13 J K -1 mol -1 for (CH 3 CN)((CH 3 ) 2 CHOH)H + . The entropy of activation was compared to the thermodynamic Δ S for the overall reaction, and larger relative changes are observed between Δ S ⧧ values than for Δ S .
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| 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 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".