Equilibrium constants for enolization in solution by computation alone
Bibliographic record
Abstract
Equilibrium free energy changes for enolization in aqueous solution can be calculated with useful accuracy (rmse = 1.3 kcal/mol for 37 reactions). These calculations involve gas phase free energy changes calculated using the G3MP2B3 method and solvation energies calculated using the IPCM method corrected by a parameterization scheme which we have reported. For chloroacetones, we find a small preference for enolization to the halogenated side and a preference for forming an enol with Cl Z to the OH. This may be partly due to weak hydrogen bonding but must be partly due to a relief of crowding; 2‐butanone also shows a preference for the Z‐enol. There are serious disagreements between calculated and experimental values for some of the enolization equilibria of 1,3,5‐cyclohexanetrione (phloroglucinol); we argue that the problems are with the experimental values. Reasonable values are obtained for the enolization of Meldrum's acid, diethyl malonate, and 1,3‐cyclohexanedione. Computational equilibrium constants in aqueous solution are now viable as supplements to and checks on experiment. Copyright © 2013 John Wiley & Sons, Ltd.
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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 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.012 | 0.003 |
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".