Multi-mechanism linear free energy relationships and isoequilibrium or isokinetic temperatures
Bibliographic record
Abstract
The equations that describe the temperature dependence of the various terms in multi-mechanism linear free energy relationships (MMLFERs) are outlined with respect to reactions of organometallics involving P-donors. Each MMLFER includes a term defining the free energy of a standard reaction characterized by a chosen standard P-donor. Other terms quantify the various mechanisms by which the free energy of the standard reaction is modified by the participation of other P-donors that have different electronic and steric properties. Several different electronic terms can be involved. The temperature dependence of the modifying terms can provide measurements of the separate enthalpic and entropic contributions to the modifying processes. For MMLFERs that involve equilibrium or rate constants, each modifying term is associated with its own isoequilibrium or isokinetic temperature (IET or IKT) which defines the temperature at which each term is reduced to zero. These temperatures are provided by the ratios of the enthalpic and entropic contributions and it is suggested that they have little or no theoretical significance in themselves, although they can of course be of practical importance. There can be no meaningful single IET or IKT for any single series of reactions that show MMLFERs. The equations defining the temperature dependence of the modifying terms are applied to an extensive set of published reduction potentials for the complexes [(η5-C5H5)(CO)LFe(COMe)]+, where L = a large selection of P-donor ligands. The main modifying terms involve opposing σ-donicity and π-acidity effects and the enthalpic and entropic contributions are examined.
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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 | 0.002 | 0.004 |
| Meta-epidemiology (narrow) | 0.002 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.002 |
| Bibliometrics | 0.002 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.002 | 0.006 |
| Open science | 0.005 | 0.002 |
| Research integrity | 0.002 | 0.005 |
| 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".