Entropic Barriers Determine Adiabatic Electron Transfer Equilibrium
Bibliographic record
Abstract
A thermodynamic analysis of the forward and reverse rate constants for adiabatic and nonadiabatic electron transfer equilibria over an 80 K temperature range is reported. The kinetic data were acquired by a spectroscopic approach that utilized excited state injection into TiO 2 by sensitizers with two redox active groups linked through aromatic bridges that allow for intramolecular adiabatic (bridge = phenyl) or nonadiabatic (bridge = xylyl) electron transfer. Two impactful results were garnered from this analysis: (1) entropic barriers controlled the adiabatic electron transfer kinetics, and (2) the free energy barriers were unaffected by the degree of electronic coupling within experimental uncertainty. The second result stands in contrast to the common expectation that enhanced electronic coupling lowers the free energy barrier. This analysis provides new insights into how electronic coupling influences the free energy and barriers for electron transfer reactions.
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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 | 0.003 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.000 |
| Science and technology studies | 0.000 | 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) | 0.003 | 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".