Defining Direct Orbital Pathways for Intermolecular Electron Transfer Using Sensitized Semiconducting Surfaces
Bibliographic record
Abstract
High-performance electronic materials and redox catalysts often rely on fast rates of intermolecular electron transfer (IET). Maximizing IET rates requires strong electronic coupling ( H DA ) between the electron donor and acceptor, yet universal structure–property relationships governing H DA in outer-sphere IET reactions have yet to be developed. For ground-state IET reactions, H DA is reasonably approximated by the extent of overlap between the frontier donor and acceptor orbitals involved in the electron-transfer reaction. Intermolecular interactions that encourage overlap between these orbitals, thereby creating a direct orbital pathway for IET, have a strong impact on H DA and, by extension, the IET rates. In this Forum Article, we present a set of intuitive molecular design strategies employing this direct orbital pathway principle to maximize H DA for IET reactions. We highlight how the careful design of redox-active molecules anchored to solid semiconducting substrates provides a powerful experimental platform for elucidating how electronic structure and specific intermolecular interactions affect IET 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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.000 | 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".