Vibrational Excitation Initiates Biomimetic Charge-Coupled Motions in the Electronic Ground State
Bibliographic record
Abstract
The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Manipulating reaction pathways to achieve product selectivity via precise control of light-molecule interactions has allured chemists for decades. Yet it remains an elusive challenge in the electronic ground state, where conventional thermally-driven chemistry occurs. Here, we demonstrate that ground-state vibrational excitation of localised bridge modes initiates charge transfer in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change in the ground-state electronic configuration is visualised by transient absorption spectroscopy, involving a mid-infrared pump and a visible probe, and detailed ab initio molecular dynamics simulations. Mapping the potential energy landscape unravels a hitherto undocumented charge-transfer-assisted double-bond isomerization channel in the electronic ground state. The reaction pathway bears remarkable parallels with the thermal isomerization process in rhodopsin, the retinal protein responsible for scotopic vision. Our results illustrate a generic protocol for activating key vibrational modes to drive photo-triggered ground-state reactions and motivate synthetic and catalytic strategies to achieving potentially new chemistry.
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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 | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".