Vibration mediated photodissociation dynamics of CH<sub>3</sub>SH: manipulation of the dynamic energy disposal into products
Bibliographic record
Abstract
The S-H bond dissociation dynamics of CH3SH have been investigated for the S1-S0 transition mediated by either the S-H stretching (2608 cm-1) or CH3 symmetric stretching (2951 cm-1) mode excitation in the S0 state. The S-H and C-S bond extensions are strongly coupled in the S1 state through the S1/S2 same-symmetry conical intersection, giving the C-S stretching mode excitation of the CH3S˙ fragment during the prompt S-H bond rupture on S1. In the IR + UV transition mediated by the S-H stretching mode, the vertical transition seems to access the Franck-Condon region where the S-H bond is shortened while the coupling to the C-S bond stretching becomes stronger compared to the case of one-photon UV transition, indicating that the intramolecular vibrational redistribution (IVR) is little activated in S0. When the IR + UV excitation is mediated by the CH3 symmetric stretching mode, on the other hand, the Franck-Condon region in S1 encompasses the enlarged molecular structures with respect to both S-H and C-S bond extensions, presumably due to the rapid IVR in S0 prior to the vertical transition. This leads to the inverted vibrational state population of the C-S bond stretching mode of the CH3S˙ fragment. This work demonstrates that the reaction dynamics upon the IR + UV excitation of CH3SH is highly mode dependent and the energy disposal dynamics could be controlled by the manipulation of the Franck-Condon region through the particular vibrational-state mediation in the ground state, shedding new light on the structure-dynamics relationship.
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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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".