Thiophosgene, A Molecule Tailor-Made for Testing Fundamental Theoretical Concepts of Radiationless Transitions: Intramolecular Dynamics of S<sub>1</sub>Cl<sub>2</sub>CS
Bibliographic record
Abstract
The collision-free S 1 [à 1 A 2 (nπ*)] thiophosgene, with small (<3484 cm -1 ) and large (>9284 cm -1 ) excess vibrational energies, does not exhibit radiationless transitions to bound electronic states (S 0 and T 1 ), as evidenced by intense à → X̃ fluorescence with nearly constant lifetimes. The lack of radiationless transitions can be traced to the absence of the promoting mode for the 1 A 2 → 1 A 1 internal conversion and the vanishingly small spin−orbit coupling and very small Franck−Condon factor for the 1 A 2 (nπ*) → 3 A 2 (nπ*) intersystem crossing. In the intermediate range of excess energies (3484−9284 cm -1 ), fluorescence is not observed, consistent with the occurrence of predissociation. Quantum beat-modulated fluorescence decays, attributable to 1 A 2 (nπ*)− 3 A 1 (ππ*) perturbations, have been observed for excitation of 1 1 2 1 3 1 4 1 and nearby S 1 vibronic levels. This places the b̃ 3 A 1 (ππ*) state at about 20 350 cm -1 above the ground electronic state, in excellent agreement with the existing estimate. Interestingly, the S 1 radiative lifetime is about an order of magnitude shorter in a supersonic jet as compared to the vapor phase at room temperature, indicating that the probability of the vibronically induced à 1 A 2 (nπ*)−X̃ 1 A 1 radiative transition is significantly reduced at higher temperatures, due probably to Coriolis coupling.
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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) | 0.001 | 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".