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
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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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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it