A one-photon laser induced fluorescence and a sequential two-photon optical–optical double resonance excitation study of the vibrational structure of the B 1A1(ππ*) state of thiophosgene, Cl2CS
Bibliographic record
Abstract
The vibrational structure of the B̃ 1A1(ππ*) electronic state of jet cooled thiophosgene, Cl2CS, has been studied by laser induced fluorescence (LIF) excitation spectroscopy through the one-photon process B̃ 1A1←X̃ 1A1 and by optical–optical double resonance (OODR), spectroscopy. Two OODR schemes were used to probe the B̃ 1A1 state. One uses selected vibronic levels of the singlet à 1A2(nπ*) state while the second scheme uses the companion triplet, ã 3A2(nπ*) as the intermediate level. The one-photon LIF and the two-photon OODR schemes use different optical selection rules and the two sets of spectra contain very different information. The analyses of the vibrational structure confirmed the existing assignments for the Q1 (C=S stretch), Q2 (C–Cl stretch), and Q4 (out-of-plane) modes, and reversed the assignments for the Q3 (sym. Cl–C–Cl bend) and Q6 (antisym. Cl–C–Cl bend) modes. The barrier height to molecular inversion was revised upwards to 1495 cm−1 from an analysis of the (−)−(+) inversion splittings extracted from the ν4″=471 cm−1 “hot” band intervals in the “warm jet” one-photon LIF spectra. The regularity of the patterns of the Dixon–Western bands and the constant connecting wave-number intervals allowed these bands to be assigned to the activity of ν3″. The loss of fluorescence and the shortening of the lifetime at higher vibrational excitation energies is attributed to the crossing of the B̃ 1A1(ππ*) and C̃ 1B2(nσ*) electronic states at longer C=S bond distances.
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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".