Giant K-doubling and in-plane/out-of-plane mixing in the asymmetric methyl-bending bands of CH3SH
Bibliographic record
Abstract
In analyzing high-resolution spectra of the methyl-deformation bands of methyl mercaptan recorded at the Canadian Light Source synchrotron, we have encountered interesting interactions between certain levels of the ν4 in-plane asymmetric CH3-bending mode and its ν10 out-of-plane bending partner below. The origin of the K = 0A ν4 substate is just 0.2 cm−1 higher than that of the K = 2A ν10 substate, while the K = 0E ν4 origin is only 0.035 cm−1 below the K = 2E ν10 origin. These very close accidental near-degeneracies lead to substantial perturbations in the spectrum. For the former, the A+/A− asymmetry K-doublet coupling rules are such that the A− component of the 2A ν10 doublet interacts and mixes strongly with the 0A+ ν4 levels whereas the 2A+ component is unaffected. The 2A− levels are pushed rapidly downwards by the coupling creating an extremely large apparent K = 2A asymmetry splitting. We call this “giant K-doubling” by analogy with a comparable phenomenon seen for methanol. The 0A+ ν4 state, in turn, is perturbed upward and passes through the descending K = 1A+ ν4 state between J = 22 and 23, leading to distinct local perturbations near the level-crossing. The 0E ν4 and 2E ν10 coupling produces a correspondingly strong repulsion and mixing between those two substates, and gives rise to a forbidden K = 0 ← 3E intermode sub-band in the spectrum via intensity borrowing.
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How this classification was reachedexpand
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 | 0.001 | 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 | 0.001 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".