Dispersion-driven conformational preference in the gas phase: Microwave spectroscopic and theoretical study of allyl isocyanate
Bibliographic record
Abstract
The conformations of allyl isocyanate (CH2=CHCH2N=C=O) were explored in the gas phase by combining theoretical calculations and Fourier transform microwave spectroscopy, including the chirped pulse and Balle-Flygare types. Three conformers (I, II, and III) were predicted using D3(BJ) dispersion-corrected B3LYP and MP2 methods; however, the lowest energy conformer (conf. I) was absent at the standard B3LYP level. The observed microwave spectra are consistent with the presence of both conf. I and III in the supersonic jet, and surprisingly, this is the first report of the global minimum conf. I both experimentally and theoretically. Rotational transitions from the parent species of both conformers as well as their minor isotopologues (13C, 15N, and 18O) in natural abundance were assigned allowing experimental geometries to be derived. For conf. I, in addition to the typical splitting pattern due to the 14N quadrupole nucleus, the transitions show a tunneling splitting which arises from the interconversion motion between its two mirror images. The experimental observation of conf. I and the absence of conf. II in the jet are rationalized using quantum-chemical calculations to explore the importance of electron correlation and in particular, demonstrate the necessity of including dispersion effects in density functional theory calculations even for seemingly small molecules.
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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".