On the simulation of photoelectron spectra complicated by conical intersections: Higher-order effects and hot bands in the photoelectron spectrum of triazolide (CH)2N3−
Bibliographic record
Abstract
We report simulated photoelectron spectra for 1,2,3-triazolide (CH)(2)N(3)(-), which reveal the vibronic energy levels of the neutral radical 1,2,3-triazolyl, (CH)(2)N(3). The spectral simulation using a quasidiabatic Hamiltonian H(d) comprised of polynomials through 4th order (thereby extending conventional quadratic expansions), is compared to both the experimental spectrum and a standard Franck-Condon (adiabatic) simulation. The quartic H(d) is far superior to the quadratic H(d), reproducing the main features of the experimental spectrum and allowing for their subsequent assignment. The contributions from excited anion states successfully reproduce the observed vibronic transitions to the red of the assigned band origin of the neutral species. The algorithmic extensions required for the determination of these hot band contributions to the total spectrum are discussed. Convergence of the spectral envelope with respect to the vibronic basis, including both the principal and hot bands, required more than 10(9) terms.
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".