Dissociative Photoionization and Threshold Photoelectron Spectra of Polycyclic Aromatic Hydrocarbon Fragments: An Imaging Photoelectron Photoion Coincidence (iPEPICO) Study of Four Substituted Benzene Radical Cations
Bibliographic record
Abstract
Four molecules were investigated by imaging photoelectron photoion coincidence (iPEPICO) spectroscopy: 1-propynylbenzene, indene, ethynylbenzene, and benzocyclobutene. Their threshold photoelectron spectrum was obtained and electronic transitions were assigned by OVGF (outer valence Green's function) calculations. Vibrational progressions observed in the electronic ground and excited states were simulated by calculating Franck-Condon factors based on the neutral as well as the cation ground and excited state geometries. iPEPICO was used to obtain ion dissociation data in threshold photoionization as a function of photon energy, which were modeled with RRKM theory to extract kinetic parameters for the reactions C9H8(+•) (1-propynylbezene) → C9H7(+) + H (R1); C9H8(+•) (indene) → C9H7(+) + H (R2); C8H8(+•) (benzocyclobutene) → C8H7(+) + H (R3); C8H8(+•) (benzocyclobutene) → C6H6(+) + C2H2 (R4); C8H6(+•) (1-ethynylbenzene, aka phenylacetylene) → C6H4(+) + C2H2 (R5). These results were compared to G3 level calculations. In addition, the enthalpy of formation of the indenyl radical was estimated to be ΔfH°0K = 249 ± 50 kJ mol(-1) based on a previously measured IE and a cation ΔfH°0K = 976 kJ mol(-1), determined herein.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.000 | 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".