Probing the pyrolysis of ethyl formate in the dilute gas phase by synchrotron radiation and theory
Bibliographic record
Abstract
Abstract The thermal decomposition of the atmospheric constituent ethyl formate was studied by coupling flash pyrolysis with imaging photoelectron photoion coincidence (iPEPICO) spectroscopy using synchrotron vacuum ultraviolet (VUV) radiation at the Swiss Light Source (SLS). iPEPICO allows photoion mass‐selected threshold photoelectron spectra (ms‐TPES) to be obtained for pyrolysis products. By threshold photoionization and ion imaging, parent ions of neutral pyrolysis products and dissociative photoionization products could be distinguished, and multiple spectral carriers could be identified in several ms‐TPES. The TPES and mass‐selected TPES for ethyl formate are reported for the first time and appear to correspond to ionization of the lowest energy conformer having a cis (eclipsed) configuration of the O = C (H)– O – C (H 2 )–CH 3 and trans (staggered) configuration of the O= C (H)– O – C (H 2 )– C H 3 dihedral angles. We observed the following ethyl formate pyrolysis products: CH 3 CH 2 OH, CH 3 CHO, C 2 H 6 , C 2 H 4 , HC(O)OH, CH 2 O, CO 2 , and CO, with HC(O)OH and C 2 H 4 pyrolyzing further, forming CO + H 2 O and C 2 H 2 + H 2 . The reaction paths and energetics leading to these products, together with the products of two homolytic bond cleavage reactions, CH 3 CH 2 O + CHO and CH 3 CH 2 + HC(O)O, were studied computationally at the M06‐2X‐GD3/aug‐cc‐pVTZ and SVECV‐f12 levels of theory, complemented by further theoretical methods for comparison. The calculated reaction pathways were used to derive Arrhenius parameters for each reaction. The reaction rate constants and branching ratios are discussed in terms of the residence time and newly suggest carbon monoxide as a competitive primary fragmentation product at high temperatures.
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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 | 0.002 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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".