Reaction mechanism and kinetics of the atmospheric oxidation of 1,4-thioxane by NO<sub>3</sub> — A theoretical study
Bibliographic record
Abstract
Volatile organic compounds (VOCs) are emitted as pollutants into the atmosphere from many natural and artificial sources. The oxidation of VOCs by atmospheric species plays a key role in the degradation of VOCs. In the present investigation, the atmospheric degradation of a cyclic organosulfur compound, 1,4-thioxane, by an NO3• radical is studied. Pathways for the reaction of 1,4-thioxane with the NO3• radical were modeled through electronic structure calculations using density functional theory methods B3LYP, M06-2X, and MP2 with the 6–31G(d,p) basis set. The NO3•-initiated reaction of 1,4-thioxane was found to proceed in three ways: by single-hydrogen atom abstraction, by direct transfer of the O atom of NO3• to the S atom moiety of 1,4-thioxane, or by two-hydrogen atom transfer reactions leading to the formation of a peroxy radical intermediate, which further undergoes secondary reactions with other atmospheric species. Structures, energies, and vibrational frequencies obtained from M06-2X/6–31G(d,p) electronic structure calculations were subsequently used to perform canonical variational transition-state theory calculations to determine the rate constants over the temperature range of 278–350 K and to study the lifetime of 1,4-thioxane in the atmosphere. The rate constant calculated for the reaction of 1,4-thioxane with the NO3• radical is in good agreement with the available experimental data.
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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 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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".