Theoretical Study on Reactions of HO<sub>2</sub> Radical with Photodissociation Products of Cl<sub>2</sub>SO (ClSO and SO)
Bibliographic record
Abstract
The possible reactions of HO2 radical with the intermediates of the Cl2SO photolysis (ClSO and SO) were studied using G3MP2//B3LYP/cc-pVTZ+d level of theory and Martin's W1U method. For the reaction between HO2 and ClSO radicals, the following mechanisms are supposed to be the main reaction pathways HO2 + ClSO --> 3HOO x ClSO --> HOO(Cl)SO --> OH + ClSO2 --> HO + Cl + SO2, HO2 + ClSO --> 3HOO x ClSO --> HOO(Cl)SO --> OH + ClSO2 --> HO(Cl)SO2. On the basis of G3MP2//B3LYP/cc-pVTZ+d and highly accurate W1U calculations, the reaction of HOO with 3SO species has also been explored, and the following dominant consecutive reactions may describe the fast oxygen transfer HO2 + 3SO --> 4HOO x SO --> 2HOOSO --> OH + SO2. In both reaction mechanisms, the first step is a barrierless formation of relatively stable van der Waals complexes that lead via intersystem crossing to intermediate adducts. Thermodynamically favored decomposition products of 2HOOSO are OH radical and SO2. In the case of the ClSO and HO2 reaction, the dissociation of HOO(Cl)SO resulted in OH and ClSO2. Further decomposition of ClSO2 to Cl atom and SO2 competes with formation of HO(Cl)SO2 via OH addition reaction to ClSO2. We also report on high-level quantum chemical calculation (W1U) to predict values for the heat of formation of 2HSO3, 2HOOSO, and 2OOS(H)O radicals using the most reliable thermodynamic data of OH and SO3: Delta(f)H(298.15K)(2HSO3) = -256.2 kJ/mol, Delta(f)H(298.15K)(2HOOSO) = -152.6 kJ/mol, and Delta(f)H(298.15K)(2OOS(H)O) = -8.3 kJ/mol. On the basis of W1U standard reaction enthalpy for the reaction ClSO + HOO --> HCl + SO3, the heat of formation for the ClSO radical was also computed to be Delta(f)H(298.15K)(ClSO) = 102.6 kJ/mol within 4 kJ mol(-1) error.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.002 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.002 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.008 | 0.001 |
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".