Dissociation Without Detonation: A DFT Analysis of the Thermally Induced Fragmentation of Binary Sulfur–Nitrogen Rings and Cages
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Bibliographic record
Abstract
Potential thermal dissociation pathways available to binary sulfur nitrides have been explored by density functional theory methods, and the results interpreted in terms of their known thermochemical behavior. The cyclic cation/anion pair S 3 N 3 ± both undergo concerted (4 + 2) cycloreversions to afford the 3-membered thiadiazirine ring c -NSN and, respectively, the SNS ± cation/anions. A similar pathway has been identified for S 4 N 2, leading to S 3 and c -NSN. More complex multistep routes for the elimination of c -NSN have been identified for the bicyclic cation/anion pair S 4 N 5 ±, as well as for the neutral cage structures S 4 N 4 and S 5 N 6 . For the S 4 N 5 + cation a transition state for competing skeletal scrambling via a 1,3-nitrogen σ-bond shift has been located. For the multiply charged cations S 3 N 2 2+ and S 4 N 4 2+, dissociation mechanisms are driven by charge repulsion effects, affording SNS + /SN + and S 3 N 3 + /SN + respectively. Channels leading to loss of NS + from the cyclic cation species S 4 N 3 + and S 5 N 5 + have also been examined, and the possible role of open-chain and cyclic S 3 N 2 -based intermediates in the formation of S 2 N 2 during the thermal cracking of S 4 N 4 over silver wool is explored.
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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) | 0.000 | 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) | 0.001 | 0.000 |
Machine scores (provisional)
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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 it