An ab initio and AIM study on the decomposition of phosphite ozonides
Bibliographic record
Abstract
DFT calculations at the Becke3PW91/631+G(d) level of theory provided optimized geometries, transition states, and wave functions suitable for the study of the reactivity and molecular structure with Atoms-in-molecules (AIM) of phosphite ozonide complexes. These calculations also provided activation energies for the extrusion of singlet oxygen from the ozonides, which occurs in a concerted manner. The molecular species investigated were trimethyl phosphite ozonide (1), triphenyl phosphite ozonide (2), trifluoromethyl phosphite ozonide (3), trifluoroethyl phosphite ozonide (4), 4-ethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane ozonide (5), 1-phospha-2,6,7-trioxabicyclo[2.2.2]octane ozonide (6), 1-phospha-2,8,9-trioxadamantane ozonide (7), and propylene phenyl phosphite ozonide (8). Single-point calculations at the Becke3PW91/6311++G(d,p) level on the geometries obtained from the lower level theory yielded activation energies of 15.1 and 16.4 kcal mol1 for the nonconstrained complexes 1 and 2, respectively. These values differed from the electronegative trifluoro derivatives 3 and 4, which had much higher barriers of 23.5 and 20.8 kcal mol1, respectively. The activation energies of the bicyclic complexes 57 were significantly higher than 1 and 2 and comparable to 3 and 4, ranging from 23 to 26 kcal mol1. An intermediate barrier of 20.5 kcal mol1 was computed for 8. AIMPAC studies showed no direct correlation between the AIM atomic charges on the phosphorus or oxygen atoms of the ozonide ring with the ease of decomposition of 18 to singlet oxygen and the corresponding phosphate.Key words: phosphite ozonide complexes, decomposition, DFT methods, AIM, activation energy.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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".