Ethylene Epoxidation with Tungsten Diperoxo Complexes: Is Relativity the Origin of Reactivity?
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
Scalar-relativistic effects on the coarctate transition states (TS) for ethylene epoxidation with Mimoun-type diperoxo complexes [MO(η2-O2)2(OPH3)], M = Cr, Mo, W, were studied using gradient-corrected density-functional theory at the BP86 level within the nonrelativistic, quasi-relativistic, and ZORA approaches. Spin−orbit effects were proved to be small. While scalar-relativistic effects scarcely influence the thermodynamics of the reaction with the tungsten complex, they shift the extent of reaction at the transition state toward the reactants and decrease the activation barrier significantly. The analysis of the transition states using a fragment-based energy-decomposition scheme shows that the reduction of the activation energy by relativistic effects is mainly due to the destabilization of the reactants rather than to the stabilization of the TS.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| 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 it