Ethylene Epoxidation with Tungsten Diperoxo Complexes: Is Relativity the Origin of Reactivity?
Bibliographic record
Abstract
Scalar-relativistic effects on the coarctate transition states (TS) for ethylene epoxidation with Mimoun-type diperoxo complexes [MO( η 2 -O 2 ) 2 (OPH 3 )], 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.
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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 | 0.000 |
| 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) | 0.001 | 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".