A Theoretical Study of Hydroxycarbene as a Model for the Homolysis of Oxy- and Dioxycarbenes
Bibliographic record
Abstract
Recent work has shown that dioxycarbenes can readily undergo homolytic fragmentations to radicals in solution. Previous workers have found some theoretical evidence for a transition state in the homolysis of dihydroxycarbene to HOCO and H radicals using the CISD method, but they were not able to conclude whether such a barrier was real or an artifact of the approximation. In this work the homolysis of hydroxycarbene is examined at the CAS and MRCI levels of theory using the cc-pVDZ basis set. The atomic and molecular properties are examined using the theory of atoms in molecules. At the highest level of theory, a transition state is found for the fragmentation of trans - but not of cis -hydroxycarbene. This transition state is rationalized in terms of the electronic states involved in the avoided crossing and by examining the evolution of several atomic and molecular properties during the homolysis. It is concluded that its origin can be traced to a mismatch of the electronic structures of these states in the region of the avoided crossing, best expressed by the dipole moments.
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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 | 0.001 |
| Bibliometrics | 0.001 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.005 | 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".