Electronic structure of organic diradicals: Evaluation of the performance of coupled-cluster methods
Bibliographic record
Abstract
The performance of (i) the reduced multireference (RMR) coupled-cluster (CC) method with singles and doubles (RMR CCSD) that employs a modest-size MR CISD wave function as an external source for the most important (primary) triples and quadruples in order to account for the nondynamic correlation effects in the presence of quasidegeneracy, (ii) the RMR CCSD(T) method that adds a perturbative correction for the remaining (secondary) triples to the RMR CCSD energy, and (iii) the recently developed partially linearized MR CCSD method, which determines primary triples and quadruples using a subset of linear CC equations projected onto the corresponding higher-than-doubly excited configurations, are tested by considering the singlet-triplet splitting for several diradicals, ranging from a prototypical methylene radical to trimethylenemethane, and benzyne and pyridynium cation isomers. Both RHF and multiconfigurational self-consistent field molecular orbitals are employed. The equilibrium geometries for the lowest-lying singlet and triplet states are determined using both the density functional theory (DFT) and various CC approaches, and a comparison with both the experiment and other theoretical results, wherever available, is made. The RMR CCSD(T) results provide the most satisfactory description in all cases. The dependence of the MR diradical character on a spatial separation of radical centers, as well as the artifactual DFT geometry in the case of benzyne and pyridynium meta-isomers, is also pointed out.
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".