Actinide(II) Dioxo Stabilization in the Dipyriamethyrin Ligand Environment: A DFT Study
Bibliographic record
Abstract
This study aims to understand the properties of mid- to late-actinide dioxo cations, [An II (η 1 - 3 O 2 )] 2+ (An = Am–Lr) in their +II oxidation state and their interaction with the dipyriamethyrin ligand. The DFT calculations of the total binding energies of the complex isomers with 7 and 8 coordination to the actinide point to the latter as relatively more stable. In the complexes, Am, Cm, and Lr shift to a more stable +III oxidation state, Bk to Es were assigned oxidation states between +II and +III, while Fm to No retained their formal +II oxidation state. The triplet dioxygen transitioned to a doublet superoxide upon complexation, as observed from Mayer bond orders (∼1.5 for O*–O bonds) and spin density (∼0.5 on O). Based on bond lengths and bond orders, the An–N bonds show weak covalency, while the An–O* and An···O bonds exhibited stronger covalent interactions. The calculated thermodynamic parameters indicate the formation of [An(O 2 )L] to be spontaneous and exothermic, with [Cm(O 2 )L] and [Lr(O 2 )L] being the most thermodynamically and energetically feasible. Energy decomposition analysis quantifies more covalent character in the former than the latter. Conversely, [No(O 2 )L] is the least stable due to the reduced availability of 6d and 7s orbitals for bonding.
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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 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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".