Bibliographic record
Abstract
Interest in the chemistry of the early actinide elements (notably uranium through americium) usually results either from the nuclear waste problem or the unique chemistry of these elements that result from 5f contributions to bonding. Computational actinide chemistry provides one useful tool for studying these processes. Theoretical actinide chemistry is challenging because three principal axes of approximation have to be optimized. These are the model chemistry (the choice of approximate electron-electron correlation method and basis sets), the approximate relativistic method, and a method for modeling solvent (condensed phase) effects. In this Account, we arrange these approximations in a three-dimensional diagram, implying that they are relatively independent of each other. A fourth level of approximation concerns the choice of suitable models for situations too complex to treat in their entirety. We discuss test cases for each of these approximations. Gas-phase data for uranium fluorides and oxofluorides such as UF(6) and UO(2)F(2) show that GGA functionals provide accurate geometries and frequencies while hybrid density functional theory (DFT) functionals are superior for energetics. MP2 is seen to be somewhat erratic for this set of compounds, and CCSD(T) gives the most accurate results. Three different relativistic methods, small-core effective core potentials (SC-ECP), ZORA, and all-electron scalar, provide comparable results. The older large-core ECP (LC-ECP) approach is consistently worse and should not be used. We confirmed these conclusions through studies of the actinyl aquo complexes [AnO(2)(OH(2))(5)](n+), (An = U, Np, or Pu and n = 1 or 2) that are also used to test solvation models. As long as the first coordination sphere of the metal is included explicitly, continuum solvation models are reliable, and we found no clear advantage for the (costly) explicit treatment of the second coordination sphere. Spin-orbit effects must be included to reproduce the correct trend in An(VI)/An(V) reduction potentials. We propose a multistep mechanism for the experimentally observed oxygen exchange of UO(2)(2+) cations in highly alkaline solutions present in tank wastes. This process involves an equilibrium between [UO(2)(OH)(4)](2-) and [UO(2)(OH)(5)](3-), followed by formation of the stable [UO(3)(OH)(3)](3-) intermediate that forms from [UO(2)(OH)(5)](3-) through intramolecular water elimination. The [UO(3)(OH)(3)](3-) intermediate facilitates oxygen exchange through proton shuttling. We explain the experimentally observed stabilization of the pentavalent oxidation state of actinyl ions by macrocyclic ligands (such as 18-crown-6) as an effect of solvation: the large macrocycle screens the positive charge of the ion from the polarizable solvent. Alkyl-substituted isoamethyrin complexes are bent despite being aromatic because of steric factors, rather than fit/misfit criteria regarding the actinyl ion. By application of an efficient DFT code, actinide molecules with more than 100 atoms can now be studied routinely. "Real" chemical questions can be answered as long as we take great care to apply methods that are accurate with respect to the three axes of approximation described above. While the exclusive focus of this Account has been on the early actinide elements, these conclusions also apply elsewhere in the periodic table.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.015 | 0.002 |
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".