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Record W2913738730 · doi:10.1021/acs.jctc.8b01296

A DFT/ZORA Study of Cadmium Magnetic Shielding Tensors: Analysis of Relativistic Effects and Electronic-State Approximations

2019· article· en· W2913738730 on OpenAlexafffund
Sean T. Holmes, Robert W. Schurko

Bibliographic record

VenueJournal of Chemical Theory and Computation · 2019
Typearticle
Languageen
FieldChemistry
TopicAdvanced NMR Techniques and Applications
Canadian institutionsUniversity of Windsor
FundersNatural Sciences and Engineering Research Council of CanadaGenentechUniversity of WindsorGenentech Foundation
KeywordsElectromagnetic shieldingDensity functional theoryCoupled clusterCadmiumParamagnetismChemistryRelativistic quantum chemistryElectronic structureHamiltonian (control theory)Scalar (mathematics)PhysicsAtomic physicsCondensed matter physicsComputational chemistryQuantum mechanicsMolecule

Abstract

fetched live from OpenAlex

Theoretical considerations are discussed for the accurate prediction of cadmium magnetic shielding tensors using relativistic density functional theory (DFT). Comparison is made between calculations that model the extended lattice of the cadmium-containing solids using periodic boundary conditions and pseudopotentials with calculations that use clusters of atoms. The all-electron cluster-based calculations afford an opportunity to examine the importance of (i) relativistic effects on cadmium magnetic shielding tensors, as introduced through the ZORA Hamiltonian at either the scalar (SC) or spin–orbit (SO) levels and (ii) variation in the class of the DFT approximation. Twenty-three combinations of pseudopotentials or all-electron methods, DFT functionals, and relativistic treatments are assessed for the prediction of the principal components of the magnetic shielding tensors of 30 cadmium sites. We find that the inclusion of SO coupling can increase the cadmium magnetic shielding by as much as ca. 1100 ppm for a certain principal values; these effects are most pronounced for cadmium sites featuring bonds to other heavy atoms such as cadmium, iodine, or selenium. The best agreement with experimental values is found at the ZORA SO level in combination with a hybrid DFT method featuring a large admixture of Hartree–Fock exchange such as BH&HLYP. Finally, a theoretical examination is presented of the magnetic shielding tensor of the Cd(I) site in Cd2(AlCl4)2.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: none
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.673
Threshold uncertainty score0.275

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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.

Opus teacher head0.005
GPT teacher head0.268
Teacher spread0.263 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

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".

Quick stats

Citations14
Published2019
Admission routes2
Has abstractyes

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