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Record W1925830238 · doi:10.1139/v11-054

[Pt@Pb<sub>12</sub>]<sup>2–</sup> — A challenging system for relativistic density functional theory calculations of <sup>195</sup>Pt and <sup>207</sup>Pb NMR parameters

2011· article· en· W1925830238 on OpenAlexvenueno aff
Boris Le Guennic, Jochen Autschbach

Bibliographic record

VenueCanadian Journal of Chemistry · 2011
Typearticle
Languageen
FieldPhysics and Astronomy
TopicAdvanced Chemical Physics Studies
Canadian institutionsnot available
FundersNational Science Foundation
KeywordsChemistryCoupling constantAtomic orbitalTensor (intrinsic definition)Chemical shiftRelativistic quantum chemistryCoupled clusterDensity functional theorySpin (aerodynamics)Coupling (piping)AnisotropyAtomic physicsJ-couplingElectronNuclear magnetic resonance spectroscopyPhysicsComputational chemistryPhysical chemistryQuantum mechanicsMoleculeThermodynamicsStereochemistry

Abstract

fetched live from OpenAlex

We report computations of NMR chemical shifts and indirect spin-spin coupling constants (J couplings) for the [Pt@Pb 12 ] 2– “superatom”. The system is strongly influenced by relativistic effects. The Pt–Pb coupling constant is predicted to be negative, with its magnitude being in reasonable agreement with experiment. Pt and Pb chemical shifts also agree reasonably well with experiment. The Pb shielding tensor is strongly anisotropic, with a large deshielding principal component dominated by magnetic coupling between frontier orbitals of the cluster that resemble atomic g orbitals. The NMR parameters are sensitive to approximations made in the computations and require the inclusion of spin-orbit coupling in the theoretical model to achieve reliable results. Computing the NMR parameters of the compact [Pt@Pb 12 ] 2– system with its many electrons proves to be a challenging test case for relativistic density functional methods.

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 categoriesMeta-epidemiology (narrow)
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 score0.614
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.001
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 head0.019
GPT teacher head0.200
Teacher spread0.181 · 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.

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

Citations16
Published2011
Admission routes1
Has abstractyes

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