Relativistic hybrid density functional calculations of indirect nuclear spin–spin coupling tensors — Comparison with experiment for diatomic alkali metal halides<sup>,</sup>
Bibliographic record
Abstract
The accurate calculation of the isotropic (Jiso) and anisotropic (ΔJ) parts of indirect nuclear spin–spin coupling tensors is a stringent test for quantum chemistry, particularly for couplings involving heavy isotopes where relativistic effects and relativity – electron correlation cross terms are expected to play an important role. Experimental measurements on diatomic molecules in the gas phase offer ideal data for testing the success of computational approaches, since the data are essentially free from intermolecular effects, and precise coupling anisotropies may be reliably extracted in favourable cases. On the basis of available experimental molecular-beam coupling-tensor parameters for diatomic alkali metal halides, we tabulate known values of Jiso and, taking rotational–vibrational corrections to the direct dipolar coupling constant into account, precise values of ΔJ are determined for the ground rovibrational state. First-principles calculations of the coupling tensors were performed using a recently developed program based on hybrid density functional theory using the two-component relativistic zeroth-order regular approximation (ZORA). Experimental trends in Jiso and ΔJ are reproduced with correlation coefficients of 0.993 and 0.977, respectively. Periodic trends in the coupling constants and their dependence on the product of the atomic numbers of the coupled nuclei are discussed. Finally, the hybrid functional method is also successfully tested against experimental data for a series of polyatomic xenon fluorides and group-17 fluorides.
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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 | 0.002 | 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 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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".