Solvent Effects on Heavy Atom Nuclear Spin−Spin Coupling Constants: A Theoretical Study of Hg−C and Pt−P Couplings
Bibliographic record
Abstract
The computation of indirect nuclear spin-spin coupling constants, based on the relativistic two-component zeroth order regular approximate Hamiltonian, has been recently implemented by us into the Amsterdam Density Functional program. Applications of the code for the calculation of one-bond metal-ligand couplings of coordinatively unsaturated compounds containing (195)Pt and (199)Hg, including spin-orbit coupling or coordination effects by solvent molecules, show that relativistic density functional calculations are able to reproduce the experimental findings with good accuracy for the systems under investigation. Spin-orbit effects are rather small for these cases, while coordination of the heavy atoms by solvent molecules has a great impact on the calculated couplings. Experimental trends for different solvents are reproduced. An orbital-based analysis of the solvent effect is presented. The scalar relativistic increase of the coupling constants is of the same order of magnitude as the nonrelativistically obtained values, making a relativistic treatment essential for obtaining quantitatively correct results. Solvent effects can be of similar importance.
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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".