Assessment and Application of Density Functional Theory for the Prediction of Structure and Reactivity of Vanadium Complexes
Bibliographic record
Abstract
We assess the performance of six density functionals, each paired with one of five basis sets (a total of 30 model chemistries) for the prediction of geometrical parameters in the coordination sphere of nine vanadium complexes (for a total of 270 structural analyses). We find that results are generally consistent over the range of functionals tested and that none fail drastically. For bond lengths, the model chemistry PBE0/QZVP performed the best overall (having a MAD of only 0.02 Å from experiment) yet PBE0/6-31G* provides nearly identical results. For bond angles, PBE0 also performed best overall and, when combined with the 6-31G* basis, produces one of the smallest error distributions of any model chemistry tested. We subsequently applied the PBE0/6-31G* model chemistry to understanding the mechanism of action of a [BIMPY]VCl3 catalyst in the polymerization of styrene (Sty) and vinyl acetate (VAc). Our results indicate that the [BIMPY]VCl3 catalyst operates through a unique, two-step reaction pathway: dehalogenation to form a reactive V(II) intermediate (a highly favorable process) followed by a potentially reversible OMRP to control the polymerization of vinyl acetate. Control over vinyl acetate is facilitated by both the higher reactivity of the radical species and the participation of the ester group in the trapping step. In both the Sty and VAc cases we predict relatively poor control of the polymerization with the vanadium catalyst, which is in good agreement with our experimental results.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot 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.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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 teacher head, 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".