Effects of Restricted Rotations and Dynamic Averaging on the Calculated Isotropic Hyperfine Coupling Constants of the <i>bis</i>-Dimethyl and <i>bis</i>-Di(trifluoromethyl) Nitroxide Radicals
Bibliographic record
Abstract
The rotational effects of the CH(3) and CF(3) groups on the electronic structure and nuclear hyperfine coupling constants (HFCCs) in dimethylnitroxide (DMNO*) and ditrifluoro-methynitroxide (TFMNO*) are investigated using the UB1LYP hybrid density functional method. The CH(3) and CF(3) HFCCs of both radicals are found to obey the McConnell relation during rotation. The two CH(3) groups of the DMNO* do not gear with each other, but the rotation of the first CH(3) group induces only a small rocking effect ( approximately 7 degrees ) in the second group. However, in TFMNO*, the fluorine atoms from different CF(3) groups are close enough so that the steric repulsion between them causes them to act as two interlocked gears, where one drives the other. Therefore, both CF(3) groups undergo full rotation. To the best of our knowledge, this is only the second example of "gearing" to be studied. Stabilization due to hyperconjugation is also a major factor that affects the magnitudes of the HFCCs of the CF(3) groups during rotational averaging. Stable configurations at specific CF(3) group orientations have a large overlap with the NO pi-electron cloud because the lobes of the hybridized p(sigma)(F(2)), p(sigma)(F(3)), p(sigma)(F(5)), and p(sigma)(F(6)) orbitals along the F-C bonds have cylindrical symmetry and are of the correct phases for hyperconjugation to occur. The calculated TFMNO* C(1)-N and C(2)-N bond orders range from 0.91 to 0.95 as the CF(3) groups are rotated. Therefore, the C-N bonds are essentially single bonds. This, in conjunction with the low rotational energy barrier of approximately 50 cm(-1), explains why the EPR intensities of the (19)F hyperfine splittings, in the range of 163-297 K, are characteristic of six equivalent rapidly rotating fluorine atoms. The TFMNO* out-of-plane NO vibrations induce additional s character at the (14)N nucleus. This increases the magnitude of the (14)N HFCC and decreases the (19)F HFCCs. As the temperature increases and because of mixing of the first excited out-of-plane vibrational state, the NO vibrational amplitudes also increase. This leads to an increased (14)N HFCC and decreased (19)F HFCCs, which is in agreement with experiment.
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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) | 0.001 | 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 | 0.001 |
| 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".