Evaluation of the SCF Combination of KS-DFT and 3D-RISM-KH; Solvation Effect on Conformational Equilibria, Tautomerization Energies, and Activation Barriers
Bibliographic record
Abstract
The effect of solvation on conformational equilibria, tautomerization energies, and activation barriers in simple SN2 reactions is reproduced by using the self-consistent field coupling of the Kohn-Sham density functional theory (KS-DFT) for electronic structure and the three-dimensional reference interaction site model with the closure approximation of Kovalenko and Hirata (3D-RISM-KH) for molecular solvation structure. These examples are used in order to validate the implementation of the 3D-RISM-KH method in the Amsterdam Density Functional package. The computations of the free energy difference in the trans/gauche conformational equilibrium for 1,2-dichloroethane in different solvents; the relative tautomerization free energy for cytosine, isocytosine, and guanine; and the free energy activation barrier for a CH3X-type (X = F, Cl, Br) SN2 reaction exhibit agreement with the experimental data. The method is also applied to the electronic and hydration structure of carbon single-wall nanotubes of different diameters, including the effect of water located in the inner space of the nanotubes. A comparison with continuum models of solvation (including COSMO) as well as with other more precise and computationally more expensive calculations is made to demonstrate the accuracy and predictive capability of the new KS-DFT/3D-RISM-KH method.
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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 | 0.002 | 0.001 |
| 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".