Solvation of the Hydroxide Anion: A Combined DFT and Molecular Dynamics Study
Bibliographic record
Abstract
The electronic structure of solvated hydroxide complexes ((OH) - H 2 O) n, n = 1−3, is studied in detail using density functional theory (DFT), MP2, and Born−Oppenheimer-Molecular Dynamics (BOMD) approaches. Several nonlocal functionals of the GGA and LAP families are employed, special attention is paid to the reliability of the LAP functionals in predicting structure, energetics, and proton transfer barriers. It is found that most of these give reasonable energetics of the quite strong hydrogen bonding in hydroxide anions (within a difference of about 2−15% from the experimental solvation enthalpies), provided that basis sets with both polarization and diffuse functions are employed and the basis set superposition error is taken care of. The performance of the various methods for the geometry of the hydroxide complexes is not so uniform, especially for the hydrogen bond distances and the shape of the complex with three water ligands. These differences are reflected also in the calculated vibrational spectra, particularly concerning the vibrations involving the hydrogen bonds. For O 2 H 3 -, the potential energy surface associated with the central proton degrees of freedom is very flat, which leads to an intriguing proton dynamics. The BOMD simulation shows that the proton population profile is rather similar for BP and PP functionals, while the dynamical proton-transfer counting autocorrelation function, is, on the other hand, very sensitive to the choice of functional.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| 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".