Simulation study of solvent shifts of vibrational overtone spectra
Bibliographic record
Abstract
Buckingham's theory of the solvent shift of vibrational spectral frequencies predicts that the shift of the v = 0 → n overtone transition is n times the shift of the fundamental v = 0 → 1. We test this prediction by molecular dynamics simulations using existing intermolecular potential models for liquid N2 and dilute N2 in liquid Ar, at standard state conditions. We extend Buckingham's theory by including additional intramolecular potential and perturbation terms which lead to solvent-induced anharmonicity, i.e. O(n 2) terms in the solvent shift. The simulations show that Buckingham's prediction is not accurate for N2 at standard liquid state conditions. We find that at these conditions there is a significant positive O(n 2) contribution to the solvent shifts and that for n ∼ 20 the shifts change sign from red to blue. Simulation results and indirect evidence from shock wave experiments with liquid N2 show that Buckingham's prediction is more accurate for high-pressure high-temperature conditions, where the shifts are blue and only slightly nonlinear in n.
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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".