The Light‐Driven Isomerization of Aqueous Nitrate: A Theoretical Perspective
Bibliographic record
Abstract
Abstract The reaction mechanism for the rearrangement of the nitrate anion to its cis and trans peroxonitrite isomers is investigated in detail by quantum theoretical methods. The electronic ground state potential energy hypersurface (PES) features a bifurcation point along the minimum energy path at high energy, while the intrinsic reaction path moves the bifurcation point towards the transition state (TS) between the two peroxynitrite isomers. Coupled‐cluster calculations reveal a high‐lying transition state (4.6 eV) for the major photochemical isomerization pathway via an S 1 /S 0 conical intersection, explaining why electronic excitation of the bright singlet states with λ =200–270 nm is required to trigger formation of peroxinitrite, while excitation of the weak band around 300 nm (wavelengths >270 nm) does instead lead to non‐radiative regeneration of NO 3 − . The influence of the aqueous solution is considered using polarizable continuum solvation in combination with explicitly solvated model systems. Despite the charged and polar nature of nitrate, we find that solvent effects exert a suprisingly small influence, neither changing the shape of the PES, nor affecting the nature of the excited states.
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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) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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".