Experimental and theoretical studies of the gas-phase reactions of O($^1$D) with H$_2$O and D$_2$O at low temperature
Bibliographic record
Abstract
Here we report the results of an experimental and theoretical study of the gas-phase reactions between O($^1$D) and H$_2$O and O($^1$D) and D$_2$O at room temperature and below. On the experimental side, the kinetics of these reactions have been investigated over the 50-127 K range using a continuous flow Laval nozzle apparatus, coupled with pulsed laser photolysis and pulsed laser induced fluorescence for the production and detection of O($^1$D) atoms respectively. Experiments were also performed at 296 K in the absence of a Laval nozzle. On the theoretical side, the existing full-dimensional ground X$^1$A potential energy surface for the H$_2$O$_2$ system involved in this process has been reinvestigated and enhanced to provide a better description of the barrierless H-atom abstraction pathway. Based on this enhanced potential energy surface, quasiclassical trajectory calculations and ring polymer molecular dynamics simulations have been performed to obtain low temperature rate constants. The measured and calculated rate constants display similar behaviour above 100 K, showing little or no variation as a function of temperature. Below 100 K, the experimental rate constants increase dramatically, in contrast to the essentially temperature independent theoretical values. The possible origins of the divergence between experiment and theory at low temperatures are discussed.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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".