Bibliographic record
Abstract
The mechanism for isotopic exchange by proton hopping and subsequent reorientation of H2O molecules in vapor-deposited, 0.1 mol % 2-naphthol containing amorphous solid water [M. Fischer and J. P. Devlin, J. Phys. Chem. 99, 11584 (1995)] has been reconsidered and an alternative mechanism in terms of diffusion controlled reactions is proposed. In this mechanism, H2O molecules diffuse within the H-bonded clusters, with or without a net increase in the number of H bonds, and isotopic exchange occurs by two processes: (i) Random diffusion of molecules in two clusters, one containing D2O and the other H3O+, leads to formation of an intercluster H bond, which in turn provides a path for proton hopping and converts one D2O (plus one H2O) to two coupled HODs by proton translocation and subsequent orientation. (ii) One H bond between two HOD neighbors in a cluster breaks and reforms with another H2O in the same cluster or in a different cluster, and hence a coupled HOD is converted to an uncoupled HOD. The decrease in D2O and the increase in HOD concentrations with time follow a stretched exponential kinetics, with exponent of 0.65 for the former and 0.54 for the latter process at 122 K. This is equivalent to the time-dependent rate constant in Plonka’s formalism [J. Chem. Phys. 96, 1128 (1992)] and is seen as characteristic of dispersive kinetics. Because fluctuation of the environment is slower than the time scale of overall barrier crossing, the mass-controlled kinetics equations do not apply to a consecutive reaction scheme. The known variation of the isotopic species concentration with time seems to be consistent with this reaction kinetics.
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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 | 0.001 |
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 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".