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.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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) | 0.001 | 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".