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Local initiation conditions for water autoionization.

ABSTRACT: The pH of liquid water is determined by the infrequent process in which water molecules split into short-lived hydroxide and hydronium ions. This reaction is difficult to probe experimentally and challenging to simulate. One of the open questions is whether the local water structure around a slightly stretched OH bond is actually initiating the eventual breakage of this bond or whether this event is driven by a global ordering that involves many water molecules far away from the reaction center. Here, we investigated the self-ionization of water at room temperature by rare-event ab initio molecular dynamics and obtained autoionization rates and activation energies in good agreement with experiments. Based on the analysis of thousands of molecular trajectories, we identified a couple of local order parameters and show that if a bond stretch occurs when all these parameters are around their ideal range, the chance for the first dissociation step (double-proton jump) increases from [Formula: see text] to 0.4. Understanding these initiation triggers might ultimately allow the steering of chemical reactions.

SUBMITTER: Moqadam M

PROVIDER: S-EPMC5960278 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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Local initiation conditions for water autoionization.

Moqadam Mahmoud M Lervik Anders A Riccardi Enrico E Venkatraman Vishwesh V Alsberg Bjørn Kåre BK van Erp Titus S TS

Proceedings of the National Academy of Sciences of the United States of America 20180430 20

The pH of liquid water is determined by the infrequent process in which water molecules split into short-lived hydroxide and hydronium ions. This reaction is difficult to probe experimentally and challenging to simulate. One of the open questions is whether the local water structure around a slightly stretched OH bond is actually initiating the eventual breakage of this bond or whether this event is driven by a global ordering that involves many water molecules far away from the reaction center. ...[more]

PMID: 29712836

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Project description:BackgroundIn order to regulate water flow, hydraulic structures such as weirs or checks, frequently equipped with gates, are used. Water can flow below or over the gate or, simultaneously, over and below the gate. Both diversifications of hydraulic gradient, being an effect of damming up a river by the structure and shear stresses at the bed, which exceeds the critical shear stress value, invoke the local scouring downstream the structure. This phenomenon has been studied in laboratory and field conditions for many years, however Researchers do not agree on the parameters that affect the size of the local scour and the intensity of its formation. There are no universal methods for estimating its magnitude However, solutions are sought in the form of calculation formulas typical for the method of flow through the structure, taking into account the parameters that characterize a given structure. These formulas are based on factors that affect the size of the local scours, that is, their dimensions and location. Examples of such formulas are those contained in this article: Franke (1960), Straube (1963), Tarajmovič (1966), Rossinski & Kuzmin (1969) equations. The need to study this phenomenon results from the prevalence of hydrotechnical structures equipped with gates (from small gated checks to large weirs) and from potential damage that may be associated with excessive development of local erosion downstream, including washing of foundations and, consequently, loss of stability of the structure.MethodsThis study verifies empirical formulas applied to estimate the geometry parameters of a scour hole on a laboratory model of a structure where water is conducted downstream the gate with bottom reinforcements of various roughness. A specially designed remote-controlled measuring device, equipped with laser scanner, was applied to determine the shape of the sandy bottom. Then the formula optimization is conducted, using Monte Carlo sampling method, followed by verification of field conditions.ResultsThe suitability of a specially designed device, equipped with laser scanner for measuring the bottom shape in laboratory conditions was demonstrated. Simple formula describing local scour geometry in laboratory conditions was derived basing on the Straube formula. The optimized formula was verified in field conditions giving very good comparative results. Therefore, it can be applied in engineering and designing practices.

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Local initiation conditions for water autoionization.

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Local initiation conditions for water autoionization.

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