The dynamic crossover in water does not require bulk water

Turton, D.A., Corsaro, C., Martin, D.F., Mallamace, F. and Wynne, K. (2012) The dynamic crossover in water does not require bulk water. Physical Chemistry Chemical Physics, 14(22), pp. 8067-8073. (doi: 10.1039/C2CP40703E)

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Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquid–liquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that “bulk” water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional Stokes–Einstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to “worm-hole” structure.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Turton, Dr David and Wynne, Professor Klaas
Authors: Turton, D.A., Corsaro, C., Martin, D.F., Mallamace, F., and Wynne, K.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Physical Chemistry Chemical Physics
Publisher:Royal Society of Chemistry
ISSN (Online):1463-9084
Published Online:24 April 2012
Copyright Holders:Copyright © 2012 Royal Society of Chemistry
First Published:First published in Physical Chemistry Chemical Physics 14(22):8067-8073
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
559071Two-dimensional terahertz/IR spectroscopy: a unique probe of ultrafast hydrogen-bond dynamics of liquid water and model systems.Klaas WynneEngineering & Physical Sciences Research Council (EPSRC)EP/F06926X/1CHEM - CHEMISTRY
571341Liquid-liquid transitions in molecular liquids: from supramolecular structure to phase separationKlaas WynneEngineering & Physical Sciences Research Council (EPSRC)EP/J004790/1CHEM - CHEMISTRY
563561Terahertz spectroscopy of aqueous ionic solutions to understand the role of hydrogen-bond network breaking and strengthening in the HofmeisterKlaas WynneEngineering & Physical Sciences Research Council (EPSRC)EP/E046541/1CHEM - CHEMISTRY