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Issue 22, 2012
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The dynamic crossover in water does not require bulk water

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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.

Graphical abstract: The dynamic crossover in water does not require bulk water

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Article information

05 Mar 2012
23 Apr 2012
First published
24 Apr 2012

Phys. Chem. Chem. Phys., 2012,14, 8067-8073
Article type

The dynamic crossover in water does not require bulk water

D. A. Turton, C. Corsaro, D. F. Martin, F. Mallamace and K. Wynne, Phys. Chem. Chem. Phys., 2012, 14, 8067
DOI: 10.1039/C2CP40703E

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