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Thermodynamic picture of vitrification of water through complex specific heat and entropy: A journey through ``no man's land''

Saito, Shinji and Bagchi, Biman (2019) Thermodynamic picture of vitrification of water through complex specific heat and entropy: A journey through ``no man's land''. In: JOURNAL OF CHEMICAL PHYSICS, 150 (5).

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Official URL: https://doi.org/10.1063/1.5079594


We investigate thermodynamic properties of supercooled water across the ``no man's land'' onto the formation of amorphous ice. The calculations are aided by very long computer simulations, often more than 50 mu s long, with the TIP4P/2005 model potential. Density fluctuations that arise from the proximity to a putative liquid-liquid (LL) transition at 228 K, cast a long shadow on the properties of water, both above and below the LL transition. We carry out the calculations of the quantum mechanical static and frequency-dependent specific heats by combining seminal studies of Lebowitz, Percus, and Verlet and Grest and Nagel with the harmonic approximation for the density of states. The obtained values are in quantitative agreement with all available experimental and numerical results of specific heats for both supercooled water and ice. We calculate the entropy at all the state points by integrating the specific heat. We find that the quantum corrected-contributions of intermolecular vibrational entropy dominate the excess entropy of amorphous phases over the crystal over a wide range of temperatures. Interestingly, the vibrational entropy lowers the Kauzmann temperature, T-K, to 130 K, just below the experimental glass-to-liquid water transition temperature, T-g, of 136 K and the calculated T-g of 135 K in our previous study. A straightforward extrapolation of high temperature entropy from 250 K to below however would give a much higher value of T-K similar to 190 K. The calculation of Lindemann ratios shows the melting of amorphous ice similar to 135 K. The amorphous state exhibits an extremely short correlation length for the distance dependence of orientational correlation. Published under license by AIP Publishing.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to AMER INST PHYSICS
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 23 Feb 2019 08:47
Last Modified: 23 Feb 2019 08:47
URI: http://eprints.iisc.ac.in/id/eprint/61813

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