Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water

Singh, Rakesh S and Bagchi, Biman (2014) Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water. In: JOURNAL OF CHEMICAL PHYSICS, 140 (16).

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Abstract

The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments. (C) 2014 AIP Publishing LLC.

Item Type:	Journal Article
Publication:	JOURNAL OF CHEMICAL PHYSICS
Publisher:	AMER INST PHYSICS
Additional Information:	Copyright for this article belongs to the AMER INST PHYSICS, CIRCULATION & FULFILLMENT DIV, 2 HUNTINGTON QUADRANGLE, STE 1 N O 1, MELVILLE, NY 11747-4501 USA
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	14 Jun 2014 05:16
Last Modified:	14 Jun 2014 05:16
URI:	http://eprints.iisc.ac.in/id/eprint/49257

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