Liquid-liquid transition in supercooled water suggested by microsecond simulations

by Li, Yaping; Li, Jicun; Wang, Feng

The putative liquid-liquid phase transition in supercooled water has been used to explain many anomalous behaviors of water. However, no direct experimental verification of such a phase transition has been accomplished, and theoretical studies from different simulations contradict each other. We investigated the putative liquid-liquid phase transition using the Water potential from Adaptive Force Matching for Ice and Liquid (WAIL). The simulation reveals a first-order phase transition in the supercooled regime with the critical point at similar to 207 K and 50 MPa. Normal water is high-density liquid (HDL). Low-density liquid (LDL) emerges at lower temperatures. The LDL phase has a density only slightly larger than that of the ice-Ih and shows more long-range order than HDL. However, the transformation from LDL to HDL is spontaneous across the first-order phase transition line, suggesting the LDL configuration is not poorly formed nanocrystalline ice. It has been demonstrated in the past that the WAIL potential provides reliable predictions of water properties such as melting temperature and temperature of maximum density. Compared with other simple water potentials, WAIL is not biased by fitting to experimental properties, and simulation with this potential reflects the prediction of a high-quality first-principle potential energy surface.

Journal
Proceedings of the National Academy of Sciences of the United States of America
Volume
110
Issue
30
Year
2013
Start Page
12209-12212
URL
https://dx.doi.org/10.1073/pnas.1309042110
ISBN/ISSN
1091-6490; 0027-8424
DOI
10.1073/pnas.1309042110