Volume analysis of supercooled water under high pressure

Abstract

Motivated by an experimental finding on the density of supercooled water at high pressure [O. Mishima, J. Chem. Phys. 133, 144503 (2010)] we performed atomistic molecular dynamics simulations study of bulk water in the isothermal-isobaric ensemble. Cooling and heating cycles at different isobars and isothermal compression at different temperatures are performed on the water sample with pressures that range from 0 to 1.0 GPa. The cooling simulations are done at temperatures that range from 40 K to 380 K using two different cooling rates, 10 K/ns and 10 K/5 ns. For the heating simulations we used the slowest heating rate (10 K/5 ns) by applying the same range of isobars. Our analysis of the variation of the volume of the bulk water sample with temperature at different pressures from both isobaric cooling/heating and isothermal compression cycles indicates a concave-downward curvature at high pressures that is consistent with the experiment for emulsified water. In particular, a strong concave down curvature is observed between the temperatures 180 K and 220 K. Below the glass transition temperature, which is around 180 K at 1GPa, the volume turns to concave upward curvature. No crystallization of the supercooled liquid state was observed below 180 K even after running the system for an additional microsecond.