Phase behaviour of metastable water

Abstract

THE metastable extension of the phase diagram of liquid water exhibits rich features that manifest themselves in the equilibrium properties of water. For example, the density maximum at 4 °C and the minimum in the isothermal compressibility at 46 °C are thought to reflect the presence of singularities in the behaviour of thermodynamic quantities occurring in the supercooled region^{1 2}. The 'stability–limit conjecture'^3–5 suggests that these thermodynamic anomalies arise from a single limit of mechanical stability (spinodal line), originating at the liquid–gas critical point, which determines the limit of both superheating at high temperatures and supercooling at low temperatures. Here we present a comprehensive series of molecular dynamics simulations which suggest that, instead, the supercooling anomalies are caused by a newly identified critical point, above which the two metastable amorphous phases of ice (previously shown to be separated by a line of first-order transitions^6,7) become indistinguishable. The two amorphous ice phases are thus incorporated into our understanding of the liquid state, providing a more complete picture of the metastable and stable behaviour of water.