Density equalisation in supercooled high- and low-density water mixtures.

The temporal evolution of two model high-density/low-density (HDL/LDL) interfaces was examined from molecular dynamics (MD) calculations at temperatures close to the predicted second critical point of water for three water models. In all cases, interfacial density equalisation occurred rapidly showing no preference for inhomogenous distribution. A uniform density (of ca. 0.99-1.067 g/cm(3), depending on the potential) was always observed at the interface, indicating the free energy of water in low- and high-density forms is metastable, and that LDL and HDL should not coexist as independent entities at thermodynamic equilibrium. It is reckoned that previous MD studies supporting the "two-liquid" model have an explicit, if inappropriate, assumption of mechanical equilibrium between the two phases. The present result challenges the notion that a second critical point exists, and that LDL/HDL mixtures could be even kinetically metastable.