Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2011 Oct 7;135(13):134503. doi: 10.1063/1.3643333.
We use numerical simulation to examine the possibility of a reversible liquid-liquid transition in supercooled water and related systems. In particular, for two atomistic models of water, we have computed free energies as functions of multiple order parameters, where one is density and another distinguishes crystal from liquid. For a range of temperatures and pressures, separate free energy basins for liquid and crystal are found, conditions of phase coexistence between these phases are demonstrated, and time scales for equilibration are determined. We find that at no range of temperatures and pressures is there more than a single liquid basin, even at conditions where amorphous behavior is unstable with respect to the crystal. We find a similar result for a related model of silicon. This result excludes the possibility of the proposed liquid-liquid critical point for the models we have studied. Further, we argue that behaviors others have attributed to a liquid-liquid transition in water and related systems are in fact reflections of transitions between liquid and crystal.
我们使用数值模拟来研究过冷水中及相关体系中可能存在的可逆液-液相变。具体来说,对于两种水分子的原子模型,我们计算了多个序参量的自由能,其中一个是密度,另一个则区分晶体和液体。在一系列温度和压力下,我们发现了液体和晶体的自由能盆地是分开的,证明了这些相之间存在相共存的条件,并确定了平衡的时间尺度。我们发现,在任何温度和压力范围内,都不存在多个液体盆地,即使在相对于晶体不稳定的无定形行为的条件下也是如此。我们在一个类似的硅模型中也得到了类似的结果。这一结果排除了我们所研究的模型中提出的液-液相变临界点的可能性。此外,我们认为其他人归因于水和相关体系中液-液转变的行为实际上是液体和晶体之间转变的反映。