Peculiar Thermodynamics of the Second Critical Point in Supercooled Water
Peculiar Thermodynamics of the Second Critical Point in Supercooled Water
复制标题
DOI：
10.1021/jp204011z
复制
发表时间：
2011-12-08
影响因子：
3.3
通讯作者：
Anisimov, M. A.
中科院分区：
文献类型：
--
作者：
Bertrand, C. E.;Anisimov, M. A.
基于临界点普遍性原理，我们研究了过冷水中液-液临界点的特殊热力学。我们表明，水中的液-液临界性代表了流体中一种特殊的临界行为，介于两种极限情况之间：晶格气体（通常用于模拟液-汽转变）和晶格液体（一种具有熵驱动相分离的弱可压缩液体）。晶格气体中的有序场与化学势相关，有序参数与密度相关，而在晶格液体中，有序场与温度相关，有序参数与熵相关。过冷水的行为更接近晶格液体行为，而不是晶格气体行为。利用三岛最近获得的新实验数据[J.化学。物理。 2010, 133, 144503]，我们修改了 Fuentevilla 和 Anisimov 之前建议的参数缩放状态方程 [Phys. 2010, 133, 144503]。莱特牧师。 2006, 97, 195702]，通过调整线性背景、临界振幅和临界压力，得到过冷水热力学异常的一致描述。我们还展示了晶格液体描述如何影响受限介质中过冷水的有限尺寸缩放描述。
On the basis of the principle of critical-point universality, we examine the peculiar thermodynamics of the liquid-liquid critical point in supercooled water. We show that the liquid-liquid criticality in water represents a special kind of critical behavior in fluids, intermediate between two limiting cases: the lattice gas, commonly used to model liquid-vapor transitions, and the lattice liquid, a weakly compressible liquid with an entropy-driven phase separation. While the ordering field in the lattice gas is associated with the chemical potential and the order parameter with the density, in the lattice liquid the ordering field is the temperature and the order parameter is the entropy. The behavior of supercooled water is much closer to lattice-liquid behavior than to lattice-gas behavior. Using new experimental data recently obtained by Mishima [J. Chem. Phys. 2010, 133, 144503], we have revised the parametric scaled equation of state, previously suggested by Fuentevilla and Anisimov [Phys. Rev. Lett. 2006, 97, 195702], and obtain a consistent description of the thermodynamic anomalies of supercooled water by adjusting linear backgrounds, one critical amplitude, and the critical pressure. We also show how the lattice-liquid description affects the finite-size scaling description of supercooled water in confined media.