论文标题
在负压下水中的异常蒸气和冰核：经典密度功能理论研究
Anomalous Vapor and Ice Nucleation in Water at Negative Pressures: A Classical Density Functional Theory Study
论文作者
论文摘要
与水的异常行为相比，水的热力学异常与从亚稳态水的相变动力学之间的关系是相对尚未探索的。在这项工作中，我们采用了经典的密度功能理论来提供亚稳态水的统一和连贯的成核图片（蒸气和冰），尤其是在负压条件下。我们的结果表明，在液态蒸气相对于冰相的液体蒸气共存是液态蒸气表面张力的特殊非单调温度依赖性。等距冷却上的蒸气成核屏障还显示出非单调温度依赖性。我们进一步指出，对于较低密度的等音方差，最小蒸气成核屏障的温度（$ t_ {ΔΩ_{\ rm v/min v/min}^*} $）与最大稳定性的最大密度（TMD）温度不一致。然而，$ t_ {δω_{\ rm v/min}^*} $与TMD之间的温度差，随着等位分线的密度增加，表明在高密度下液体水的液化倾向与液体稳定性之间存在很强的相关性。沿等速冷却的蒸气成核势垒显示出有趣的交叉行为，在降低温度时首先增加，然后在Widom线附近显示出非单调的行为，以进一步降低温度。我们对亚稳态水的冰成核的结果表明，沿等热的冰成核屏障的反回反性行为，理论上验证了最近的发现，即冰核动力学动力学的重新入侵冰（IH） - 液可以诱导急剧变化。此外，这项研究还提供了更深入的见解，可最大程度地对等温冷却的原始可压缩性。
In contrast to the abundance of work on the anomalous behavior of water, the relationship between the water's thermodynamic anomalies and kinetics of phase transition from metastable water is relatively unexplored. In this work, we have employed classical density functional theory to provide a unified and coherent picture of nucleation (both vapor and ice) from metastable water, especially at negative pressure conditions. Our results suggest a peculiar non-monotonic temperature dependence of liquid-vapor surface tension at temperatures where liquid-vapor coexistence is metastable with respect to the ice phase. The vapor nucleation barrier on isochoric cooling also shows a non-monotonic temperature dependence. We further note that, for lower density isochores, the temperature of minimum vapor nucleation barrier ($T_{ΔΩ_{\rm v/min}^*}$) does not coincide with the temperature of maximum density (TMD) where metastability is maximum. The temperature difference between the $T_{ΔΩ_{\rm v/min}^*}$ and the TMD, however, decreases with increasing the density of the isochore, suggesting a strong correlation between the propensity of cavitation and metastability of the liquid water at high densities. The vapor nucleation barrier along isobaric cooling shows an interesting crossover behavior where it first increases on lowering the temperature and then shows a non-monotonic behavior in the vicinity of the Widom line on further lowering the temperature. Our results on the ice nucleation from metastable water show an anomalous retracing behavior of the ice nucleation barrier along isotherms and theoretically validate the recent findings that the reentrant ice(Ih)-liquid coexistence can induce a drastic change in the kinetics of ice nucleation. In addition, this study also provides deeper insights into the origin of the isothermal compressibility maximum on isochoric cooling.
