标题： 水异常可能的热力学起源在负压下非经典蒸汽凝结中的表现 显示英文标题

标题： Manifestations of the possible thermodynamic origin of water's anomalies in non-classical vapor nucleation at negative pressures

摘要： 多年来，提出了各种情景——如稳定性极限猜想（SLC）、两个临界点（TCP）、无临界点（CPF）和无奇点（SF）——以解释过冷水异常的热力学起源。 然而，由于亚稳态水的快速相变，直接的实验验证具有挑战性。 在本研究中，我们探讨了亚稳态水的相变路径是否能为这些异常的热力学起源提供见解。 使用具有现实理论水模型的经典密度泛函理论方法，我们研究了不同热力学情景如何影响负压下的蒸发成核动力学。 我们的研究结果表明，在等压和等容冷却过程中，成核动力学和机制存在显著变化。 在TCP情景中，等压冷却期间成核势垒持续增加，在较低温度（Ts）处接近Widom线时略有下降。 相反，SF情景显示成核势垒单调增加。 对于CPF情景，我们观察到一种非经典机制，例如润湿介导的成核（生长的蒸汽核被中间低密度液相润湿）以及低温下的Ostwald步骤规则。 等容冷却路径也揭示了TCP和CPF情景之间T依赖的成核势垒趋势的显著差异。 总体而言，这项研究强调了分析相变动力学和机制的重要性，以理解过冷水异常的精确热力学起源。 显示英文摘要

摘要： Over the years, various scenarios -- such as the stability-limit conjecture (SLC), two critical point (TCP), critical point-free (CPF), and singularity-free (SF) -- have been proposed to explain the thermodynamic origin of supercooled waters anomalies. However, direct experimental validation is challenging due to the rapid phase transition from metastable water. In this study, we explored whether the phase transition pathways from metastable water provide insight into the thermodynamic origin of these anomalies. Using a classical density functional theory approach with realistic theoretical water models, we examined how different thermodynamic scenarios influence vapor nucleation kinetics at negative pressures. Our findings show significant variations in nucleation kinetics and mechanism during both isobaric and isochoric cooling. In the TCP scenario, the nucleation barrier increases steadily during isobaric cooling, with a slight decrease near the Widom line at lower temperatures (Ts). In contrast, the SF scenario shows a monotonic increase in the nucleation barrier. For the CPF scenario, we observed a non-classical mechanism, such as wetting-mediated nucleation (where the growing vapor nucleus is wetted by the intermediate low-density liquid phase) and the Ostwald step rule at low temperatures. Isochoric cooling pathways also revealed notable differences in T-dependent nucleation barrier trends between the TCP and CPF scenarios. Overall, this study underscores the importance of analyzing phase transition kinetics and mechanism to understand the precise thermodynamic origin of supercooled waters anomalies.