Caupin Frédéric, Anisimov Mikhail A
Institut Lumière Matière, Université de Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622 Villeurbanne, France.
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742, USA.
Phys Rev Lett. 2021 Oct 29;127(18):185701. doi: 10.1103/PhysRevLett.127.185701.
Liquid polyamorphism is the intriguing possibility for a single component substance to exist in multiple liquid phases. We propose a minimal model for this phenomenon. Starting with a binary lattice model with critical azeotropy and liquid-liquid demixing, we allow interconversion of the two species, turning the system into a single-component fluid with two states differing in energy and entropy. Unveiling the phase diagram of the noninterconverting binary mixture gives unprecedented insight on the phase behaviors accessible to the interconverting fluid, such as a liquid-liquid transition with a critical point, or a singularity-free scenario, exhibiting thermodynamic anomalies without polyamorphism. The model provides a unified theoretical framework to describe supercooled water and a variety of polyamorphic liquids with waterlike anomalies.
液体多晶型现象是指单一成分物质能够以多种液相形式存在的一种有趣可能性。我们针对这一现象提出了一个极简模型。从具有临界共沸和液 - 液分离的二元晶格模型出发,我们允许两种组分相互转化,从而将系统转变为具有两种能量和熵不同状态的单一组分流体。揭示非相互转化二元混合物的相图,能为相互转化流体可呈现的相行为提供前所未有的见解,比如具有临界点的液 - 液转变,或者无奇异点的情形,即展现出无多晶型现象的热力学异常。该模型提供了一个统一的理论框架,用于描述过冷水以及各种具有类似水异常的多晶型液体。