Advances in Computational Studies of the Liquid–Liquid Transition in Water and Water-Like Models,Chemical Reviews

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Advances in Computational Studies of the Liquid–Liquid Transition in Water and Water-Like Models
Chemical Reviews ( IF 51.4 ) Pub Date : 2018-08-28 00:00:00 , DOI: 10.1021/acs.chemrev.8b00228
Jeremy C. Palmer ₁ , Peter H. Poole ₂ , Francesco Sciortino ₃ , Pablo G. Debenedetti ₄

Affiliation

There has been uninterrupted interest in supercooled water ever since the pioneering experiments of Speedy and Angell revealed sharp increases in this substance’s response functions upon supercooling. One intriguing hypothesis that was formulated to explain this behavior involves the existence of a metastable liquid–liquid transition (LLT) at deeply supercooled conditions. The preponderance of experimental evidence is consistent with this hypothesis, although no definitive proof exists to date. Computational studies have played an important role in this area, because ice nucleation can in principle be controlled in silico. It has been claimed, controversially, that the LLT is a misinterpreted liquid–solid transition in all models of water. Recent studies disprove this viewpoint by providing unambiguous counter-examples of distinct liquid–liquid and liquid–crystal transitions in tetrahedral models. In one, state-of-the-art sampling methods were used to compute the free energy surface of a molecular model of water and revealed the existence of two liquid phases in metastable equilibrium with each other and a stable crystal phase, at the same, deeply supercooled thermodynamic conditions. Further studies showed that, by tuning the potential parameters of a model tetrahedral system, it is possible to make the LLT evolve continuously from metastability to being thermodynamically stable with respect to crystallization. Most recently, it has been shown that the simulation code used to challenge the hypothesis of an LLT contains conceptual errors that invalidate the results on which the challenge was based, definitively resolving the controversy. The debate has vastly expanded the range of fundamental questions being pursued about phase transitions in metastable systems and ushered the use of increasingly sophisticated computational methods to explore the possible existence of LLTs in model systems.

中文翻译：

水和水样模型中液体-液体转变的计算研究进展

自从Speedy和Angell的开创性实验揭示了这种物质在过冷时的响应功能急剧增加以来，对过冷水的兴趣就一直不间断。为解释这种行为而提出的一个有趣的假设涉及在过冷状态下存在亚稳态的液-液转变（LLT）。尽管迄今为止还没有确切的证据，但实验证据的优势与这一假设是一致的。计算研究在该领域发挥了重要作用，因为原则上可以通过计算机控制冰核化。有争议的是，在所有水模型中，LLT是一种误解的液-固转变。最近的研究通过在四面体模型中提供明显的液-液和液-晶转变的反例，从而证明了这一观点。一种方法是使用最新的采样方法来计算水分子模型的自由能表面，并揭示存在两个处于亚稳平衡状态的液相和一个稳定的结晶相，深度过冷的热力学条件。进一步的研究表明，通过调节模型四面体系统的潜在参数，可以使LLT从亚稳性到结晶的热力学稳定连续发展。最近，已经表明，用于挑战LLT假设的仿真代码包含概念错误，这些错误使挑战所基于的结果无效，从而最终解决了争议。辩论极大地扩展了有关亚稳态系统中相变的基本问题的范围，并引发了越来越复杂的计算方法的使用，以探索模型系统中LLT的可能存在。

更新日期：2018-08-28

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