Phase behavior of metastable water from large-scale simulations of a quantitative accurate model: The liquid-liquid critical point

TL;DR

This study uses large-scale simulations with an accurate water model to confirm the existence of a liquid-liquid critical point in supercooled water, revealing the role of hydrogen bond cooperativity in water's anomalies.

Contribution

It provides the first large-system simulation evidence of the LLCP in water, accurately locating it and linking it to hydrogen bond cooperativity, surpassing previous computational limitations.

Findings

Confirmation of the LLCP at TC = 186 +/- 4 K and PC = 174 +/- 14 MPa.

Large cooperative fluctuations in hydrogen bond networks at nanometer scales.

Alignment of simulation predictions with recent experimental data.

Abstract

Water's unique anomalies are vital in various applications and biological processes, yet the molecular mechanisms behind these anomalies remain debated, particularly in the metastable liquid phase under supercooling and stretching conditions. Experimental challenges in these conditions have led to simulations suggesting a liquid-liquid phase transition between low-density and high-density water phases, culminating in a liquid-liquid critical point (LLCP). However, these simulations are limited by computational expense, small system sizes, and reliability of water models. Using the FS model, we improve accuracy in predicting water's density and response functions across a broad range of temperatures and pressures. The FS model avoid by design first-order phase transitions towards crystalline phases, allowing thorough exploration of the metastable phase diagram. We employ advanced numerical techniques to bypass dynamical slowing down and perform finite-size scaling on systems significantly larger than those used in previous analyses. Our study extrapolates thermodynamic behavior in the infinite-system limit, accurately demonstrating the existence of the LLCP in the 3D Ising universality class at TC = 186 +/- 4 K and PC = 174 +/- 14 MPa, following a liquid-liquid phase separation below 200 MPa. These predictions align with recent experimental data and more sophisticated models, highlighting that hydrogen bond cooperativity governs the LLCP and the origin of water anomalies. Moreover, we observe that the hydrogen bond network exhibits substantial cooperative fluctuations at scales larger than 10 nm, even at temperatures relevant to biopreservation. These findings have significant implications for fields such as nanotechnology and biophysics, offering new insights into water's behavior under varied conditions.