Phase behavior of metastable water from large-scale simulations of a quantitatively accurate model near ambient conditions: The liquid-liquid critical point

Abstract

The molecular mechanisms of water’s unique anomalies are still debated upon. Experimental challenges have led to simulations suggesting a liquid–liquid (LL) phase transition, culminating in the supercooled region’s LL critical point (LLCP). Computational expense, small system sizes, and the reliability of water models often limit these simulations. We adopt the CVF model, which is reliable, transferable, scalable, and efficient across a wide range of temperatures and pressures around ambient conditions. By leveraging the timescale separation between fast hydrogen bonds and slow molecular coordinates, the model allows a thorough exploration of the metastable phase diagram of liquid water. Using advanced numerical techniques to bypass dynamical slowing down, we perform finite-size scaling on larger systems than those used in previous analyses. Our study extrapolates thermodynamic behavior in the infinite-system limit, demonstrating the existence of the LLCP in the 3D Ising universality class in the low-temperature, low-pressure side of the line of temperatures of maximum density, specifically at <em>TC </em>= 186 ± 4 K and <em>PC </em>= 174 ± 14 MPa, at the end of a liquid–liquid phase separation stretching up to ∼200 MPa. These predictions align with recent experimental data and sophisticated models, highlighting that hydrogen bond cooperativity governs the LLCP and the origin of water anomalies. We also observe substantial cooperative fluctuations in the hydrogen bond network at scales larger than 10 nm, even at temperatures relevant to biopreservation. These findings have significant implications for nanotechnology and biophysics, providing new insights into water’s behavior under varied conditions.