Corresponding states for mesostructure and dynamics of supercooled water

TL;DR

This paper develops a theoretical framework using scaling arguments and simulations to analyze the mesostructure and dynamics of supercooled water, revealing phase behavior and dynamical arrest phenomena.

Contribution

It introduces a corresponding states approach for water and water-like materials, providing a phase diagram and insights into equilibrium and non-equilibrium behaviors.

Findings

Derived a phase diagram for bulk and confined water.

Identified two reversible condensed phases: ice and liquid.

Explained dynamical arrest and polyamorphism in supercooled water.

Abstract

Water famously expands upon freezing, foreshadowed by a negative coefficient of expansion of the liquid at temperatures close to its freezing temperature. These behaviors, and many others, reflect the energetic preference for local tetrahedral arrangements of water molecules and entropic effects that oppose it. Here, we provide theoretical analysis of mesoscopic implications of this competition, both equilibrium and non-equilibrium, including mediation by interfaces. With general scaling arguments bolstered by simulation results, and with reduced units that elucidate corresponding states, we derive a phase diagram for bulk and confined water and water-like materials. For water itself, the corresponding states cover the temperature range of 150 K to 300 K and the pressure range of 1 bar to 2 kbar. In this regime, there are two reversible condensed phases - ice and liquid. Out of equilibrium, there is irreversible polyamorphism, i.e., more than one glass phase, reflecting dynamical arrest of coarsening ice. Temperature-time plots are derived to characterize time scales of the different phases and explain contrasting dynamical behaviors of different water-like systems.