Signatures of Surprising Diffusion-Entropy Scaling across Pressure Induced Glass Transition in Water

TL;DR

This study investigates the pressure-induced glass transition in water, revealing entropy signatures, molecular realignment, and a potential order parameter, across various temperatures, highlighting unique diffusion and structural behaviors.

Contribution

It uncovers novel entropy and molecular realignment signatures associated with water's vitrification under pressure, introducing the O-O-O angle distribution difference as a potential order parameter.

Findings

Sharp entropy crossover at vitrification pressure

Exponential dependence of diffusion on excess entropy

Pressure-induced realignment of water molecules with two peaks in O-O-O angles

Abstract

Because of the negative inclination of the solid-liquid phase separation line in water, ice Ih melts on compression. On further increase in pressure the liquid water transforms into a high density metastable glassy state, characterized by a rapid approach to zero diffusion coefficient and an absence of any crystalline order in the static structure factor. The vitrification is found to occur even at high temperatures (T > 250 K). We study this glass transition process at four temperatures (80 K, 250 K, 300 K and 320 K). The transition pressure increases with increase in temperature, as expected. Interestingly, we find that the total entropy of the system exhibits a sharp crossover near the glass transition pressure where the diffusion of water goes to zero. The diffusion coefficient shows an exponential dependence on the properly defined excess entropy. In an interesting result not reported before, we find a pressure induced realignment of water molecules resulting in two well separated peaks in the O-O-O angle distribution among neighbouring molecules. The difference between the positions of these two peaks undergoes a sharp change at the vitrification pressure suggesting that it can serve as an appropriate order parameter to detect the glass transition point.