Structural and topological changes across the liquid-liquid transition in water

TL;DR

This study uses simulations of the TIP4P/Ice water model to visualize and analyze the structural and topological changes in water during the liquid-liquid transition, revealing that high-density liquid structures arise from the folding of long rings in the hydrogen-bond network.

Contribution

It provides new insights into the topological mechanisms underlying the liquid-liquid transition in water, focusing on the role of ring structures in the hydrogen-bond network.

Findings

High-density liquid features interstitial molecules from folded long rings.

Structural changes involve the collapse of the second neighbor shell.

Topological analysis reveals the importance of ring folding in the transition.

Abstract

It has recently been shown that the TIP4P/Ice model of water can be studied numerically in metastable equilibrium at and below its liquid-liquid critical temperature. We report here simulations along a subcritical isotherm, for which two liquid states with the same pressure and temperature, but different density, can be equilibrated. This allows for a clear visualisation of the structural changes taking place across the transition. We specifically focus on how the topological properties of the H-bond network change across the liquid-liquid transition. Our results demonstrate that the structure of the high-density liquid, characterised by the existence of interstitial molecules and commonly explained in terms of the collapse of the second neighbour shell, actually originates from the folding back of long rings, bringing pairs of molecules separated by several hydrogen-bonds close by in space.