A Local Structural Basis to Resolve Amorphous Ices

TL;DR

This study introduces a probabilistic framework to identify local structural variables that distinguish low-density and high-density amorphous ices, revealing a simple redistribution mechanism during phase transitions.

Contribution

The paper presents a novel data-driven approach to characterize local structures in amorphous phases, specifically applied to water, uncovering the microscopic basis of phase distinctions.

Findings

Local density descriptors distinguish LDA and HDA

Phase transition involves redistribution of local environments

Transitions occur without intermediate structures, resembling first-order transitions

Abstract

Phases with distinct thermodynamic properties must differ in their underlying distributions of microscopic structures. While ordered phases are readily distinguished by unit cells and space groups, the local structural basis differentiating amorphous phases is less apparent. Here, using a new probabilistic data-driven framework applied to molecular simulation data on water, we identify local collective variables that discriminate low-density and high-density amorphous (LDA and HDA) ices and characterize pressure-induced transitions between these phases. As expected, descriptors related to local density capably distinguish LDA and HDA; however, phase identity is surprisingly encoded within the first coordination shell. Furthermore, LDA transitions to HDA by a simple redistribution of LDA- and HDA-like environments with no evident intermediate structures, in accordance with a first-order-like transition that contrasts with the gradual evolution observed in other amorphous systems such as metallic glasses. These findings are robust across force fields, which themselves exhibit structural differences, and exemplify how other systems lacking obvious distinguishing features can be characterized.