Link between the diversity, heterogeneity and kinetic properties of amorphous ice structures

TL;DR

This study reveals how the preparation conditions of amorphous ice influence its microscopic heterogeneity and transformation kinetics, identifying only two homogeneous disordered structures and linking heterogeneity to transformation speed.

Contribution

It establishes a correlation between preparation conditions, heterogeneity, and kinetics in amorphous ice, highlighting the roles of static structure factors and pressure-temperature treatments.

Findings

Homogeneous structures are vHDA and LDA.

Heterogeneity decreases with higher pressure and temperature.

Less heterogeneous structures transform more slowly.

Abstract

Based on neutron wide-angle diffraction and small-angle neutron scattering experiments, we show that there is a correlation between the preparational conditions of amorphous ice structures, their microscopic structural properties, the extent of heterogeneities on a mesoscopic spatial scale and the transformation kinetics. There are only two modifications that can be identified as homogeneous disordered structures, namely the very high-density vHDA and the low-density amorphous LDA ice. Structures showing an intermediate static structure factor with respect to vHDA and LDA are heterogeneous phases. This holds independently from their preparation procedure, i.e. either obtained by pressure amorphisation of ice I_h or by heating of vHDA. The degree of heterogeneity can be progressively suppressed when higher pressures and temperatures are applied for the sample preparation. In accordance with the suppressed heterogeneity the maximum of the static structure factor displays a pronounced narrowing of the first strong peak, shifting towards higher Q-numbers. Moreover, the less heterogeneous the obtained structures are the slower is the transformation kinetics from the high--density modifications into LDA. The well known high-density amorphous structure HDA does not constitute any particular state of the amorphous water network. It is formed due to the preparational procedure working in liquid nitrogen as thermal bath, i.e. at about 77 K.