Translational diffusion in supercooled water at and near the glass transition temperature -- 136 K

TL;DR

This study investigates whether water becomes a true ergodic liquid with translational diffusion at the glass transition temperature of 136 K by measuring diffusion in nanoscale water films.

Contribution

It provides experimental evidence that water exhibits translational diffusion at the glass transition, supporting the hypothesis that water is a strong liquid near 136 K.

Findings

Water diffuses in nanoscale films at 136 K with an Arrhenius activation energy of 40.8 kJ/mol.

Diffusive mixing occurs prior to crystallization in films 20-100 nm thick.

The measured diffusion coefficient at 136 K is 6.25 x 10^{-21} m^2/s.

Abstract

The properties of amorphous solid water at and near the calorimetric glass transition temperature, $T_{g}$, of 136 K have been debated for years. One hypothesis is that water turns into a "true" liquid at $T_{g}$ (i.e., it becomes ergodic) and exhibits all the characteristics of an ergodic liquid, including translational diffusion. A competing hypothesis is that only rotational motion becomes active at $T_{g}$, while the "real" glass transition in water is at a considerably higher temperature. To address this dispute, we have investigated the diffusive mixing in nanoscale water films, with thicknesses up to ~100 nm, using infrared (IR) spectroscopy. The experiments used films that were composed of at least 90% $H_{2}O$ with $D_{2}O$ making up the balance and were conducted in conditions where H/D exchange was essentially eliminated. Because the IR spectra of multilayer $D_{2}O$ films (e.g., thicknesses of ~3 - 6 nm) embedded within thick $H_{2}O$ films are distinct from the spectrum of isolated $D_{2}O$ molecules within $H_{2}O$, the diffusive mixing of (initially) isotopically layered water films could be followed as a function of annealing time and temperature. The results show that water films with total thicknesses ranging from ~20 to 100 nm diffusively mixed prior to crystallization for temperatures between 120 and 144 K. The translational diffusion had an Arrhenius temperature dependence with an activation energy of 40.8 kJ/mol, which indicates that water at and near $T_{g}$ is a strong liquid. The measured diffusion coefficient at 136 K is 6.25 x 10$^{-21} m^{2}/s$.