Supercooling and freezing processes in nanoconfined water by time-resolved optical Kerr effect spectroscopy

TL;DR

This study uses time-resolved optical Kerr effect spectroscopy to explore how water confined in nanometer-scale pores behaves dynamically and structurally at various hydration levels and temperatures, revealing partial freezing and supercooling phenomena.

Contribution

It provides new insights into the vibrational and relaxation dynamics of nanoconfined water, highlighting the effects of hydration and temperature on freezing and supercooling behaviors.

Findings

No freezing occurs at low hydration levels, water remains mobile.

Ice formation occurs at about 248 K in fully hydrated samples.

Structural relaxation times are strongly affected by hydration level.

Abstract

Using heterodyne-detected optical Kerr effect (HD-OKE) measurements, we investigate the vibrational dynamics and the structural relaxation of water nanoconfined in Vycor porous silica samples (pore size $\simeq~4~nm$ ) at different levels of hydration and temperatures. At low level of hydration, corresponding to two complete superficial water layers, no freezing occurs and water remains mobile at all the investigated temperatures with dynamic features similar, but not equal, to the bulk water. The fully hydrated sample shows formation of ice at about 248 K, this process does not involve all the contained water; a part of it remains in a supercooled phase. The structural relaxation times measured from the decay of the time-dependent HD-OKE signal shows temperature dependence largely affected by the hydration level; the low frequency ($\nu<500~cm^{-1}$) vibrational spectra, obtained by the Fourier transforms of HD-OKE signal, appears less affected by confinement.