Polyamorphism in Water: Amorphous Ices and their Glassy States

Abstract:

Water is ubiquitous and of general importance for our environment. But it is also known as the most anomalous liquid. The fundamental origin of the numerous anomalies of water is still under debate. An understanding of these anomalous properties of water is closely linked to an understanding of the phase diagram of the metastable non-crystalline states of ice.

The process of pressure induced amorphization of ice was first observed by Mishima et al. [1]. The authors pressurized hexagonal ice at 77 K up to a pressure of 1.6 GPa to form high density amorphous ice (HDA). So far three distinct structural states of amorphous water are known [2], they are called low- (LDA), high- (HDA) and very high density amorphous ice (VHDA). Since the discovery of multiple distinct amorphous states it is controversy discussed whether this phenomenon of polyamorphism at high pressures is connected to the occurrence of more than one supercooled liquid phase [3]. Alternatively, amorphous ices have been suggested to be of nanocrystalline nature, unrelated to liquids. Indeed inelastic X-ray scattering measurements indicate sharp crystal-like phonons in the amorphous ices [4]. In case of LDA the connection to the low-density liquid (LDL) was inferred from several experiments including the observation of a calorimetric glass-to-liquid transition at 136 K and ambient pressure [5]. Recently also the glass transition in HDA was observed at 116 K at ambient pressure [6] and at 140 K at elevated pressure of 1 GPa [7], using calorimetric measurements as well as dielectric spectroscopy.

We discuss here the general importance of amorphous ices and their liquid counterparts and present calorimetric and dielectric measurements on LDA and HDA. The good agreement between dielectric and calorimetric results convey for a clearer picture of water's vitrification phenomenon.

[1] O. Mishima, L. D. Calvert, and E. Whalley, Nature 314, 76, 1985

[2] D.T. Bowron, J. L. Finney, A. Hallbrucker, et al., J. Chem. Phys. 125, 2006

[3] P.G. Debenedetti, J. Phys.: Condens. Matter 15, R1669, 2003

[4] H. Schober, M.M. Koza et al., PRL 85, 4100, 2000

[5] G.P. Johari, A. Hallbrucker and E. Mayer Nature 330, 552, 1987

[6] K. Amann-Winkel, C. Gainaru, et al., PNAS 110, 17720, 2013

[7] Andersson, O., PNAS 108, 11013, 2011