The glassy states of water are of common interest as the majority of H 2 O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water's calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules. This "double T g scenario" is related to the coexistence of two liquid phases. The calorimetric signature of the second glass transition is much less feeble, with a heat capacity increase at T g,2 about five times as large as at T g,1 . By using broadband-dielectric spectroscopy we resolve loss peaks yielding relaxation times near 100 s at 126 K for low-density amorphous ice and at 110 K for high-density amorphous ice as signatures of these two distinct glass transitions. Temperature-dependent dielectric data and heating-rate-dependent calorimetric data allow us to construct the relaxation map for the two distinct phases of water and to extract fragility indices m = 14 for the low-density and m = 20-25 for the high-density liquid. Thus, low-density liquid is classified as the strongest of all liquids known ("superstrong"), and also high-density liquid is classified as a strong liquid.

Many acronyms are used in the literature for describing different kinds of amorphous ice, mainly because many different preparation routes and many different sample histories need to be distinguished. We here introduce these amorphous ices and discuss the question of how many of these forms are of relevance in the context of polyamorphism. We employ the criterion of reversible transitions between amorphous "states" in finite intervals of pressure and temperature to discriminate between independent metastable amorphous "states" and between "substates" of the same amorphous "state". We argue that the experimental evidence suggests we should consider there to be three polyamorphic "states" of ice, namely low-(LDA), high-(HDA) and very high-density amorphous ice (VHDA). In addition to the realization of reversible transitions between them, they differ in terms of their properties, e.g., compressibility, or number of "interstitial" water molecules. Thus they cannot be regarded as structurally relaxed variants of each other and so we suggest considering them as three distinct megabasins in an energy landscape visualization.

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water–water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid–liquid transition that could take place in the no-man’s land, the temperature–pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form.

The isobaric transformation behavior of unannealed (uHDA) and expanded (eHDA) high-density amorphous ice at pressures up to 0.20 GPa is compared using powder x-ray diffraction and dilatometry. eHDA shows high thermal stability and crystallizes to a single ice phase only, whereas uHDA shows much lower thermal stability and always crystallizes to a mixture of ice phases. Unexpectedly, at low temperatures hexagonal ice grows first from uHDA, whereas this phase never crystallizes from eHDA. This leads us to conclude that hidden structural order in the form of nanocrystalline domains is present in uHDA, which triggers growth of hexagonal ice. By contrast, these ordered domains are absent in eHDA, which appears to be a homogeneous material and, thus, could be considered as a candidate for the low-temperature proxy of the proposed high-density liquid phase of water. The present work provides the basis for further experimental studies aiming at investigating this possibility since it establishes that the well-studied uHDA is not the right material to be studied in this context, whereas the more recently discovered eHDA is.