Nucleation and growth of crystalline ices from amorphous ices.

We here review mostly experimental and some computational work devoted to nucleation in amorphous ices. In fact, there are only a handful of studies in which nucleation and growth in amorphous ices are investigated as two separate processes. In most studies, crystallization temperatures Tx or crystallization rates RJG are accessed for the combined process. Our Review deals with different amorphous ices, namely, vapor-deposited amorphous solid water (ASW) encountered in many astrophysical environments; hyperquenched glassy water (HGW) produced from µm-droplets of liquid water; and low density amorphous (LDA), high density amorphous (HDA), and very high density amorphous (VHDA) ices produced via pressure-induced amorphization of ice I or from high-pressure polymorphs. We cover the pressure range of up to about 6 GPa and the temperature range of up to 270 K, where only the presence of salts allows for the observation of amorphous ices at such high temperatures. In the case of ASW, its microporosity and very high internal surface to volume ratio are the key factors determining its crystallization kinetics. For HGW, the role of interfaces between individual glassy droplets is crucial but mostly neglected in nucleation or crystallization studies. In the case of LDA, HDA, and VHDA, parallel crystallization kinetics to different ice phases is observed, where the fraction of crystallized ices is controlled by the heating rate. A key aspect here is that in different experiments, amorphous ices of different "purities" are obtained, where "purity" here means the "absence of crystalline nuclei." For this reason, "preseeded amorphous ice" and "nuclei-free amorphous ice" should be distinguished carefully, which has not been done properly in most studies. This makes a direct comparison of results obtained in different laboratories very hard, and even results obtained in the same laboratory are affected by very small changes in the preparation protocol. In terms of mechanism, the results are consistent with amorphous ices turning into an ultraviscous, deeply supercooled liquid prior to nucleation. However, especially in preseeded amorphous ices, crystallization from the preexisting nuclei takes place simultaneously. To separate the time scales of crystallization from the time scale of structure relaxation cleanly, the goal needs to be to produce amorphous ices free from crystalline ice nuclei. Such ices have only been produced in very few studies.

Oxygen NMR of high-density and low-density amorphous ice.

Using oxygen-17 as a nuclear probe, spin relaxometry was applied to study the high-density and low-density states of amorphous ice, covering temperatures below and somewhat above their glass transitions. These findings are put in perspective with results from deuteron nuclear magnetic resonance and with calculations based on dielectrically detected correlation times. This comparison reveals the presence of a wide distribution of correlation times. Furthermore, oxygen-17 central-transition echo spectra were recorded for wide ranges of temperature and pulse spacing. The spectra cannot be described by a single set of quadrupolar parameters, suggesting a distribution of H-O-H opening angles that is broader for high-density than for low-density amorphous ice. Simulations of the pulse separation dependent spin-echo spectra for various scenarios demonstrate that a small-step frequency diffusion process, assigned to the presence of homonuclear oxygen-oxygen interactions, determines the shape evolution of the pulse-separation-dependent spectra.

Advances in the study of supercooled water.

In this review, we report recent progress in the field of supercooled water. Due to its uniqueness, water presents numerous anomalies with respect to most simple liquids, showing polyamorphism both in the liquid and in the glassy state. We first describe the thermodynamic scenarios hypothesized for the supercooled region and in particular among them the liquid-liquid critical point scenario that has so far received more experimental evidence. We then review the most recent structural indicators, the two-state model picture of water, and the importance of cooperative effects related to the fact that water is a hydrogen-bonded network liquid. We show throughout the review that water's peculiar properties come into play also when water is in solution, confined, and close to biological molecules. Concerning dynamics, upon mild supercooling water behaves as a fragile glass former following the mode coupling theory, and it turns into a strong glass former upon further cooling. Connections between the slow dynamics and the thermodynamics are discussed. The translational relaxation times of density fluctuations show in fact the fragile-to-strong crossover connected to the thermodynamics arising from the existence of two liquids. When considering also rotations, additional crossovers come to play. Mobility-viscosity decoupling is also discussed in supercooled water and aqueous solutions. Finally, the polyamorphism of glassy water is considered through experimental and simulation results both in bulk and in salty aqueous solutions. Grains and grain boundaries are also discussed.

The impact of temperature and unwanted impurities on slow compression of ice.

For slowly compressed hexagonal ice pressure-induced amorphisation to high-density amorphous ice (HDA) takes place below and at 130 K, but polymorphic transformation to ice IX takes place at 140-170 K. Stable ice II only forms above 170 K. Ice IX impurities trigger ice IX growth even at 120 K. HDA and ice IX are equally long-lived, where both can be regarded as metastable phases.

Near-Infrared Spectra of High-Density Crystalline H2O Ices II, IV, V, VI, IX, and XII.

High-pressure ice polymorphs are important for our understanding of hydrogen bonding and exist in the interior of the earth and icy moons. Nonetheless, spectroscopic information about them is scarce, where no information about their optical properties in the near-infrared (NIR) region is available at all. We here report NIR spectra of six ice polymorphs differing in terms of their density and O-atom topology, namely, ices II, IV, V, VI, IX, and XII, in comparison with the known spectra of ice Ih. By contrast to earlier work, we do not use mulling agents or transmission of thin films but use diffuse reflectance on powdered samples in liquid nitrogen. The first overtone of the OH-stretching mode is identified as the marker band most suitable to distinguish between these ices. There is a clear blue shift of this band that increases with increasing topological density in addition to a significant narrowing of the band.

Enthalpy Change from Pure Cubic Ice Ic to Hexagonal Ice Ih.

The preparation of pure cubic ice without hexagonal stacking faults has been realized only recently by del Rosso et al. ( Nat. Mater. 2020, 19, 663-668) and Komatsu et al. ( Nat. Commun. 2020, 11, 464). With our present calorimetric study on the transition from pure cubic ice to hexagonal ice we are able to clarify the value of the enthalpy change ΔHc→h to be -37.7 ± 2.3 J mol-1. The transition temperature is identified as 226 K, much higher than in previous work on ice Isd. This is due to a catalytic effect of hexagonal faults on the transition, but even more importantly due to a relaxation exotherm that was not properly identified in the past.

Infrared Spectroscopy on Equilibrated High-Density Amorphous Ice.

High-density (HDA) and low-density amorphous ices (LDA) are believed to be counterparts of the high- and low-density liquid phases of water, respectively. In order to better understand how the vibrational modes change during the transition between the two solid states, we present infrared spectroscopy measurements, following the change of the decoupled OD-stretch (vOD) (∼2460 cm-1) and OH-combinational mode (vOH + v2, vOH + 2vR) (∼5000 cm-1). We observe a redshift from HDA to LDA, accompanied with a drastic decrease of the bandwidth. The hydrogen bonds are stronger in LDA, which is caused by a change in the coordination number and number of water molecules interstitial between the first and second hydration shell. The unusually broad uncoupled OD band also clearly distinguishes HDA from other crystalline high-pressure phases, while the shape and position of the in situ prepared LDA are comparable to those of vapor-deposited amorphous ice.

High-density amorphous ice: nucleation of nanosized low-density amorphous ice.

The pressure dependence of the crystallization temperature of different forms of expanded high-density amorphous ice (eHDA) was scrutinized. Crystallization at pressures 0.05-0.30 GPa was followed using volumetry and powder x-ray diffraction. eHDA samples were prepared via isothermal decompression of very high-density amorphous ice at 140 K to different end pressures between 0.07-0.30 GPa (eHDA0.07-0.3). At 0.05-0.17 GPa the crystallization line T x (p) of all eHDA variants is the same. At pressures >0.17 GPa, all eHDA samples decompressed to pressures <0.20 GPa exhibit significantly lower T x values than eHDA0.2 and eHDA0.3. We rationalize our findings with the presence of nanoscaled low-density amorphous ice (LDA) seeds that nucleate in eHDA when it is decompressed to pressures <0.20 GPa at 140 K. Below ~0.17 GPa, these nanosized LDA domains are latent within the HDA matrix, exhibiting no effect on T x of eHDA<0.2. Upon heating at pressures ⩾0.17 GPa, these nanosized LDA nuclei transform to ice IX nuclei. They are favored sites for crystallization and, hence, lower T x . By comparing crystallization experiments of bulk LDA with the ones involving nanosized LDA we are able to estimate the Laplace pressure and radius of ~0.3-0.8 nm for the nanodomains of LDA. The nucleation of LDA in eHDA revealed here is evidence for the first-order-like nature of the HDA → LDA transition, supporting water's liquid-liquid transition scenarios.