Hexagonal Ice Research Articles

Structures of ions accommodated in salty ice Ih crystals.

Frozen aqueous electrolytes are ubiquitous and involved in various phenomena occurring in the natural environment. Although salts are expelled from ice during freezing of aqueous solutions, minor amounts of the constituent ions are accommodated in the crystal lattice of ice. This phenomenon was associated with the generation of the Workman-Reynolds freezing potential. Molecular simulations also confirmed the ion incorporation in the crystal lattice of ice Ih upon freezing of aqueous electrolytes and identified possible local structures of the ions. However, no experimental information is available on the structure of ions accommodated in the crystal lattice of ice Ih. In this work, we use X-ray absorption fine structure (XAFS) to study the local structures of K+ and Cl- accommodated in ice Ih single crystals. Previous molecular simulations predicted that ions are trapped in the hexagonal cavities of the ice structure or replace two water molecules in the crystal lattice. Four possible configurations are considered and optimized by the calculations using ONIOM (QM/QM/QM). The results are evaluated in terms of the agreement between the experimental XAFS spectra and those simulated from the optimized structures. The spectra are most reasonably interpreted by assuming that K+ replaces one water molecule in the ice crystal lattice and is accommodated in a tetrahedral coordination cage. Similarly, Cl- probably adopts the same configuration, because it explains the coordination number better than other structures, such as that assuming the replacement of two water molecules belonging to the same hexagonal planes.

Grain-Boundary Sliding in Ice Ih: Tribology and Rheology at the Nanoscale

Using nonequilibrium molecular dynamics simulations, we investigate the process of grain-boundary (GB) sliding in ice Ih. We focus on the ∑35 symmetric tilt boundary, which has been observed experi...

Structure and thermodynamics of empty clathrate hydrates below the freezing point of water.

Recently prepared as a new H2O phase, ice XVI was obtained by degassing a Ne-sII clathrate hydrate under vacuum, however very little is known of that crystalline solid under temperatures (T ≤ 220 K) and pressures (p ≤ 5000 bar) relevant for the Earth's environment and geochemistry. In this work, atomically detailed calculations using long time-scale molecular simulations, seldom paralelled before, are employed to probe empty sII clathrate hydrates. It is found that the volumetric response to an applied pressure-temperature gradient is accurately described by the Parsafar and Mason equation of state with an accuracy of at least 99.7%. Structural deformation induced upon the crystals is interpreted by monitoring the unit cell length and isobaric thermal expansivity, whilst benchmarked against previous neutron diffraction measurements of ice XVI and hexagonal ice under room pressure conditions; a critical comparison is established with other sII guest occupied lattices (CH4, CO2 and CnH2n+2 with n = 2, 3, 4), often found in permafrost regions and in the margins of continental shelves. Such an analysis reveals that empty sII frameworks are slightly more stable to thermal deformation than their sI analogues and that hexagonal ice is the structurally most stable of the condensed H2O phases addressed here. Of paramount importance for the oil and natural gas industries, heat capacities obtained from enthalpy profiles are identical for the sI and sII empty clathrates up to 2000 bar and diverge by only ∼7.3% at 5000 bar. The canonical tetrahedral symmetry of water-bonded networks is analysed in terms of an angular and a distance order parameters, which are observed to decrease (increase) as pressure (temperature) increases (decreases). The results now being reported constitute a landmark for future studies dealing with high-pressure and very low-temperature conditions, characteristic of the Earth's permafrost environment and other planetary interiors, whilst contributing to expand our knowledge regarding the recently discovered ice XVI phase.

Ice nucleation activity of iron oxides via immersion freezing and an examination of the high ice nucleation activity of FeO.

Heterogeneous ice nucleation is a common process in the atmosphere, but relatively little is known about the role of different surface characteristics on the promotion of ice nucleation. We have used a series of iron oxides as a model system to study the role of lattice mismatch and defects induced by milling on ice nucleation activity. The iron oxides include wüstite (FeO), hematite (Fe2O3), magnetite (Fe3O4), and goethite (FeOOH). The iron oxides were characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) surface area measurements. The immersion freezing experiments were performed using an environmental chamber. Wüstite (FeO) had the highest ice nucleation activity, which we attribute to its low lattice mismatch with hexagonal ice and the exposure of Fe-OH after milling. A comparison study of MnO and wüstite (FeO) with milled and sieved samples for each suggests that physical defects alone result in only a slight increase in ice nucleation activity. Despite differences in the molecular formula and surface groups, hematite (Fe2O3), magnetite (Fe3O4), and goethite (FeOOH) had similar ice nucleation activities, which may be attributed to their high lattice mismatch to hexagonal ice. This study provides further insight into the characteristics of a good heterogeneous ice nucleus and, more generally, helps to elucidate the interactions between aerosol particles and ice particles in clouds.

CH3O Radical Binding on Hexagonal Water Ice and Amorphous Solid Water.

Binding energies of the CH3O radical on hexagonal water ice (Ih) and amorphous solid water (ASW) were calculated using the ONIOM(QM:MM) method. A range of binding energies is found (0.10-0.50 eV), and the average binding energy is 0.32 eV. The CH3O radical binding on the ASW surfaces is stronger than on the Ih surfaces. The computed binding energies from the ONIOM(wB97X-D/def2-TZVP:AMBER) and wB97X-D/def2-TZVP methods agree quite well. Therefore, the ONIOM(QM:MM) method is expected to give accurate binding energies at a low computational cost. Binding energies from the ONIOM(wB97X-D/def2-TZVP:AMBER) and ONIOM(wB97X-D/def2-TZVP:AMOEBA09) methods differ noticeably, indicating that the choice of force field matters. According to the energy decomposition analysis, the electrostatic interactions and Pauli repulsions between the CH3O radical and ice play a crucial role in the binding energy. This study gives quantitative insights into the CH3O radical binding on interstellar ices.

Experimental measures of topological sector fluctuations in the F-model

The two dimensional F-model is an ice-rule obeying model, with a low temperature antiferroelectric state and high temperature critical Coulomb phase. Polarization in the system is associated with topological defects in the form of system-spanning windings which makes it an ideal system on which to observe topological sector fluctuations, as have been discussed in the context of spin ice and Berezinskii-Kosterlitz-Thouless (BKT) systems. Here we develop Lieb and Baxter's historic solutions of the F-model to exactly calculate relevant properties, several apparently for the first time. We further calculate properties not amenable to exact solution by an approximate cavity method and by referring to established scaling results. Of particular relevance to topological sector fluctuations are the exact results for the applied field polarization and the "energetic susceptibility". The latter is a both a measure of topological sector fluctuations and, surprisingly, in this case, a measure of the order parameter correlation exponent. In the high temperature phase, the temperature tunes the density of topological defects and algebraic correlations, with the energetic susceptibility undergoing a jump to zero at the antiferroelectric ordering temperature, analogous to the "universal jump" in BKT systems. We discuss how these results are relevant to experimental systems, including to spin ice thin films and three-dimensional dipolar spin ice and water ice, where we find that an analogous "universal jump" has previously been established in numerical studies. This unexpected result suggests a universal limit on the stability of perturbed Coulomb phases that is independent of dimension and of the order of the transition. Experimental results on water ice Ih are not inconsistent with this proposition. We complete the paper by relating our results to experimental studies of artificial spin ice arrays.

Crystallisation competition between cubic and hexagonal ice structures: molecular-dynamics insight

ABSTRACT Under ambient pressure, two different ice polytypes of ice, cubic (Ic ) and hexagonal (Ih ) can be crystallised. Here, we elucidate the mechanism and kinetics of the phase transition of cubic ice with no stacking disorder to a perfect hexagonal ice at various temperatures, via molecular simulation. The study was performed through non-isothermal and isothermal molecular-dynamics simulations; these conditions were enforced on an equilibrated Ic /LDA/Ih system. Different results have been drawn from analysis in terms of local density, annealing kinetics, and phase transition. The evolution from cubic to hexagonal ice becomes prevalent at higher temperatures during the performed non-isothermal studies; to this end, a model-free kinetic study was proposed to address this phenomenon’s kinetic properties over a characteristic temperature range. Ice crystallisation is also studied in solid/liquid systems, where cubic or hexagonal ice was in contact with liquid water at sub-zero temperatures. It was revealed that water molecules have a propensity to follow and crystalise in the existing ice structure rather than forming a new interface.

Molecular Perspective on Water Vapor Accommodation into Ice and Its Dependence on Temperature.

Accommodation of vapor-phase water molecules into ice crystal surfaces is a fundamental process controlling atmospheric ice crystal growth. Experimental studies investigating the accommodation process with various techniques report widely spread values of the water accommodation coefficient on ice, αice, and the results on its potential temperature dependence are inconclusive. We run molecular dynamics simulations of molecules condensing onto the basal plane of ice Ih using the TIP4P/Ice empirical force field and characterize the accommodated state from this molecular perspective, utilizing the interaction energy, the tetrahedrality order parameter, and the distance below the instantaneous interface as criteria. Changes of the order parameter turn out to be a suitable measure to distinguish between the surface and bulk states of a molecule condensing onto the disordered interface. In light of the findings from the molecular dynamics, we discuss and re-analyze a recent experimental data set on αice obtained with an environmental molecular beam (EMB) setup [KongX.; J. Phys. Chem. A2014, 118 ( (22), ), 3973−397924814567] using kinetic molecular flux modeling, aiming at a more comprehensive picture of the accommodation process from a molecular perspective. These results indicate that the experimental observations indeed cannot be explained by evaporation alone. At the same time, our results raise the issue of rapidly growing relaxation times upon decreasing temperature, challenging future experimental efforts to cover relevant time scales. Finally, we discuss the relevance of the water accommodation coefficient on ice in the context of atmospheric cloud particle growth processes.

Stagnant lid convection with temperature-dependent thermal conductivity and the thermal evolution of icy worlds

SUMMARY Convection is an efficient process to release heat from planetary interiors, but its efficiency depends on the detailed properties of planetary mantles and materials. A property whose impact has not yet been studied extensively is the temperature dependence of thermal conductivity. Because thermal conductivity controls heat fluxes, its variations with temperature may alter heat transfer. Here, I assess qualitatively and quantitatively the influence of temperature-dependent thermal conductivity on stagnant lid convection. Assuming that thermal conductivity varies as the inverse of temperature $(k \propto 1/T)$, which is the case for ice Ih, the main component of outer shells of solar System large icy bodies, I performed numerical simulations of convection in 3-D-Cartesian geometry with top-to-bottom viscosity and conductivity ratios in the ranges 105 ≤ Δη ≤ 108 and 1 ≤ Rk ≤ 10, respectively. These simulations indicate that with increasing Rk, and for given values of the Rayleigh number and Δη, heat flux is reduced by a factor Rk0.82, while the stagnant lid is thickening. These results have implications for the structures and thermal evolutions of large icy bodies, the impact of temperature-dependent conductivity being more important with decreasing surface temperature, Tsurf. The heat fluxes and thermal evolutions obtained with temperature-dependent conductivity are comparable to those obtained with constant conductivity, provided that the conductivity is fixed to its value at the bottom or in the interior of the ice shell, that is, around 2.0–3.0 W m−1 K−1, depending on the body. By contrast, temperature-dependent conductivity leads to thicker stagnant lids, by about a factor 1.6–1.8 at Pluto (Tsurf = 40 K) and a factor 1.2–1.4 at Europa (Tsurf = 100 K), and smaller interior temperatures. Overall, temperature-dependent thermal conductivity therefore provides more accurate descriptions of the thermal evolutions of icy bodies.

Theoretical study of the self-preservation effect in CF4 gas hydrates

This work studies thermodynamic properties of CF4 gas hydrates using the statistical thermodynamic model of inclusion compounds, developed in our laboratory and closely associated with Quasiharmonic Lattice Dynamic (QLD) and Molecular Dynamic Simulation (MD). Thermal expansion coefficient of CF4 gas hydrate is calculated at different hydrate composition. The thermal expansion coefficient is shown to be lesser than the thermal expansion coefficient of CH4 hydrates, but larger than ice Ih, that still indicates the presence of the self-preservation effect. The thermal expansion coefficient is very sensitive to the composition of the hydrate and can vary in a wide range. The same is true for the hydrate lattice parameter as well; it is shown that at certain conditions it may be even less than for hypothetical empty hydrate structure. The self-preservation effect may be applied for many aspects related to CF4 compound, especially for storage and transportation purposes in producing semiconductor electronics.

Thermal expansion of ice based gas hydrates

This work aims at studying thermal expansion of ice Ih based gas hydrates that play important role in self-preservation effect of classical gas hydrates. Linear thermal expansion of ice Ih based hydrogen hydrates are calculated using a very effective statistical thermodynamic model of gas hydrates developed by the authors of this work. Molecular structures of all studied systems are obtained by MD simulations, and all parameters required by the model are obtained by using Quasiharmonic Lattice Dynamic approach. In accordance with our calculations, introduction of hydrogen into the system not only significantly affects the unit cell parameter of ice, but also increases linear thermal expansion and makes it comparable to the classical gas hydrates such as CH4, CO2, etc.

Influence of ice structure on the soft UV photochemistry of PAHs embedded in solid water

Context. The UV photoreactivity of polycyclic aromatic hydrocarbons (PAHs) in porous amorphous solid water has long been known to form both oxygenated photoproducts and photofragments. Aims. The aim of this study is to examine the influence of ice structure on reactivity under soft UV irradiation conditions. Methods. Mixtures of PAHs with amorphous solid water (porous and compact) and crystalline (cubic and hexagonal) ices were prepared in a high vacuum chamber and irradiated using a mercury lamp for up to 2.5 h. Results. The results show that the production of oxygenated PAHs is efficient only in amorphous water ice, while fragmentation can occur in both amorphous and crystalline ices. We conclude that the reactivity is driven by PAH–water interactions in favourable geometries, notably where dangling bonds are available at the surface of pores. Conclusions. These results suggest that the formation of oxygenated PAH molecules is most likely to occur in interstellar environments with porous (or compact) amorphous solid water and that this reactivity could considerably influence the inventory of aromatics in meteorites.

Adsorption of CO and N2 molecules at the surface of solid water. A grand canonical Monte Carlo study.

The adsorption of carbon monoxide and nitrogen molecules at the surface of four forms of solid water is investigated by means of grand canonical Monte Carlo simulations. The trapping ability of crystalline Ih and low-density amorphous ices, along with clathrate hydrates of structures I and II, is compared at temperatures relevant for astrophysics. It is shown that when considering a gas phase that contains mixtures of carbon monoxide and nitrogen, the trapping of carbon monoxide is favored with respect to nitrogen at the surface of all solids, irrespective of the temperature. The results of the calculations also indicate that some amounts of molecules can be incorporated in the bulk of the water structures, and the molecular selectivity of the incorporation process is investigated. Again, it is shown that incorporation of carbon monoxide is favored with respect to nitrogen in most of the situations considered here. In addition, the conclusions of the present simulations emphasize the importance of the strength of the interactions between the guest molecules and the water network. They indicate that the accuracy of the corresponding interaction potentials is a key point, especially for simulating clathrate selectivity. This highlights the necessity of having interaction potential models that are transferable to different water environments.

Water content thresholds in glycerol/water system: Low- and high-wavenumber Raman spectroscopy study

Water structure is the key in such diverse processes as protein folding, catalysis of chemical reactions, and stability of pharmaceuticals and biopharmaceuticals. In the current investigation, glycerol-water mixtures are studied by low- and high-wavenumber Raman spectroscopy. Three water content regions, which are separated by two water content thresholds (WT), WT1 at 6.1 ± 0.7 wt% water and WT2 at 18.6 ± 4.4 wt% water, are identified, based on the trends in the hydrogen bond strength and the cage effect. It is hypothesized that WT1 corresponds to a transition from predominantly unclustered water molecules to small water clusters, and is associated with facilitation of proton transfer as water content exceeds WT1. The WT2 is proposed to mark formation of large (>100 molecules) water clusters, which can form stable nucleus of hexagonal ice at lower temperatures. These findings, if confirmed for other polyhydroxycompounds, could facilitate development of novel pharmaceuticals and vaccines, and also contribute to fundamental understanding of mechanisms of cryo- and lyo-protection of proteins, viruses, and cells.

Slow Crystal Growth of Cubic Ice with Stacking Faults in a Glassy Dilute Glycerol Aqueous Solution

Control of ice formation is an important issue as catastrophic ice growth influences our life activities and many industrial systems. We prepared a homogeneous glass of a dilute glycerol aqueous solution by a pressure liquid cooling vitrification method and examined the effect of solute on the ice formation of solvent water using a powder X-ray diffraction method. The solvent water immediately after the crystallization is composed of nanosized pure cubic ice (ice Ic). The crystal growth of ice Ic with stacking faults is much slower than that of pure water. The presence of glycerol molecules dispersing homogeneously may hinder crystal growth. The macroscopic segregation occurs rapidly during the transformation from stacking disordered ice to hexagonal ice. The results suggest that ice formation can be controlled by changing the solute type and concentration. This study has implications for thawing technology in cryobiology and frozen food engineering.

Neural Network Classification of Ice-Crystal Images Observed by an Airborne Cloud Imaging Probe

ABSTRACT In the atmosphere, cloud particles have different shapes. The study of cloud particle shapes plays an important role in understanding cloud precipitation processes, radiative transfer, and weather modification. The image resolution and data quality of cloud probes affect the accuracy of the classification of particle shapes. To solve the occlusion of the photosensitive edge of the particle image and achieve automatic, high-precision ice-crystal classification of airborne Cloud Imaging Probe (CIP) ice-crystal images, this study uses a traditional image processing algorithm for data quality control and applies artificial intelligence algorithms to classify ice-crystal images. At present, there are mainly two types of ice-crystal classification methods, one classifies the shape of ice crystals using a pattern parameterization scheme, and the other uses an artificial intelligence network model to classify the shape. Combined with data quality control, the dataset was tested on eight models, and the TL-EfficientNet-b6 model was found to be the most accurate. Therefore, the TL-EfficientNet-b6 classifier model was used in this study, which is a newly developed convolutional neural network (CNN) based on a transfer learning method. Experimental results show that the TL-EfficientNet-b6 model can reach 100% in the single-class precision of tiny and hexagonal ice crystals, and the average precision can reach 98%. These results are more accurate than those using traditional classification methods. This method could be valuable in cloud microphysics research and weather modification.

Asymmetric Hydrogen-Bonding Structure at a Water/Ice Interface

The interface between liquid water and the basal plane of crystal ice Ih at the melting point temperature is investigated via molecular dynamics (MD) simulations to examine the molecular structure ...

Atomic Steps Induce the Aligned Growth of Ice Crystals on Graphite Surfaces.

Heterogeneous ice nucleation on atmospheric aerosols strongly affects the earth's climate, and at the microscopic level, surface-irregularity-induced ice crystallization behaviors are common but crucial. Because of the lack of visual evidence and effective experimental methods, the mechanism of atomic-structure-dependent ice formation on aerosol surfaces is poorly understood. Here we chose highly oriented pyrolytic graphite (HOPG) to represent soot (a primary aerosol), and environmental scanning electron microscopy (ESEM) was performed for in situ observations of ice formation. We found that hexagonal ice crystals show an aligned growth pattern via a two-stage pathway with one a axis coinciding with the direction of atomic step edges on the HOPG surface. Additionally, the ice crystals grow at a noticeably higher speed along this direction. This study reveals the role of atomic surface defects in heterogeneous ice nucleation and may pave the way to control icing-related processes in practical applications.

Compiling the cold hard facts about imperfections in ice

Review summarizes the different types of crystal defects and how each affects the properties of hexagonal ice, but it’s only the tip of the iceberg.

Use of Ion Exchange To Regulate the Heterogeneous Ice Nucleation Efficiency of Mica.

Heterogeneous ice nucleation (HIN) triggered by mineral surfaces typically exposed to various ions can have a significant impact on the regional atmosphere and climate. However, the dependence of HIN on the nature of the mineral surface ions is still largely unexplored due to the complexity of mineral surfaces. Because K+ on the atomically flat (001) surface of mica can be readily replaced by different cations through ion exchange, muscovite mica was selected; its simple nature provides a very straightforward system that can serve as the model for investigating the effects of mineral surface ions on HIN. Our experiments show that the surface (001) of H+-exchanged mica displays markedly higher HIN efficiencies than that of Na-/K-mica. Vibrational sum-frequency generation spectroscopy reveals that H-mica induces substantially less orientation ordering than Na-/K-mica within the contact water layer at the interface. Molecular dynamics simulations suggest that the HIN efficiency of mica depends on the positional arrangement and orientation of the interfacial water. The formation of the hexagonal ice Ih basal-type structure in the first water layer atop the mica surface facilitates HIN, which is determined by the size of the protruding ions atop the mica surface and by the surface adsorption energy. The orientational distribution is optimal for HIN when 25% of the water molecules in the first water layer atop the mica surface have one OH group pointing up and 25% have one OH group pointing down, which, in turn, is determined by the surface charge distribution.