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Atmospheric gases trapped in polar ice have been used to reconstruct polar and global climate changes, providing better time resolution when less diffused. Experiments have shown that gas diffusion...

International audience; We explore the links between strain localisation and microstructural evolution in ice Ih deformed by dislocation creep. Using digital image correlation (DIC), we monitored the evolution of the strain field in two coarse-grained columnar ice samples deformed by creep (uniaxial compression at constant load) at −7 °C and 0.5 MPa up to 9.5% bulk shortening. After a brief transient (

Although hexagonal ice (ice Ih) is the most common and highly studied crystalline form of ice, its nucleation from clathrate hydrates is poorly understood. Here, we report the formation of ice Ih t...

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.

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...

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.

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.

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 ...

Thermal properties of gas hydrates and their underlying fundamental characterization are limited and incomplete but crucial in ongoing basic science research and technological applications. The con...

Insights into energy flow dynamics at ice surfaces are essential for understanding chemical dynamics relevant to atmospheric and geographical sciences. Here, employing ultrafast surface-specific spectroscopy, we report the interfacial vibrational dynamics of ice Ih. A comparison to liquid water surfaces reveals accelerated vibrational energy relaxation and dissipation at the ice surface for hydrogen-bonded OH groups. In contrast, free-OH groups sticking into the vapor phase exhibit substantially slower vibrational dynamics on ice. The acceleration and deceleration of vibrational dynamics of these different OH groups at the ice surface are attributed to enhanced intermolecular coupling and reduced rotational mobility, respectively. Our results highlight the unique properties of free-OH groups on ice, putatively linked to the high catalytic activities of ice surfaces.

Among the many ice polymorphs, ice I, that is present in nature at ambient pressure, occurs with two different structures, i.e. the stable hexagonal (Ih) or the metastable cubic (Ic) one. An accura...

Water freezes below 0 °C at ambient pressure ordinarily to ice Ih, with hexagonal stacking sequence. Under certain conditions, ice with a cubic stacking sequence can also be formed, but ideal ice Ic without stacking-disorder has never been formed until recently. Here we demonstrate a route to obtain ice Ic without stacking-disorder by degassing hydrogen from the high-pressure form of hydrogen hydrate, C2, which has a host framework isostructural with ice Ic. The stacking-disorder free ice Ic is formed from C2 via an intermediate amorphous or nano-crystalline form under decompression, unlike the direct transformations occurring in ice XVI from neon hydrate, or ice XVII from hydrogen hydrate. The obtained ice Ic shows remarkable thermal stability, until the phase transition to ice Ih at 250 K, originating from the lack of dislocations. This discovery of ideal ice Ic will promote understanding of the role of stacking-disorder on the physical properties of ice as a counter end-member of ice Ih., Metastable cubic ice has been identified in several conditions relevant to geo and astrochemistry, but was always characterized by stacking disorder. Here the authors synthesize a hydrogen hydrate and degas hydrogen, obtaining pure non-defected cubic ice, observed by X-ray and neutron diffraction.

Among numerous crystalline phases of ice, the Ih phase is the most stable above 72 K at atmospheric pressure. It is well established that the orientations of water molecules in the bulk of ice Ih are statistical without long-range order. However, the orientational order of water at the surface of ice Ih has been enigmatic. Here we show that the surface of ice Ih at 100 K has hydrogen order with the OH group pointing upward to the air (“H-up” orientation). We applied nonlinear optical spectroscopy and theoretical modeling to the surface of isotopically pure and diluted ice Ih and observed OH stretch vibrational signatures attributed to H-up ordering. Furthermore, we found that this hydrogen order takes place despite a more inhomogeneous microenvironment at the surface than in the bulk. Our results suggest the prominent role of the surface to allow the reorientation of water molecules for hydrogen ordering that is virtually prohibited in the bulk.

Reflection absorption infrared spectroscopic investigations of multilayer films of acetonitrile (ACN) and water in an ultrahigh vacuum under isothermal conditions showed the emergence of cubic (ice Ic) and hexagonal (ice Ih) ices depending on the composition of the film. The experiments were conducted with a mixed film of 300 monolayers in thickness and the ACN : H2O monolayer ratios were varied from 1 : 5 to 5 : 1. Mixed films were deposited at 10 K and warmed to 130–135 K, where ACN desorbed subsequently and IR spectral evolution was monitored continuously. While the emergence of ice Ic at 130 K has been reported, the occurrence of ice Ih at this temperature was seen for the first time. Detailed investigations showed that ice Ih can form at 125 K as well. Crystallization kinetics and activation energy (Ea) for the emergence of ice Ih were evaluated using the Avrami equation.

Water monolayer can form in layered confined systems. Here, CaF2 (111) and graphene are chosen as modeling systems to explore the structure and stability of confined monolayer water. First, water molecules tend to intercalate into a confined space between graphene and CaF2, rather than on a bare surface of graphene. Water molecules can move fast in the confined space due to a low diffusion barrier. These water molecules are likely to aggregate together, forming monolayer ice. Four ice phases including ice II, ice III, ice IV, and ice Ih are compared in this confined system. Intriguingly, all the ice phases undergo very small deformation, indicating the 2D monolayer ice can be stable in the CaF2–graphene–confined system. Beyond, projected band structures are also plotted to understand the electronic behavior of these confined ice phases. Nearly all the bands originated from confined ices are flat and locate about 2–3 eV below the Fermi level. Binding energy calculations suggest that the stability sequence in this confined system as follows: Ih-up ≈ Ih-down ≈ II < IV < III. Our results bring new insights into the formation of water monolayer production in such a confined condition.

Significance The question of whether a first-order liquid-to-liquid transition is at the origin of water’s anomalous properties has been controversial since the pioneering experiments by Mishima et al. in 1985 and molecular simulations by Poole et al. in 1992. Since then, experiments aimed at shedding light on this question have been performed using amorphous ices made from crystalline ice, fueling criticism about their crystal-like nature. In the present study, we avoid crystalline ice at any time of the experiment yet still observe a first-order glass-to-glass transition in vitrified liquid droplets. This makes the strong case for glass polymorphism and the direct thermodynamic connection to the liquid-to-liquid transition at higher temperatures, dismissing the criticism voiced for three decades., The nature of amorphous ices has been debated for more than 35 years. In essence, the question is whether they are related to ice polymorphs or to liquids. The fact that amorphous ices are traditionally prepared from crystalline ice via pressure-induced amorphization has made a clear distinction tricky. In this work, we vitrify liquid droplets through cooling at ≥106 K ⋅ s−1 and pressurize the glassy deposit. We observe a first order–like densification upon pressurization and recover a high-density glass. The two glasses resemble low- and high-density amorphous ice in terms of both structure and thermal properties. Vitrified water shows all features that have been reported for amorphous ices made from crystalline ice. The only difference is that the hyperquenched and pressurized deposit shows slightly different crystallization kinetics to ice I upon heating at ambient pressure. This implies a thermodynamically continuous connection of amorphous ices with liquids, not crystals.

International audience; New data on the variation of the thermal expansion of ice Ih with temperature at ambient pressure together with new evaluations of the bulk modulus and earlier data for the heat capacity provide the basis for a coherent thermodynamic modeling of the main thermophysical properties of ice Ih over its whole range of stability. The quasi-harmonic approximation with one Debye term and seven Einstein terms, together with explicit anharmonicity, represents the dominant contribution next to minor “anomalies” from hydrogen ordering and lattice defects. The model accurately fits the main features of all experimental data and provides a basis for the comparison with earlier determinations of the phonon density of states and the Grüneisen parameters.

The measurement of the H-projected density of phonon states (H-DOPS) of polycrystalline ice Ic has been performed with an unprecedented accuracy, and in a sample having an almost perfect crystallographic purity, as it was obtained from the transformation of ice XVII. Results are compared with new accurate measurements of H-DOPS in ice Ih, and with centroid molecular-dynamics (MD) computations. The differences between the experimental H-DOPS in these two forms of ice are subtle, but quantitatively measurable. In addition, they are reproduced semi-quantitatively by computational methods, demonstrating the effectiveness of this innovative simulation tool for reproducing the dynamical properties of the ice structures.

Due to their great importance in science, technology, and the life sciences, water and ice have been extensively investigated over many years. In particular, hexagonal ice Ih has been of great interest since it is the most common form of ice, and several modifications, Ih(a), Ih(b) and Ih(c) are known, whose structural details are still under discussion. In this study, we present an alternative theoretical model, called Ih(d), for the hexagonal ice modification in space group P63/mmc (no. 194), based on first-principles calculations that have been performed using DFT-LDA, GGA-PBE, and hybrid B3LYP and PBE0 functionals.

Crystallization kinetics of water on Ru(0001) with and without adspecies was investigated using reflection high energy electron diffraction (RHEED). Amorphous solid water is formed on the bare Ru(0001) substrate during water vapor deposition at 135 K; randomly oriented ice Ic crystallites grow after some incubation time. The nucleation and epitaxial growth tend to be aborted on the oxygenated Ru(0001) substrate, whereas ice Ih crystallites having considerable stacking disorders grow epitaxially on the CO-adsorbed Ru(0001) substrate immediately after water deposition at 135 K. Results indicate that epitaxy is controlled by the interfacial ice nucleation time and the water deposition rate.

Water ice is one of the most fundamental and well-studied molecular solids, which continues to provide surprising and useful insights into its emergent complexity as ever more precise experimental techniques are applied. Using one of the highest resolution neutron powder diffraction instruments in the world, I report a small but systematic distribution in the c/a axial ratios of D2O ice Ih below 160 K that depends upon both the preparation method and the thermal history of the sample. The general decrease in c/a on cooling is interpreted as a consequence of short-range partial ordering in the hydrogen-atom substructure: the synthesis-dependent variation then follows from there being a spectrum of relaxation times between samples formed by slow natural freezing, samples formed by very rapid quench-freezing and samples formed with a small amount of alkali hydroxide dopant, probably due to differences in the relative abundance of orientational versus ionic point defects.

Because of the negative inclination of the solid���liquid phase separation line in water, ice Ih melts on compression. We carry out molecular dynamics simulations using TIP4P/Ice water model. We find that increase in pressure drives the liquid water into a high density metastable glassy state, at relatively high pressure (greater than ���30 kbar). The crystal-to-glass transition is characterised by a rapid approach to a zero diffusion state and absence of crystalline order in the static structure factor. The vitrification is found to occur even at high temperatures (T > 250 K). We study this novel glass transition process at four temperatures (80, 250, 300 and 320 K). The transition pressure increases with an increase in temperature, as expected. Interestingly, we find that the total rate of change of entropy with pressure undergoes a change at/near the glass transition. We discover a pressure-induced realignment of water molecules resulting in two well-separated peaks in the O���O���O angle distribution among neighbouring molecules. The difference between the positions of these two peaks undergoes a sharp change at the vitrification pressure suggesting that it can serve as an appropriate order parameter to detect the glass transition point.

[Image: see text] Force field-based molecular simulations were used to calculate thermal expansivities, heat capacities, and Joule–Thomson coefficients of binary (standard) hydrogen–water mixtures for temperatures between 366.15 and 423.15 K and pressures between 50 and 1000 bar. The mole fraction of water in saturated hydrogen–water mixtures in the gas phase ranges from 0.004 to 0.138. The same properties were calculated for pure hydrogen at 323.15 K and pressures between 100 and 1000 bar. Simulations were performed using the TIP3P and a modified TIP4P force field for water and the Marx, Vrabec, Cracknell, Buch, and Hirschfelder force fields for hydrogen. The vapor–liquid equilibria of hydrogen–water mixtures were calculated along the melting line of ice Ih, corresponding to temperatures between 264.21 and 272.4 K, using the TIP3P force field for water and the Marx force field for hydrogen. In this temperature range, the solubilities and the chemical potentials of hydrogen and water were obtained. Based on the computed solubility data of hydrogen in water, the freezing-point depression of water was computed ranging from 264.21 to 272.4 K. The modified TIP4P and Marx force fields were used to improve the solubility calculations of hydrogen–water mixtures reported in our previous study [ A. Rahbari;J. Chem. Eng. Data2019, 64, 4103−4115] for temperatures between 323 and 423 K and pressures ranging from 100 to 1000 bar. The chemical potentials of ice Ih were calculated as a function of pressure between 100 and 1000 bar, along the melting line for temperatures between 264.21 and 272.4 K, using the IAPWS equation of state for ice Ih. We show that at low pressures, the presence of water has a large effect on the thermodynamic properties of compressed hydrogen. Our conclusions may have consequences for the energetics of a hydrogen refueling station using electrochemical hydrogen compressors.

Ice Ih, the common form of ice in the biosphere, contains proton disorder. Its proton-ordered counterpart, ice XI, is thermodynamically stable below 72 K. However, even below this temperature the formation of ice XI is kinetically hindered and experimentally it is obtained by doping ice with KOH. Doping creates ionic defects that promote the migration of protons and the associated change in proton configuration. In this article, we mimic the effect of doping in molecular dynamics simulations using a bias potential that enhances the formation of ionic defects. The recombination of the ions thus formed proceeds through fast migration of the hydroxide and results in the jump of protons along a hydrogen bond loop. This provides a physical and expedite way to change the proton configuration, and to accelerate diffusion in proton configuration space. A key ingredient of this approach is a machine learning potential trained with density functional theory data and capable of modeling molecular dissociation. We exemplify the usefulness of this idea by studying the order-disorder transition using an appropriate order parameter to distinguish the proton environments in ice Ih and XI. We calculate the changes in free energy, enthalpy, and entropy associated with the transition. Our estimated entropy agrees with experiment within the error bars of our calculation., 17 pages, 9 figures

A framework for investigating the mechanics of snow is proposed based on an advanced micro-scale approach. Varying strain rates, densities and temperatures are taken into account. Natural hazards i.e. snow avalanches are triggered by snow deforming at low rates, while a large group of industrial applications concerning driving safety or winter sport activities require an understanding of snow behaviour under high deformation rates. On the micro-scale, snow is considered to consist of ice grains joined by ice bonds to build a porous structure. Deformation and failure of bonds and the inter-granular collisions of ice grains determine the macroscopic response under mechanical load. Therefore, this study proposes an inter-granular bond and collision model for snow based on the discrete element method to describe interaction on a grain-scale. It aims at predicting the mechanical behaviour of ice particles under different strain rates using a unified approach. Thus, the proposed algorithm predicts the displacement of each individual grains due to inter-granular forces and torques that derive from bond deformation and grain collision. For this purpose, the inter-granular characteristics are approximated by an elastic viscous-plastic material law which is based on the temperature-dependent properties of poly-crystalline ice Ih.

Machine learning models are rapidly becoming widely used to simulate complex physicochemical phenomena with ab initio accuracy. Here, we use one such model as well as direct density functional theory (DFT) calculations to investigate the phase equilibrium of water, hexagonal ice (Ih), and cubic ice (Ic), with an eye towards studying ice nucleation. The machine learning model is based on deep neural networks and has been trained on DFT data obtained using the SCAN exchange and correlation functional. We use this model to drive enhanced sampling simulations aimed at calculating a number of complex properties that are out of reach of DFT-driven simulations and then employ an appropriate reweighting procedure to compute the corresponding properties for the SCAN functional. This approach allows us to calculate the melting temperature of both ice polymorphs, the driving force for nucleation, the heat of fusion, the densities at the melting temperature, the relative stability of ice Ih and Ic, and other properties. We find a correct qualitative prediction of all properties of interest. In some cases, quantitative agreement with experiment is better than for state-of-the-art semiempirical potentials for water. Our results also show that SCAN correctly predicts that ice Ih is more stable than ice Ic., Comment: 20 pages, 9 figures

Direct coexistence simulations on a microsecond time scale have been performed for different types of ice (Ih, Ic, III, V, and VI) in contact with a NaCl aqueous solution at different pressures. In line with the previous results obtained for ice Ih [Conde et al., Phys. Chem. Chem. Phys., 2017, 19, 9566–9574], our results reveal the spontaneous growth of a new ice doped phase and the formation of a brine rejection phase in all ices studied. However, both the preferential incorporation of ions into the ice lattice and the inclusion mechanisms depend on the crystalline structure of each ice. This work shows the inclusion of Cl− and Na+ ions in ice from salt using molecular dynamics simulation, in agreement with the experimental evidence found in the literature. The model used for water is TIP4P/2005. For NaCl we employ a set of potential parameters that uses unit charges for the ions.

Funding Information: This work was supported by the ERC Grant 692891-DAMOCLES, the Academy of Finland Flagship funding (grant no. 337549), the University of Helsinki, Faculty of Science ATMATH project, and the National Center of Meteorology (NCM), Abu Dhabi, UAE, under the UAE Research Program for Rain Enhancement Science. Supercomputing resources were provided by CSC–IT Center for Science, Ltd., Finland. B.R. is grateful to Dr. Stephen Ingram for his advice on setting up the antifreeze protein simulations. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Center of Meteorology, Abu Dhabi, UAE, funder of the research. Publisher Copyright: © 2021 American Chemical Society. All rights reserved. Copyright: Copyright 2021 Elsevier B.V., All rights reserved. We propose a novel method based on template matching for the recognition of liquid water, cubic ice (ice Ic), hexagonal ice (ice Ih), clathrate hydrates, and different interfacial structures in atomistic and coarse-grained simulations of water and ice. The two template matrices represent staggered and eclipsed conformations, which are the building blocks of hexagonal and cubic ice and clathrate crystals. The algorithm is rotationally invariant and highly robust against imperfections in the ice structure, and its sensitivity for recognizing ice-like structures can be tuned for different applications. Unlike most other algorithms, it can discriminate between cubic, hexagonal, clathrate, mixed, and other interfacial ice types and is therefore well suited to study complex systems and heterogeneous ice nucleation.

The uniqueness of the supramolecular structure of the water ensembles is the reason for the formation and special properties of supercooled and supercritical water and ice. One of the most intriguing anomalies of water is its ability to exist as distinct amorphous ice forms, glass polymorphism, or polyamorphism. Supercooled water contains a greater number of tetrahedral hydrogen-bonding water molecule and pentametric water clusters. Two liquid forms, low-density-liquid (LDL)-like and high-density-liquid (HDL)-like, take place also in the supercooled state. A supercritical water is a substance at a temperature and pressure above its critical point, where distinct liquid and gas phases do not exist. Supercritical liquid–gas boundaries (Widom line) are lines in the pressure–temperature (pT) diagram that delimit more liquid-like and more gas-like states of a supercritical fluid, and 19 recognized forms of ice crystals are composed of water molecules held in a regular tetrahedral arrangement by hydrogen bonding. Virtually all ice in the biosphere is ice Ih. Other states of ices can be formed with changes in temperature and pressure and are characterized by molecular and supermolecular details. Low-density amorphous ice and high-(HDA) to low-density amorphous ice (LDA) can be created by cooling the liquid rapidly below Tg or by vapor deposition onto a cold plate, kept below Tg at near-atmospheric pressure (Loerting et al. in J. Phys. Chem. B 115:14167, 2011 [1]). Alternatively, amorphous ice has been formed by temperature- or pressure-induced transformations. The use of physical methods to study the properties of various forms of water is illustrated by typical examples.

We estimated the residual entropy of ice Ih by the recently developed simulation protocol, namely, the combination of Replica-Exchange Wang-Landau algorithm and Multicanonical Replica-Exchange Method. We employed a model with the nearest neighbor interactions on the three-dimensional hexagonal lattice, which satisfied the ice rules in the ground state. The results showed that our estimate of the residual entropy is found to be within 0.038 % of series expansion estimate by Nagle and within 0.000077 % of PEPS algorithm by Vanderstraeten. In this article, we not only give our latest estimate of the residual entropy of ice Ih but also discuss the importance of the uniformity of a random number generator in MC simulations., 15 pages, , (Revtex4-1), 12 figures

Atomic force microscopy showed that the reconstruction of ice-I surfaces occurs with a short-range (2 × 2) H-atom order., Understanding the precise atomic structure of ice surfaces is critical for revealing the mechanisms of physical and chemical phenomena at the surfaces, such as ice growth, melting, and chemical reactions. Nevertheless, no conclusive structure has been established. In this study, noncontact atomic force microscopy was used to address the characterization of the atomic structures of ice Ih(0001) and Ic(111) surfaces. The topmost hydrogen atoms are arranged with a short-range (2 × 2) order, independent of the ice thickness and growth substrates used. The electrostatic repulsion between non–hydrogen-bonded water molecules at the surface causes a reduction in the number of the topmost hydrogen atoms together with a distortion of the ideal honeycomb arrangement of water molecules, leading to a short-range–ordered surface reconstruction.

We investigated if the Raman spectrum of snow is affected by the highly differentiated snow morphology. The latter is subjected to continuous changes driven by the variation of ambient parameters, mainly temperature and humidity as snow progresses from freshly deposited, to compact, to icy. We measured the Raman spectrum of snow grains of different size and morphology on the temperature interval between −5.5 °C and −0.5 °C approaching the melting point. We found systematic differences with respect to bulk ice Ih in the OH-stretching band of snows with different histories. We attribute the observed spectral differences to the change of the molecular arrangement of water molecules between bulk and surface sites. We investigate this characteristic via molecular dynamics DFT simulations of bulk ice and of three thin slabs cut along specific surfaces. We analysed the simulated Raman spectra and compared their distinguishing features to those of experimental spectra of snow. The Raman features of the OH-stretching band allow to distinguish among layers inside a snowpack, each layer being characterized by a different specific surface area. This is relevant to estimate the mechanical stability of the snowpack itself. The influence of UV-A irradiation on snow is discussed.

The intercalated water into nanopores exhibits anomalous properties such as an ultralow dielectric constant. Multiscale modeling and simulations are used to investigate the dielectric properties of various crystalline two-dimensional ices and bulk ices. Although the structural properties of two-dimensional (2D) ices have been extensively studied, much less is known about their electronic and optical properties. First, by using density functional theory and density functional perturbation theory (DFPT), we calculate the key electronic, optical, and dielectric properties of 2D ices. Performing DFPT calculations, both the ionic and electronic contributions of the dielectric constant are computed. The in-plane electronic dielectric constant is found to be larger than the out-of-plane dielectric constant for all the studied 2D ices. The in-plane dielectric constant of the electronic response (${\ensuremath{\varepsilon}}_{el}$) is found to be isotropic for all the studied ices. Second, we determined the dipolar dielectric constant of 2D ices using molecular dynamics simulations at finite temperature. The total out-of-plane dielectric constant is found to be larger than 2 for all the studied 2D ices. Within the framework of the random-phase approximation, the absorption energy ranges for 2D ices are found to be in the ultraviolet spectra. For comparison purposes, we also elucidate the electronic, dielectric, and optical properties of four crystalline ices (ice VIII, ice XI, ice Ic, and ice Ih) and bulk water.

When a dilute aqueous solution freezes at 1 atm, it is segregated into water-rich ice Ih and solute-rich freeze-concentrated glassy solution. A similar segregation is observed at the crystallization of homogeneous glassy aqueous solutions by heating. The influence of solutes on the nucleation of solvent water and the solute discharge process from the crystalline ice are not clear. In this study, I made a homogeneous dilute glassy glycerol aqueous solution (0.07 mol fraction) using pressure liquid cooling vitrification (PLCV), measured the specific volume and the sample temperature during the compression and decompression processes, and examined the polyamorphic and crystallization behaviors. It is found that the sample crystallized slightly above the crystallization temperature is amorphized homogeneously under pressure, and that the amorphized sample is equivalent to the homogeneous glassy sample made by PLCV. This indicates that glycerol solutes in the crystalline sample are dispersed homogeneously and the crystalline sample does not segregate. These experimental results suggest that nucleation does not involve segregation and that crystal growth induces segregation. The discovery of the non-segregated crystalline state has an implication in not only the understanding of crystallization of glassy ice in meteorology and planetary physics but also the application to cell thawing techniques in cryobiology and food engineering.

We study the phase equilibrium between liquid water and ice Ih modeled by the TIP4P/Ice interatomic potential using enhanced sampling molecular dynamics simulations. Our approach is based on the calculation of ice Ih-liquid free energy differences from simulations that visit reversibly both phases. The reversible interconversion is achieved by introducing a static bias potential as a function of an order parameter. The order parameter was tailored to crystallize the hexagonal diamond structure of oxygen in ice Ih. We analyze the effect of the system size on the ice Ih-liquid free energy differences and we obtain a melting temperature of 270 K in the thermodynamic limit. This result is in agreement with estimates from thermodynamic integration (272 K) and coexistence simulations (270 K). Since the order parameter does not include information about the coordinates of the protons, the spontaneously formed solid configurations contain proton disorder as expected for ice Ih., 9 pages, 6 figures

Using molecular dynamics simulations, we study the nanoindentation response of the ice Ih basal surface using two popular water models, namely, the all-atom TIP4P/Ice potential and the coarse-grained mW model. In particular, we consider two markedly different temperatures at which a quasi-liquid layer (QLL) is or is not present. We discuss loading curves, hardness estimates, deformation mechanisms, and residual imprints, considering the effect of the QLL, indenter size, and penetration rate. At very low temperatures, in the absence of a QLL, both potentials produce similar loading curves and deformation mechanisms. Close to the melting temperature, however, important differences were found, including deviations in the QLL thickness and fraction as well as the presence of a competition between pressure-induced melting and recrystallization events. Nevertheless, both potentials exhibit similar deformation mechanisms and steady-state hardness estimates that are consistent with experimental data. In addition to contributing to the discussion regarding the interpretation of experimental AFM loading curves, the present results provide valuable information concerning the simulation of contact problems involving ice and the behavior of these two popular water models under such circumstances. Fil: Santos Flórez, Pedro Antonio. Universidade Estadual de Campinas; Brasil Fil: Ruestes, Carlos Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; Argentina Fil: De Koning, Maurice. Universidade Estadual de Campinas; Brasil

In this work, we consider low-enthalpy polymorphs of ice, predicted previously using a modified basin-hopping algorithm for crystal-structure prediction with the TIP4P empirical potential at three pressures (0, 4 and 8 kbar). We compare and (re)-rank the reported ice polymorphs in order of energetic stability, using high-level quantum-chemical calculations, primarily in the guise of sophisticated Density-Functional Theory (DFT) approaches. In the absence of applied pressure, ice Ih is predicted to be energetically more stable than ice Ic, and TIP4P-predicted results and ranking compare well with the results obtained from DFT calculations. However, perhaps not unexpectedly, the deviation between TIP4P- and DFT-calculated results increases with applied external pressure.

We proposed a new algorithm to generate proton disordered ice Ih, which greatly improves the operation efficiency. The direct coexistence technology was used to simulate the freezing of aqueous solution of TIP4P/Ice water and NaCl under seawater concentration. Taking the water freezing point at normal pressure of 273.15 K as the reference point of the simulated temperature, the doping of salt ions and the growth of ice were observed at three temperatures. The results presented that only a small amount of chloride ions were found to be doped into the structure of the growing ice, no sodium ions were observed.

We build on results from our previous investigation into ice Ih using a combination of classical many-body molecular dynamics (MB-MD) and normal mode (NM) calculations to obtain molecular-level inf...