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Much attention has been devoted to water’s metastable phase behavior, including polyamorphism (multiple amorphous solid phases), and the hypothesized liquid-liquid transition and associated critical point. However, the possible relationship between these phenomena remains incompletely understood. Using molecular dynamics simulations of the realistic TIP4P/2005 model, we found a striking signature of the liquid-liquid critical point in the structure of water glasses, manifested as a pronounced increase in long-range density fluctuations at pressures proximate to the critical pressure. By contrast, these signatures were absent in glasses of two model systems that lack a critical point. We also characterized the departure from equilibrium upon vitrification via the non-equilibrium index; water-like systems exhibited a strong pressure dependence in this metric, whereas simple liquids did not. These results reflect a surprising relationship between the metastable equilibrium phenomenon of liquid-liquid criticality and the non-equilibrium structure of glassy water, with implications for our understanding of water phase behavior and glass physics. Our calculations suggest a possible experimental route to probing the existence of the liquid-liquid transition in water and other fluids., The subtle connections between water’s supercooled liquid and glassy states are difficult to characterize. Gartner et al. suggest with MD simulations that the long-range structure of glassy water may reflect signatures of water’s debated second critical point in the supercooled liquid.

In this paper, we examine a new method for isotope separation involving the embedding of atoms and molecules into ice. This method is based upon isotope dependent embedding, i.e. capture, in a cryogenic matrix which exhibits excellent single-pass enrichment as demonstrated successfully for selected isotopes of Xe. This is a totally new method that holds significant promise as a quite general method for enrichment and purification. It is based upon exploiting the energetic and momentum barriers that need to be overcome in order to embed a given isotope or isotopologue into the capture matrix, initially amorphous ice. From our previous experiments, we know that there is a strong dependence of the embedding probability with incident momentum. Using supersonic molecular beam techniques, we generated Xe atomic beams of controlled velocities, relatively narrow velocity distributions due to supersonic expansion, and with all of the entrained isotopes having identical velocities arising from the seeded molecular beam expansion. As we had postulated, the heavier isotope becomes preferentially absorbed, i.e., embedded, in the ice matrix. Herein we demonstrate the efficacy of this method by comparing the capture of 134Xe and 136Xe to the reference isotope, 129Xe. Enrichment of the heavier isotopes in the capture matrix was 1.2 for 134Xe and 1.3 for 136Xe greater than that expected for natural abundance. Note that enriched isotopic fractions can be collected from either the condensate or the reflected fraction depending on interest in either the heavier or lighter isotope, respectively. Cycling of these single-step enrichment events for all methods can lead to significantly higher levels of purification, and routes to scale-up can be realistically envisioned. This method holds significant promise to be quite general in applicability, including both atomic isotopes or molecular isotopologues across a wide range of particle masses spanning, essentially, the periodic table. This topic has profound implications and significant potential impact for a wide-variety of isotope-based technologies in the physical and biological sciences, medicine, advanced energy and energetic systems, including isotopically-purified materials that exhibit high-performance electronic and thermal characteristics, as well as isotopically purified spin-free materials for use in quantum information science platforms.

Carbon and ice make up a substantial proportion of our Universe. Recent space exploration has shown that these two chemical species often coexist including on comets, asteroids and in the interstellar medium. Here we prepare mixtures of C60 fullerene and H2O by vapor co-deposition at 90 K with molar C60:H2O ratios ranging from 1:1254 to 1:5. The C60 percolation threshold is found between the 1:132 and 1:48 samples, corresponding to a transition from matrix-isolated C60 molecules to percolating C60 domains that confine the H2O. Below this threshold, the crystallization and thermal desorption properties of H2O are not significantly affected by the C60, whereas the crystallization temperature of H2O is shifted towards higher temperatures for the C60-rich samples. These C60-rich samples also display exotherms corresponding to the crystallization of C60 as the two components undergo phase separation. More than 60 volume percent C60 is required to significantly affect the desorption properties of H2O. A thick blanket of C60 on top of pure amorphous ice is found to display large cracks due to water desorption. These findings may help understand the recently observed unusual surface features and the H2O weather cycle on the 67P/Churyumov-Gerasimenko comet.

We numerically investigate the metastable equilibrium structure of deep supercooled and glassy water under pressure, covering the range of densities corresponding to the experimentally produced high-density and very-high-density amorphous phases. At $T = 188$ K, a continuous increase in density is observed on varying pressure from $2.5$ to $13$ kbar, with no signs of first-order transitions. Exploiting a recently proposed approach to the analysis of the radial distribution function -- based on topological properties of the hydrogen-bond network -- we are able to identify well-defined local geometries that involve pair of molecules separated by multiple hydrogen bonds, specific of the high and very high density structures., Main text: 5 pages, 6 figures. Supplemental material: 19 pages, 18 figures. Accepted for publication in Physical Review Letters

The stability of gas-saturated layers of amorphous ice created via the deposition of supersonic molecular beams of rarefied water vapor and methane on a substrate cooled with liquid nitrogen was experimentally studied. The adiabatic expansion of the molecular vapor beam at the exit from the supersonic nozzle leads to a decrease in temperature and the formation of crystalline nanoclusters in the flow. The presence of ready crystalline centers in nonequilibrium amorphous condensates shifts the onset of crystallization to low temperatures. The shape of the signal of differential thermal analysis, which consists of several exothermic peaks, indicates crystallization from different centers and a random nature of their distribution in the volume of the amorphous medium. Methane hydrate forms during the crystallization of water–gas condensates. Under conditions of deep metastability, the avalanche-like nucleation of crystallization centers captures gas molecules; therefore, they are not displaced by the movement of the crystallization front.

We present research detailing the sticking probability of CH4 on various D2O ices of terrestrial and astrophysical interest using a combination of time-resolved, in situ reflection absorption infra...

To investigate the surface diffusion of protons on amorphous ice, we performed molecular dynamics calculations. The diffusion mechanisms were analyzed by observing the trajectories of protons on the surface. The results show that the protons diffuse on the surface of amorphous ice via repeated formation and dissociation of H3O+. From the frequencies of the formation and dissociation of H3O+, the diffusion coefficients and activation energy were estimated in the temperature range of 40–130 K. The surface diffusion is an important factor for chemical reactions that occur on ice dust in interstellar molecular clouds.

In order to gain a molecular-level insight on the structure and performance of cement-based materials in high temperature environment, this paper investigates the structure, dynamics and mechanical properties of their main hydration product, calcium aluminosilicate hydrate (C-A-S-H), at elevated temperatures by using reactive molecular dynamics simulation. The results show that rising temperature can destroy the H-bond network of interlayer water molecules in C-A-S-H, leading to pronounced expansion of the interlayer regions. Meanwhile, interlayer water molecules lose its glassy water dynamics and exhibit dramatically high diffusivity with rising temperature. In addition, the calcium atoms show inhomogeneous dynamics at high temperature. At 1500K, the interlayer calcium atoms can escape from their coordination “cages” and diffuse, while the motion of those located in the principal layer are restricted by the Si–O and Al–O bonds throughout the simulation. Furthermore, reactive force field couples the mechanical response and chemical reaction during the uniaxial tensile test for C-A-S-H gel. The de-polymerization and hydrolytic reaction happens frequently in the deformed C-A-S-H gel at high temperature, resulting in degradation of stiffness and strength. On the other hand, the atomic rearrangement at elevated temperature contributes to the re-connection of broken chemical bonds, enhancing ductility of C-A-S-H.

Since Bridgman’s discovery of five solid water (H2O) ice phases1 in 1912, studies on the extraordinary polymorphism of H2O have documented more than seventeen crystalline and several amorphous ice structures2,3, as well as rich metastability and kinetic effects4,5. This unique behaviour is due in part to the geometrical frustration of the weak intermolecular hydrogen bonds and the sizeable quantum motion of the light hydrogen ions (protons). Particularly intriguing is the prediction that H2O becomes superionic6–12—with liquid-like protons diffusing through the solid lattice of oxygen—when subjected to extreme pressures exceeding 100 gigapascals and high temperatures above 2,000 kelvin. Numerical simulations suggest that the characteristic diffusion of the protons through the empty sites of the oxygen solid lattice (1) gives rise to a surprisingly high ionic conductivity above 100 Siemens per centimetre, that is, almost as high as typical metallic (electronic) conductivity, (2) greatly increases the ice melting temperature7–13 to several thousand kelvin, and (3) favours new ice structures with a close-packed oxygen lattice13–15. Because confining such hot and dense H2O in the laboratory is extremely challenging, experimental data are scarce. Recent optical measurements along the Hugoniot curve (locus of shock states) of water ice VII showed evidence of superionic conduction and thermodynamic signatures for melting16, but did not confirm the microscopic structure of superionic ice. Here we use laser-driven shockwaves to simultaneously compress and heat liquid water samples to 100–400 gigapascals and 2,000–3,000 kelvin. In situ X-ray diffraction measurements show that under these conditions, water solidifies within a few nanoseconds into nanometre-sized ice grains that exhibit unambiguous evidence for the crystalline oxygen lattice of superionic water ice. The X-ray diffraction data also allow us to document the compressibility of ice at these extreme conditions and a temperature- and pressure-induced phase transformation from a body-centred-cubic ice phase (probably ice X) to a novel face-centred-cubic, superionic ice phase, which we name ice XVIII2,17. The atomic structure of H2O is documented at several million atmospheres of pressure and temperatures of several thousand degrees, revealing shockwave-induced ultrafast crystallization and a novel water ice phase, ice XVIII, with exotic superionic properties.

Detailed knowledge about photo-induced electron dynamics in water is key to the understanding of several biological and chemical mechanisms, in particular for those resulting from ionizing radiation [1] . While several studies reporting on detailed low-energy electron scattering cross sections in amorphous ice, liquid water and large water clusters [2] and a time-resolved approach to investigate electron scattering in water has been reported [3] , such investigations in gas-phase water clusters have shown to be a promising bridge in between the gas and liquid phase, allowing for many technological limitations to be overcome and setting a clear route to perform attosecond-resolved spectroscopy of hydrated molecules. Indeed, extreme ultraviolet (XUV) attosecond pulses may be used to photo-ionize a water sample and to investigate the electron dynamics and transport properties with extremely high temporal resolution [4] .

The adsorption of a series of atoms and small molecules and radicals (H, C, N, O, NH, OH, H2O, CH3, and NH3) on hexagonal crystalline and amorphous ice clusters were obtained via classical molecular dynamics and electronic structure methods. The geometry and binding energies were calculated using a QMHigh:QMLow hybrid method on model clusters. Several combination of basis sets, density functionals and semi-empirical methods were compared and tested against previous works. More accurate binding energies were also refined via single point Coupled Cluster calculations. Most species, except carbon atom, physisorb on the surface, leading to rather small binding energies. The carbon atom forms a COH2 molecule and in some cases leads to the formation of a COH-H3O+ complex. Amorphous ices are characterized by slightly stronger binding energies than the crystalline phase. A major result of this work is to also access the dispersion of the binding energies since a variety of adsorption sites is explored. The interaction energies thus obtained may serve to feed or refine astrochemical models. The present methodology could be easily extended to other types of surfaces and larger adsorbates.

Water ice clouds form in the mesospheres of terrestrial planets in the solar system (and most likely elsewhere) by vapor deposition at low pressures and temperatures. Under these conditions a range of crystalline and amorphous phases of ice might form. The phase is important because it influences nucleation kinetics, density, vapor pressure over the solid, growth rates and particle shape. In the past, the temperature range over which these different phases exist has been defined on the basis of depositing ice at low temperature and warming it while observing phase changes. However, the direct deposition of ice at a range of temperatures relevant for the terrestrial planets has not been systematically investigated. Here we present X-ray Diffraction (XRD) measurements of water ice deposited at temperature intervals between 88 and 145 K in a vacuum chamber. XRD patterns showed that low density amorphous ice was formed at ≤120 K, stacking disordered ice I formed from 121 to 135 K and hexagonal ice I formed at 140 and 145 K. Direct deposition results in the stable hexagonal phase at much lower temperatures than when warming stacking disordered ice. All three phases of water ice observed here are possible in clouds in the mesospheres of Earth and Mars, while on Venus only amorphous ice is likely to form.

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. Graphic abstract: [Figure not available: see fulltext.].

In the heating process, monolayer ice will transform into liquid phase, while this melting behavior under high lateral pressure is seldom concerned. This chapter focuses on the superheating of monolayer ice in graphene nanocapillaries. We observed four different melting scenarios and monolayer triangular amorphous ice from MD simulations.

We introduce a parameter-free structural indicator to classify local environments of water molecules in stable and supercooled liquid states, which reveals a clear two-peak distribution of local properties. The majority of molecules are tetrahedrally coordinated (T molecules), via low-energy hydrogen bonds. The minority component, whose relative concentration decreases with a decrease in the temperature at constant pressure, is characterized by prevalently three-coordinated molecules, giving rise to a distorted local network around them (D molecules). The inter-conversion between T and D molecules explains the increasing specific heat at constant pressure on cooling. The local structure around a T molecule resembles the one found experimentally in low-density amorphous ice (a network structure mostly composed by T molecules), while the local structure around a D molecule is reminiscent of the structural properties of high-density amorphous ice (a network structure composed by a mixture of T and D molecules). Fil: Montes de Oca, Joan Manuel. University of Chicago; Estados Unidos Fil: Sciortino, Francesco. Sapienza Universidad de Roma. Dipartimento di Fisica; Italia Fil: Appignanesi, Gustavo Adrian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina

Both carbon dioxide (CO 2 ) and water (H 2 O) are triatomic molecules that are ubiquitous in nature, and both are among the five most abundant gases in the Earth’s atmosphere. At low temperature and ambient pressure, both CO 2 and H 2 O form molecular crystals––dry ice I and ice I h . Because water possesses distinctive hydrogen bonds, it exhibits intricate and highly pressure-dependent phase behavior, including at least 17 crystalline ice phases and three amorphous ice phases. In contrast, due to its weak van der Waals intermolecular interactions, CO 2 exhibits fewer crystalline phases except at extremely high pressures, where nonmolecular ordered structures arise. Herein, we show the molecular dynamics simulation results of numerous 2D polymorphs of CO 2 molecules in slit nanopores. Unlike bulk polymorphs of CO 2 , 2D CO 2 polymorphs exhibit myriad crystalline and amorphous structures, showing remarkable polymorphism and polyamorphism. We also show that depending on the thermodynamic path, 2D solid-to-solid phase transitions can give rise to previously unreported structures, e.g., wave-like amorphous CO 2 structures. Our simulation also suggests intriguing structural connections between 2D and 3D dry ice phases (e.g., Cmca and PA-3) and offers insights into CO 2 polyamorphic transitions through intermediate liquid or amorphous phases.

Akin to bulk water, water confined to an isolated nanoslit can show a wealth of new 2D phases of ice and amorphous ice, as well as unusual phase behavior. Indeed, 2D water phases, such as bilayer hexagonal ice and monolayer square ice, have been detected in the laboratory, confirming earlier computational predictions. Herein, we report theoretical evidence of a hitherto unreported state, namely, bilayer very low density amorphous ice (BL-VLDA), as well as evidence of a strong first-order transition between BL-VLDA and the BL amorphous ice (BL-A), and a weak first-order transition between BL-VLDA and the BL very low density liquid (BL-VLDL) water. The diffusivity of BL-VLDA is typically in the range of 10−9 cm2/s to 10−10 cm2/s. Similar to bulk (3D) water, 2D water can exhibit two forms of liquid in the deeply supercooled state. However, unlike supercooled bulk water, for which the two forms of liquid can coexist and merge into one at a critical point, the 2D BL-VLDL and BL high-density liquid (BL-HDL) phases are separated by the highly stable solid phase of BL-A whose melting line exhibits the isochore end point (IEP) near 220 K in the temperature−pressure diagram. Above the IEP temperature, BL-VLDL and BL-HDL are indistinguishable. At negative pressures, the metastable BL-VLDL exhibits a spatially and temporally heterogeneous structure induced by dynamic changes in the nanodomains, a feature much less pronounced in the BL-HDL.

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1–0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential of the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid., The electron affinity of liquid water is a fundamental property which has not yet been accurately measured. Here, the authors predict this property by coupling path-integral molecular dynamics with ab initio potentials and electronic structure calculations, revisiting several estimates used in the literature.

In this paper, molecular dynamics simulation was used to study the decomposition process of nanoscale methane hydrate at 1 atm and 227 K. The results predict that methane hydrate decomposes into supercooled water (SCW) and methane gas and the resulting SCW turns into very high density amorphous ice (VHDA). The density of the VHDA is as high as 1.2–1.4 g cm−3. The X-ray diffraction phase analysis showed that VHDA has a broad peak at 2θ of around 30°. The VHDA encapsulates the methane hydrate crystal so that the crystal can survive for a long time. The dissolved gas from the hydrate melt cannot escape out of the VHDA in a short time. The simulation results reveal new molecular insights into the decomposition behaviour of nanoscale methane hydrate below the ice point.

Interactions of N2O5 with water media are of great importance in atmospheric chemistry and have been the topic of extensive research for over two decades. Nevertheless, many physical and chemical properties of N2O5 at the surface or in bulk water are unknown or not microscopically understood. This study presents extensive new results on the physical properties of N2O5 in water and at the surface of water, with a focus on their microscopic basis. The main results are obtained using ab initio molecular dynamics and calculations of a potential of mean force. These include: (1) collisions of N2O5 with water at 300 K lead to trapping at the surface for at least 20 ps and with 95% probability. (2) During that time, there is no N2O5 hydrolysis, evaporation, or entry into the bulk. (3) Charge separation between the NO2 and NO3 groups of N2O5, fluctuates significantly with time. (4) Energy accommodation of the colliding N2O5 at the surface takes place within picoseconds. (5) The binding energy of N2O5 to a nanosize amorphous ice particle at 0 K is on the order of 15 kcal mol−1 for the main surface site. N2O5 binding to the cluster is due to one weak hydrogen bond and to interactions between partial charges on the N2O5 and on water. (6) The free-energy profile was calculated for transporting N2O5 from the gas phase through the interface and into bulk water. The corresponding concentration profile exhibits a propensity for N2O5 at the aqueous surface. The free energy barrier for entry from the surface into the bulk was determined to be 1.8 kcal mol−1. These findings are used to interpret recent experiments. We conclude with implications of this study for atmospheric chemistry.

In this paper we discuss apparent contradictions in the literature between dynamical results on supercooled confined water obtained by different experimental methods. The reason for the lack of a clear glass transition of confined water is also discussed. Dielectric relaxation data and results from differential scanning calorimetry measurements provide a consistent picture, but it is still unclear why the glass transition related structural (α) relaxation disappears before the normal time-scale of a calorimetric glass transition (i.e. about 100 s) is reached. From recent results on amorphous bulk ice we propose that this anomalous phenomenon may not be an effect of confinement, but an intrinsic property of water when it transforms to a crystal-like glassy state, probably around 225 K. Thus, the results from the studies of confined water in the so-called no man's land (the temperature range 150-235 K) where bulk water rapidly crystallizes may be of more relevance for supercooled and glassy bulk water than previously thought. Furthermore, the structural difference between glassy water (or amorphous ice) and crystalline ice is likely to be rather small, due to the large degree of disorder in crystalline ice.

Some biological particles, such as Snomax, are very active ice nucleating particles, inducing heterogeneous freezing in supercooled water at temperatures above −15 and up to −2 °C. Despite their exceptional freezing abilities, large uncertainties remain regarding the atmospheric abundance of biological ice nucleating particles, and their contribution to atmospheric ice nucleation. It has been suggested that small biological ice nucleating macromolecules or fragments can be carried on the surfaces of dust and other atmospheric particles. This could combine the atmospheric abundance of dust particles with the ice nucleating strength of biological material to create strongly enhanced and abundant ice nucleating surfaces in the atmosphere, with significant implications for the budget and distribution of atmospheric ice nucleating particles, and their consequent effects on cloud microphysics and mixed-phase clouds. The new critical surface area g framework that was developed by Beydoun et al. (2016) is extended to produce a heterogeneous ice nucleation mixing model that can predict the freezing behavior of multicomponent particle surfaces immersed in droplets. The model successfully predicts the immersion freezing properties of droplets containing Snomax bacterial particles across a mass concentration range of 7 orders of magnitude, by treating Snomax as comprised of two distinct distributions of heterogeneous ice nucleating activity. Furthermore, the model successfully predicts the immersion freezing behavior of a low-concentration mixture of Snomax and illite mineral particles, a proxy for the biological material–dust (bio-dust) mixtures observed in atmospheric aerosols. It is shown that even at very low Snomax concentrations in the mixture, droplet freezing at higher temperatures is still determined solely by the second less active and more abundant distribution of heterogeneous ice nucleating activity of Snomax, while freezing at lower temperatures is determined solely by the heterogeneous ice nucleating activity of pure illite. This demonstrates that in this proxy system, biological ice nucleating particles do not compromise their ice nucleating activity upon mixing with dust and no new range of intermediary freezing temperatures associated with the mixture of ice nucleating particles of differing activities is produced. The study is the first to directly examine the freezing behavior of a mixture of Snomax and illite and presents the first multicomponent ice nucleation model experimentally evaluated using a wide range of ice nucleating particle concentration mixtures in droplets.

A silicious material containing massive array of spherical nanocages connected to each other by small micropores was used to study ice nucleation in confined water under conditions of well-defined pore geometry. By purposefully selecting small size of the interconnecting pores below 2 nm, ice nucleation and growth were limited to occur only within the nanocages. By exploitation of nuclear magnetic resonance, ice nucleation rates at different temperatures were accurately measured. These rates were obtained to be substantially higher than those typically observed for micrometer-sized water droplets in air. In addition, the occurrence of correlations between ice nucleation in one nanocage with the phase state in the adjacent cages were observed. These results have important implication for a deeper understanding of ice nucleation, especially in confined geometries.

This density functional theory study compares water adsorption on the ceria (111) and (100) surfaces. In the absence of water, the (111) surface is more stable than the polar (100) surface, but at higher water coverages the (100) surface is favored due to the formation of a highly stable “square ice” layer on top of the fully hydroxylated surface. At ceria (111), an amorphous ice layer is favored that consists predominantly of molecularly adsorbed water. This change in the water–surface interactions stems from the different surface terminations: the lower coordination numbers of ions at the (100) surface lead to higher water adsorption energies and a preference toward dissociative adsorption. Furthermore, the distance between neighboring surface oxygen ions (274 pm) is very close to the O–O distance in bulk ice, which facilitates the growth of a well-ordered ice layer. At the (111) surface, the distance between neighboring surface oxygen ions is significantly larger (388 pm), which hampers water–water int...

To investigate the surface structure, we performed molecular dynamics calculations of amorphous ice. The result shows that a low density layer, which forms a few hydrogen bonds with weaker strength, exists in the surface. Furthermore, the sintering processes were simulated to investigate the structure of grain boundary formed from the adsorption of two surfaces. The result indicates that a low density region exists in a boundary between amorphous ice grains. The structures of surface and interface of amorphous ice have important implications for adsorption, diffusion, and chemical reaction in ice grains of interstellar molecular clouds.

Layers of amorphous ice were prepared by deposition of supersonic molecular beams of rarefied vapor on a substrate cooled by liquid nitrogen. Molecular beam entered a vacuum chamber through Laval nozzle, which accelerated it to a supersonic speed. An adiabatic expansion of molecular beam leads to a decrease in the temperature at the nozzle outlet and formation of crystalline nanoclusters of water. Under heating of nonequilibrium condensates one could observe a glass transition (softening) and subsequent spontaneous crystallization. The presence of water clusters introduced into nonequilibrium condensates artificially ensured conditions for the initiation of “hot” centers and a transition to an explosive regime of crystallization in an amorphous medium. A theoretical analysis has been made of the role of the thermal conditions in which the crystallization of an amorphous substance proceeds, with allowance for the nonstationary nucleation.

The formation of molecules in the interstellar medium is significantly driven by grain chemistry, ranging from simple (e.g. H2) to relatively complex (e.g. CH3OH) products. The movement of atoms and molecules on amorphous ice surfaces is not well constrained, and this is a quintessential component of surface chemistry. We show that ice structure created by utilizing an off-lattice Monte Carlo kinetics model is highly dependent on deposition parameters (i.e. angle, rate, and temperature). The model, thus far, successfully predicts the densities of deposition rate- and temperature-dependent laboratory experiments. The simulations indicate, when angle and deposition rate increase, the density decreases. On the other hand, temperature has the opposite effect and will increase the density. We can make ices with desired densities and monitor how molecules, like CO, percolate through H2O ice pores. The strength of this model lies in the ability to replicate TPD-like experiments by monitoring molecules diffusing on and desorbing from user-defined surfaces.

Hydrogen (H) atom diffusion on dust grain surfaces is the rate-limiting step in many hydrogenation reactions taking place in interstellar clouds. In cold (10–30 K) molecular clouds, the dust grains are coated by amorphous water ice. Therefore, H adatom mobility on ice surfaces is of fundamental importance in this context. We have calculated H atom adsorption and diffusion on both crystalline and amorphous ice surfaces using an analytic interaction potential for H2O–H. Tunneling rates for H atom hops between adsorption sites are explicitly calculated, the kinetic Monte Carlo method is used to simulate long time scale evolution and the diffusion coefficient, D, is evaluated for the temperature range 5–120 K. For ice Ih, we find D = 1.6 × 10–7 cm2/s at 10 K and below that temperature tunneling becomes the dominant diffusion mechanism. On the amorphous ice surface, the mobility of H is much slower than for ice Ih, D = 5.8 × 10–11 cm2/s at 25 K. Below 25 K, the H adatom becomes trapped in the deepest adsorptio...

This work is a study of CO and H2O molecules as adsorbates that interact on the surface of olivine dust grains. Olivine (forsterite) is present on the Earth, planetary dust, in the interstellar medium (ISM) and in particular in comets. The composition of amorphous ice is very important for the interpretation of processes that occur in the solar system and the ISM. Dust particles in ISM are composed of a heterogeneous mixture of amorphous or crystalline silicates (e.g. olivine) organic material, carbon, and other minor constituents. These dust grains are embedded in a matrix of ices, such as H2O, CO, CO2, NH3, and CH4. We consider that any amorphous ice will interact and grow faster on dust grain surfaces. In this work we explore the adsorption of CO-H2O amorphous ice onto several (100) forsterite surfaces (dipolar and non-dipolar), by using first principle calculations based on density functional theory (DFT). These models are applied to two possible situations: i) adsorption of CO molecules mixed into an amorphous ice matrix (gas mixture) and adsorbed directly onto the forsterite surface. This interaction has lower adsorption energy than polar molecules (H2O and NH3) adsorbed on this surface; ii) adsorption of CO when the surface has previously been covered by amorphous water ice (onion model). In this case the calculations show that adsorption energy is low, indicating that this interaction is weak and therefore the CO can be desorbed with a small increase of temperature. Vibration spectroscopy for the most stable complex was also studied and the frequencies were in good agreement with experimental frequency values.

Structural properties and microscopic dynamics of water and amorphous ice have been studied by the molecular dynamics method. It has been found that the distribution function of the tetrahedricity parameter exhibits two ranges, which correspond to local molecular formations with low and high degrees of tetrahedricity. The number of molecular clusters with a high degree of tetrahedricity grows as temperature decreases. It has been shown that the vibrational density of states comprises two vibrational modes. A low-frequency vibrational mode strongly depends on pressure and is almost independent of temperature, while a high-frequency mode is relevant to the pressure-independent heat motion of molecules. The geometric criterion of hydrogen bonds has been used to evaluate their continuous lifetime as depending on temperature for molecules with different coordination values. The average lifetime of a hydrogen bond substantially depends on the coordination of molecules, with the temperature dependence of the coordination obeying the activation dynamics.

This work reports on frequency dependent ambient-pressure dielectric measurements of hyperquenched glassy water, ice IV, ice VI, as well as a CO2-filled clathrate hydrate, the latter featuring a chiral water network. The dipolar time scales and the spectral shapes of the loss spectra of these specimens are mapped out and compared with literature data on low-density and high-density amorphous ices as well as on amorphous solid water. There is a trend that the responses of the more highly dense amorphous ices are slightly more dynamically heterogeneous than those of the lower-density amorphous ices. Furthermore, practically all of the amorphous ices, for which broadband dielectric spectra are available, display a curved high-frequency wing. Conversely, the high-frequency flanks of the nominally pure ice crystals including ice V and ice XII can be characterized by an approximate power-law behavior. While the spectral shapes of the nominally pure ices thus yield some hints regarding their amorphicity or crystallinity, a comparison of their time scale appears less distinctive in this respect. In the accessible temperature range, the relaxation times of the crystalline ices are between those of low-density and high-density amorphous ice. Hence, with reference also to previous work, the application of suitable doping currently seems to be the best dielectric spectroscopy approach to distinguish amorphous from crystalline ices.

Here I show that experimental and simulation data on liquid water using vibrational (infrared and Raman) and X-ray (absorption and emission) spectroscopies, as well as recent data from X-ray scattering, are fully consistent with a two-state picture of water. At ambient conditions there are fluctuations between a dominating high-density liquid (HDL) and a low-density form (LDL). These are related to the two forms of amorphous ice at very low temperature, high-density amorphous (HDA) and low-density amorphous (LDA), which interconvert in a first-order-like transition. This transition line is assumed to continue into the so-called “No-man’s land” as a liquid-liquid transition and terminate in a critical point with very large fluctuations between the two liquid forms. These fluctuations extend in a funnel-like region up to ambient temperatures and pressures and give water its unusual properties which are fundamental to life. With this picture we find simple, intuitive explanations of the anomalous properties of water, such as the density maximum at 4 °C, why ice floats, and why the compressibility and heat capacity grow as the liquid is cooled. We summarize by noting that in this picture, water is not a complicated liquid, but two normal liquids with a complicated relationship.

Low-density amorphous ice (LDA) is of paramount importance not only for fields such as astronomy, meteorology and biology from a scientific point of view, but also for technological applications like cryo-scanning electron microscopy and electron-beam lithography utilizing ice resists. Recent advances in LDA have been reviewed, focusing on its formation and crystallization processes. The specific aspects of this review include: (a) the LDA formation methods and the corresponding required conditions, (b) the measurement principles of the density, thermal conductivity and the growth rate of LDA, (c) the monitoring of the phase transformation, (d) the transformation kinetics of LDA to crystalline ice. Finally, open questions as well as future challenges relating to LDA are discussed.

Ice crystals in the atmosphere nucleate from supercooled liquid water and grow by vapor uptake. The structure of the ice polymorph grown has strong impact on the morphology and light scattering of the ice crystals, modulates the amount of water vapor in ice clouds, and can impact the molecular uptake and reactivity of atmospheric aerosols. Experiments and molecular simulations indicate that ice nucleated and grown from deeply supercooled liquid water is metastable stacking disordered ice. The ice polymorph grown from vapor has not yet been determined. Here we use large-scale molecular simulations to determine the structure of ice that grows as a result of uptake of water vapor in the temperature range relevant to cirrus and mixed-phase clouds, elucidate the molecular mechanism of the formation of ice at the vapor interface, and compute the free energy difference between cubic and hexagonal ice interfaces with vapor. We find that vapor deposition results in growth of stacking disordered ice only under conditions of extreme supersaturation, for which a nonequilibrium liquid layer completely wets the surface of ice. Such extreme conditions have been used to produce stacking disordered frost ice in experiments and may be plausible in the summer polar mesosphere. Growth of ice from vapor at moderate supersaturations in the temperature range relevant to cirrus and mixed-phase clouds, from 200 to 260 K, produces exclusively the stable hexagonal ice polymorph. Cubic ice is disfavored with respect to hexagonal ice not only by a small penalty in the bulk free energy (3.6 ± 1.5 J mol(-1) at 260 K) but also by a large free energy penalty at the ice-vapor interface (89.7 ± 12.8 J mol(-1) at 260 K). The latter originates in higher vibrational entropy of the hexagonal-terminated ice-vapor interface. We predict that the free energy penalty against the cubic ice interface should decrease strongly with temperature, resulting in some degree of stacking disorder in ice grown from vapor in the tropical tropopause layer, and in polar stratospheric and noctilucent clouds. Our findings support and explain the evolution of the morphology of ice crystals from hexagonal to trigonal symmetry with decreasing temperature, as reported by experiments and in situ measurements in clouds. We conclude that selective growth of the elusive cubic ice polymorph by manipulation of the interfacial properties can likely be achieved at the ice-liquid interface but not at the ice-vapor interface.

The glass transitions of low-density amorphous ice (LDA) and high-density amorphous ice (HDA) are the topic of controversial discussions. Understanding their exact nature may be the key to explaining the anomalies of liquid water but has also got implications in the general context of polyamorphism, the occurrence of multiple amorphous forms of the same material. We first show that the glass transition of hydrogen-disordered ice VI is associated with the kinetic unfreezing of molecular reorientation dynamics by measuring the calorimetric responses of the corresponding H2O, H2(18)O, and D2O materials in combination with X-ray diffraction. Well-relaxed LDA and HDA show identical isotopic-response patterns in calorimetry as ice VI, and we conclude that the glass transitions of the amorphous ices are also governed by molecular reorientation processes. This "reorientation scenario" seems to resolve the previously conflicting viewpoints and is consistent with the fragile-to-strong transition from water to the amorphous ices.

We present an overview of recent static and time-resolved vibrational spectroscopic studies of liquid water from ambient conditions to the supercooled state, as well as of crystalline and amorphous ice forms. The structure and dynamics of the complex hydrogen-bond network formed by water molecules in the bulk and interphases are discussed, as well as the dissipation mechanism of vibrational energy throughout this network. A broad range of water investigations are addressed, from conventional infrared and Raman spectroscopy to femtosecond pump-probe, photon-echo, optical Kerr effect, sum-frequency generation, and two-dimensional infrared spectroscopic studies. Additionally, we discuss novel approaches, such as two-dimensional sum-frequency generation, three-dimensional infrared, and two-dimensional Raman terahertz spectroscopy. By comparison of the complementary aspects probed by various linear and nonlinear spectroscopic techniques, a coherent picture of water dynamics and energetics emerges. Furthermore, we outline future perspectives of vibrational spectroscopy for water researches.

Using molecular dynamics simulation, we investigate the phase behavior of water confined in graphene nanocapillaries at room temperature (300 K). Here, the lateral pressure Pzz is used as the primary controlling variable, and its effect on the behavior of trilayer water is systematically studied. Three (meta)stable trilayer (TL) crystalline/amorphous ice phases, namely, TL-ABAI, TL-ABA, and TL-AAAI, are observed in our simulations with the lateral pressure in the range of 1.0 GPa ≤ Pzz ≤ 6.0 GPa. TL-ABAI exhibits a square lattice in every layer, and the three layers exhibit the ABA stacking pattern; i.e., the oxygen atoms in the two outer layers are in registry. This new trilayer ice structure can also be viewed as a bilayer clathrate hydrate with water molecules in the middle layer serving as the guest molecules. With increasing lateral pressure, typically, the solid-to-liquid-to-solid phase transition occurs, during which the structural transformation from triangular to square-like in the ice layer is a...

The detection of nanobubbles on surfaces is well established (e.g., AFM and optical microscopy methods), but currently no methods exist for the direct detection of bulk nanobubbles. Here, cryo-electron microscopy (cryo-EM) has been employed to observe bubbles in aqueous solutions for the first time. Nitrogen bubbles generated by a chemical reaction were observed in amorphous ice trapped between two carbon films. The cryo-EM images of bubbles showed the same features as predicted by theory. The fact that no bubbles were observed near an air–water interface suggests that bubbles may diffuse to the nearby air–water interface and escape. The estimate of the bubble diffusion coefficient is about 30–250 μm2/s.

In spite of the resurgence in ice nucleation research a comparatively small number of studies deal with the phenomenon of pre-activation in heterogeneous ice nucleation. Fifty years ago, it was shown that various mineral dust and volcanic ash particles can be pre-activated to become nuclei for ice crystal formation even at temperatures as high as 270–271 K. Pre-activation was achieved under ice-subsaturated conditions without any preceding macroscopic ice growth by just temporarily cooling the particles to temperatures below 228 K. A two-step mechanism involving capillary condensation of supercooled water and subsequent homogeneous freezing was proposed to account for the particles' enhanced ice nucleation ability at high temperatures. This work reinvestigates the efficiency of the proposed pre-activation mechanism in temperature-cycling experiments performed in a large cloud chamber with suspended particles. We find the efficiency to be highest for the clay mineral illite as well as for highly porous materials like zeolite and diatomaceous earth, whereas most aerosols generated from desert dust surface samples did not reveal a measurable pre-activation ability. The pre-activation efficiency is linked to particle pores in a certain size range. As estimated by model calculations, only pores with diameters between about 5 and 8 nm contribute to pre-activation under ice-subsaturated conditions. This range is set by a combination of requirements from the negative Kelvin effect for condensation and a critical size of ice embryos for ice nucleation and melting. In contrast to the early study, pre-activation is only observed for temperatures below 260 K. Above that threshold, the particles' improved ice nucleation ability disappears due to the melting of ice in the pores.

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H2O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol-1 on the silica surface below 25 K and 0 kJ mol-1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.

Crystallization of ice from deeply supercooled water and amorphous ices - a process of fundamental importance in the atmosphere, interstellar space, and cryobiology - results in stacking disordered ices with a wide range of metastabilities with respect to hexagonal ice. The structural origin of this high variability, however, has not yet been elucidated. Here we use molecular dynamics simulations with the mW water model to characterize the structure of ice freshly grown from supercooled water at temperatures from 210 to 270 K, the thermodynamics of stacking faults, line defects, and interfaces, and to elucidate the interplay between kinetics and thermodynamics in determining the structure of ice. In agreement with experiments, the ice grown in the simulations is stacking disordered with a random distribution of cubic and hexagonal layers, and a cubicity that decreases with growth temperature. The former implies that the cubicity of ice is determined by processes at the ice/liquid interface, without memory of the structure of buried ice layers. The latter indicates that the probability of building a cubic layer at the interface decreases upon approaching the melting point of ice, which we attribute to a more efficient structural equilibration of ice at the liquid interface as the driving force for growth wanes. The free energy cost for creating a pair of cubic layers in ice is 8.0 J mol(-1) in experiments, and 9.7 ± 1.9 J mol(-1) for the mW water model. This not only validates the simulations, but also indicates that dispersion in cubicity is not sufficient to explain the large energetic variability of stacking disordered ices. We compute the free energy cost of stacking disorder, line defects, and interfaces in ice and conclude that a characterization of the density of these defects is required to predict the degree of metastability and vapor pressure of atmospheric ices.

Water, when constrained between two graphene sheets and under ultrahigh pressure, can manifest dramatic differences from its bulk counterparts such as the van der Waals pressure induced water-to-ice transformation, known as the metastability limit of two-dimensional (2D) liquid. Here, we present result of a new crystalline structure of bilayer ice with the AB-stacking order, observed from molecular dynamics simulations of constrained water. This AB-stacked bilayer ice (BL-ABI) is transformed from the puckered monolayer square-like ice (pMSI) under higher lateral pressure in the graphene nanocapillary at ambient temperature. BL-ABI is a proton-ordered ice with square-like pattern. The transition from pMSI to BL-ABI is through crystal-to-amorphous-to-crystal pathway with notable hysteresis-loop in the potential energy during the compression/decompression process, reflecting the compression/tensile limit of the 2D monolayer/bilayer ice. In a superheating process, the BL-ABI transforms into the AB-stacked bilayer amorphous ice with the square-like pattern.

To investigate the structure of interface between forsterite glass and amorphous H2O ice, we performed molecular dynamics calculations. The result shows that a low-density layer for both forsterite and ice exists in the interface. Furthermore, the decomposition of water molecules was observed in the interface, although the decomposition rate decreases as the temperature decreases. The decomposition mechanisms of H2O are important to understand not only to the origin of water on terrestrial planets but also to the chemical evolution processes of various molecules in interstellar molecular clouds.

Water Phases Theoretical simulations suggest that deeply supercooled water undergoes a transition between high- and low-density forms, but this transition is difficult to study experimentally because it occurs under conditions in which ice crystallization is extremely rapid. Kim et al. combined x-ray lasers for rapid structure determination with infrared femtosecond pulses for rapid heating of amorphous ice layers formed at about 200 kelvin. The heating process created high-density liquid water at increased pressures. As the layer expanded and decompressed, low-density liquid domains appeared and grew on time scales between 20 nanoseconds and 3 microseconds, which was much faster than competing ice crystallization. Science , this issue p. [978][1] [1]: /lookup/doi/10.1126/science.abb9385

The water-solid interaction is fundamentally important for understanding and controlling the structures of interfacial water. Here we study the initial stage of water adsorption and nucleation on a Cd(0001) surface, through a combination of low temperature scanning tunnelling microscopy (STM) experiments and first-principles density-functional theory (DFT) calculation. Water is found to aggregate into various clusters with the dominant of water dimers. Particularly, the amorphous ice nanoflakes are built exclusively from water dimers. Driven by the electric field from a STM tip, the water dimers can hop across the surface, detach from a cluster with subsequent attaching to another, or rotate or diffuse within the amorphous ice nanoflakes. DFT calculations demonstrate that the ultrahigh stability of water dimers results from the adsorption-induced enhancement of dipole moment of water.

Amorphous ice has long been invoked as a means for trapping extreme volatiles into solids, explaining the abundances of these species in comets and planetary atmospheres. Experiments have shown that such trapping is possible and have been used to estimate the abundances of each species in primitive ices after they formed. However, these experiments have been carried out at deposition rates which exceed those expected in a molecular cloud or solar nebula by many orders of magnitude. Here we develop a numerical model which reproduces the experimental results and apply it to those conditions expected in molecular clouds and protoplanetary disks. We find that two regimes of ice trapping exist: `burial trapping' where the ratio of trapped species to water in the ice reflects that same ratio in the gas and `equilibrium trapping' where the ratio in the ice depends only on the partial pressure of the trapped species in the gas. The boundary between these two regimes is set by both the temperature and rate of ice deposition. Such effects must be accounted for when determining the source of trapped volatiles during planet formation., 13 pages, 6 figures

We combine 1H, 2H, and 7Li NMR methods to investigate the dynamics of water molecules and lithium ions in LiCl aqueous solutions over wide ranges of time and length scales down to their glass transitions. Structural relaxation times τ and self-diffusion coefficients D reveal that water and lithium dynamics are faster for lower salt content at ambient temperatures, while the differences vanish upon cooling when fractional freezing leads to similar salt concentrations in the remaining liquid phases. Relaxation times and diffusion coefficients of water molecules agree with those of lithium ions in the weakly supercooled regime, indicating that the dynamics are strongly coupled. Furthermore, non-Arrhenius temperature dependence is found and the Stokes-Einstein relation is obeyed in this temperature range. However, we observe various decoupling phenomena for the motion of the constituents and for dynamics on different length scales in the deeply supercooled regime. Most notably, the rotational motion of the water molecules does not follow the glassy slowdown of the studied salt solutions below ∼145 K, but it rather resembles that in nanoscopic confinement, molecular solutions, and high-density amorphous ice at low temperatures. This common low-temperature water dynamics is characterized by large-angle reorientation and Arrhenius temperature dependence.

Formation of molecular oxygen in and on amorphous ice in the interstellar medium requires oxygen diffusion to take place. Recent experiments suggest that this process involves quantum tunneling of the oxygen atoms at sufficiently low temperatures. Fit- ting experimental diffusion rates between 6 and 25 K to an expression that accounts for the roughness of the surface yields excellent agreement. The molecular dynamics of adsorbed oxygen is characterized by rapid intrasite dynamics followed by intersite transitions over distances of ∼ 10 ̊ A. Explicit simulations using a realistic free energy surface for oxygen diffusion on amorphous ice down to 10 K show that quantum tun- neling is not required for mobility of adsorbed oxygen. This is confirmed by comparing quantum and classical simulations using the same free energy surface. The ratio of diffusional and desorption energy E dif /E des = 275/1082 ≈ 0.3 is at the lower end of typically used values but still consistent with assumptions made in models for inter- stellar chemistry.

Some two-dimensional liquid systems are theoretically predicted to have an anomalous phase transition due to unique intermolecular interactions, for example the first-order transition between two-dimensional high-density water and low-density amorphous ice. However, it has never been experimentally observed, to the best of our knowledge. Here we report an entropy-driven phase transition between a high-density liquid crystal and low-density crystalline solid, directly observed by scanning tunneling microscope in carbon monoxide adsorbed on Cu(111). Combined with first principle calculations, we find that repulsive dipole–dipole interactions between carbon monoxide molecules lead to unconventional thermodynamics. This finding of unconventional thermodynamics in two-dimensional carbon monoxide not only provides a platform to study the fundamental principles of anomalous phase transitions in two-dimensional liquids at the atomic scale, but may also help to design and develop more efficient copper-based catalysis., Intermolecular interactions have a crucial role in the adsorption of molecules on a surface, however their role in promoting phase transitions is less well known. Here, the authors report an abnormal phase transition between a high-density liquid crystal and low-density solid in the case of carbon monoxide on Cu(111), driven by intermolecular interactions and entropy.

Nucleation of ice by airborne particles is a process vital to weather and climate, yet our understanding of the mechanisms underlying this process is limited. Kaolinite is a clay that is a significant component of airborne particles and is an effective ice nucleus. Despite receiving considerable attention, the microscopic mechanism(s) by which kaolinite nucleates ice is not known. We report molecular dynamics simulations of heterogeneous ice nucleation by kaolinite (001) surfaces. Both the Al-surface and the Si-surface nucleate ice. For the Al-surface, reorientation of the surface hydroxyl groups is essential for ice nucleation. This flexibility allows the Al-surface to adopt a structure which is compatible with hexagonal ice, Ih, at the atomic level. On the rigid Si-surface, ice nucleates via an unusual structure that consists of an ordered arrangement of hexagonal and cubic ice layers, joined at their basal planes where the interfacial energy cost is low. This ice structure provides a good match to the atomistic structure of the Si-surface. This example is important and may have far-reaching implications because it demonstrates that potential ice nuclei need not be good atomic-level matches to particular planes of ice Ih or cubic ice, Ic. It suggests that surfaces can act as effective ice nuclei by matching one of the much larger set of planes that can be constructed by regular arrangements of hexagonal and cubic ice.