Water Ice Structures Research Articles

Diffusion of CH4in amorphous solid water

Context.The diffusion of volatile species on amorphous solid water ice affects the chemistry on dust grains in the interstellar medium as well as the trapping of gases enriching planetary atmospheres or present in cometary material.Aims.The aim of the work is to provide diffusion coefficients of CH4on amorphous solid water (ASW) and to understand how they are affected by the ASW structure.Methods.Ice mixtures of H2O and CH4were grown in different conditions and the sublimation of CH4was monitored via infrared spectroscopy or via the mass loss of a cryogenic quartz crystal microbalance. Diffusion coefficients were obtained from the experimental data assuming the systems obey Fick’s law of diffusion. Monte Carlo simulations were used to model the different amorphous solid water ice structures investigated and were used to reproduce and interpret the experimental results.Results.Diffusion coefficients of methane on amorphous solid water have been measured to be between 10−12and 10−13cm2s−1for temperatures ranging between 42 K and 60 K. We show that diffusion can differ by one order of magnitude depending on the morphology of amorphous solid water. The porosity within water ice and the network created by pore coalescence enhance the diffusion of species within the pores. The diffusion rates derived experimentally cannot be used in our Monte Carlo simulations to reproduce the measurements.Conclusions.We conclude that Fick’s laws can be used to describe diffusion at the macroscopic scale, while Monte Carlo simulations describe the microscopic scale where trapping of species in the ices (and their movement) is considered.

Water-Ice Analogues of Polycyclic Aromatic Hydrocarbons: Water Nanoclusters on Cu(111).

Water has an incredible ability to form a rich variety of structures, with 16 bulk ice phases identified, for example, as well as numerous distinct structures for water at interfaces or under confinement. Many of these structures are built from hexagonal motifs of water molecules, and indeed, for water on metal surfaces, individual hexamers of just six water molecules have been observed. Here, we report the results of low-temperature scanning tunneling microscopy experiments and density functional theory calculations which reveal a host of new structures for water–ice nanoclusters when adsorbed on an atomically flat Cu surface. The H-bonding networks within the nanoclusters resemble the resonance structures of polycyclic aromatic hydrocarbons, and water–ice analogues of inene, naphthalene, phenalene, anthracene, phenanthrene, and triphenylene have been observed. The specific structures identified and the H-bonding patterns within them reveal new insight about water on metals that allows us to refine the so-called “2D ice rules”, which have so far proved useful in understanding water–ice structures at solid surfaces.

SUBSURFACE CHARACTERIZATION OF 67P/CHURYUMOV–GERASIMENKO’S ABYDOS SITE

ABSTRACT On 2014 November 12, the ESA/Rosetta descent module Philae landed on the Abydos site of comet 67P/Churyumov–Gerasimenko. Aboard this module, the Ptolemy mass spectrometer measured a CO/CO2 ratio of 0.07 ± 0.04, which differs substantially from the value obtained in the coma by the Rosetta/ROSINA instrument, suggesting a heterogeneity in the comet nucleus. To understand this difference, we investigated the physicochemical properties of the Abydos subsurface, leading to CO/CO2 ratios close to that observed by Ptolemy at the surface of this region. We used a comet nucleus model that takes into account different water ice phase changes (amorphous ice, crystalline ice, and clathrates) as well as diffusion of molecules throughout the pores of the matrix. The input parameters of the model were optimized for the Abydos site, and the ROSINA CO/CO2 measured ratio is assumed to correspond to the bulk value in the nucleus. We find that all considered structures of water ice are able to reproduce the Ptolemy observation with a time difference not exceeding ∼50 days, i.e., lower than ∼2% on 67P/Churyumov–Gerasimenko’s orbital period. The suspected heterogeneity of 67P/Churyumov–Gerasimenko’s nucleus is also found possible only if it is constituted of crystalline ices. If the icy phase is made of amorphous ice or clathrates, the difference between Ptolemy and ROSINA’s measurements would rather originate from the spatial variations in illumination on the nucleus surface. An eventual new measurement of the CO/CO2 ratio at Abydos by Ptolemy could be decisive to distinguish between the three water ice structures.

Perspective: How good is DFT for water?

Kohn-Sham density functional theory (DFT) has become established as an indispensable tool for investigating aqueous systems of all kinds, including those important in chemistry, surface science, biology, and the earth sciences. Nevertheless, many widely used approximations for the exchange-correlation (XC) functional describe the properties of pure water systems with an accuracy that is not fully satisfactory. The explicit inclusion of dispersion interactions generally improves the description, but there remain large disagreements between the predictions of different dispersion-inclusive methods. We present here a review of DFT work on water clusters, ice structures, and liquid water, with the aim of elucidating how the strengths and weaknesses of different XC approximations manifest themselves across this variety of water systems. Our review highlights the crucial role of dispersion in describing the delicate balance between compact and extended structures of many different water systems, including the liquid. By referring to a wide range of published work, we argue that the correct description of exchange-overlap interactions is also extremely important, so that the choice of semi-local or hybrid functional employed in dispersion-inclusive methods is crucial. The origins and consequences of beyond-2-body errors of approximate XC functionals are noted, and we also discuss the substantial differences between different representations of dispersion. We propose a simple numerical scoring system that rates the performance of different XC functionals in describing water systems, and we suggest possible future developments.

How to link the relative abundances of gas species in coma of comets to their initial chemical composition?

Comets are expected to be the most primitive objects in the Solar System. The chemical composition of these objects is frequently assumed to be directly provided by the observations of the abundances of volatile molecules in the coma. The present work aims to determine the relationship between the chemical composition of the coma, the outgassing profile of volatile molecules and the internal chemical composition, and water ice structure of the nucleus, and physical assumptions on comets. To do this, we have developed a quasi 3D model of a cometary nucleus which takes into account all phase changes and water ice structures (amorphous, crystalline, clathrate, and a mixture of them); we have applied this model to the Comet 67P/Churyumov-Gerasimenko, the target of the Rosetta mission. We find that the outgassing profile of volatile molecules is a strong indicator of the physical and thermal properties (water ice structure, thermal inertia, abundances, distribution, physical differentiation) of the solid nucleus. Day/night variations of the rate of production of species helps to distinguish the clathrate structure from other water ice structures in nuclei, implying different thermodynamic conditions of cometary ice formation in the protoplanetary disc. The relative abundance (to H2O) of volatile molecules released from the nucleus interior varies by some orders of magnitude as a function of the distance to the Sun, the volatility of species, their abundance and distribution between the ”trapped” and ”condensed” states, the structure of water ice, and the thermal inertia and other physical assumptions (dust mantle, …) on the nucleus. For the less volatile molecules such as CO2 and H2S, the relative (to H2O) abundance of species in coma remain similar to the primitive composition of the nucleus (relative deviation less than 25%) only around the perihelion passage (in the range −3 to −2 to +2–3AU), whatever is the water ice structure and chemical composition, and under the conditions that the nucleus is not fully covered by a dust mantle. The relative (to H2O) abundance of highly volatile molecules such as CO and CH4 in the coma remain approximately equal to the primitive nucleus composition only for nuclei made of clathrates. The nucleus releases systematically lower relative abundances of highly volatile species (up to one order of magnitude) around perihelion (in the range −3 to −2 to +2–3AU) in the cases of the crystalline and amorphous water ice structures in the nuclei. The rate of production, the outgassing profile and the relative abundances (to H2O) of volatile molecules are the key parameters allowing one to retrieve the chemical composition and thermodynamic conditions of cometary ice formation in the early Solar System. The coming observations of the coma and nucleus by the Rosetta mission instruments (VIRTIS, MIRO, …) should provide the necessary constraints to the model to allow it to infer the primordial ice structure and composition of the comet.

First-principles energetics of water clusters and ice: A many-body analysis

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Recent work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.

Energy benchmarks for water clusters and ice structures from an embedded many-body expansion

We show how an embedded many-body expansion (EMBE) can be used to calculate accurate ab initio energies of water clusters and ice structures using wavefunction-based methods. We use the EMBE described recently by Bygrave et al. [J. Chem. Phys. 137, 164102 (2012)], in which the terms in the expansion are obtained from calculations on monomers, dimers, etc., acted on by an approximate representation of the embedding field due to all other molecules in the system, this field being a sum of Coulomb and exchange-repulsion fields. Our strategy is to separate the total energy of the system into Hartree-Fock and correlation parts, using the EMBE only for the correlation energy, with the Hartree-Fock energy calculated using standard molecular quantum chemistry for clusters and plane-wave methods for crystals. Our tests on a range of different water clusters up to the 16-mer show that for the second-order Møller-Plesset (MP2) method the EMBE truncated at 2-body level reproduces to better than 0.1 mE(h)/monomer the correlation energy from standard methods. The use of EMBE for computing coupled-cluster energies of clusters is also discussed. For the ice structures Ih, II, and VIII, we find that MP2 energies near the complete basis-set limit reproduce very well the experimental values of the absolute and relative binding energies, but that the use of coupled-cluster methods for many-body correlation (non-additive dispersion) is essential for a full description. Possible future applications of the EMBE approach are suggested.

A cometary nucleus model taking into account all phase changes of water ice: amorphous, crystalline, and clathrate

Context. Current theories, models of cometary nuclei and of ice formation in the protoplanetary disk, and laboratory studies suggest that cometary materials could be formed of pure crystalline water ice, amorphous water ice, clathrate hydrate, or a mixture of these structures of water ice. However, current models of cometary nuclei consider only two forms of ice during the thermodynamic evolution of comets: amorphous and crystalline water ices. Aims. In this work, we have developed a model of cometary nucleus that takes into account all water ice structures and phase changes in order to predict the outgassing profile of volatile molecules that could be measured by the Rosetta mission and can be used to constrain the structural type of ice existing in the interior of the Comet 67P/Churyumov-Gerasimenko, the target comet of the Rosetta mission, and, hopefully, its initial composition.Methods. We added the physic of formation/dissociation of clathrate hydrates in addition to others physical processes that are taken into account in models without clathrate hydrates. All thermal changes, as well as the release and trapping of gas with water phase changes are taken into account.Results. This model describes heat transmission, latent heat exchanges, all water ices structures and transitions (amorphous-to-pure crystalline, amorphous-to-clathrate hydrates and pure crystalline-to-clathrate hydrates and vise versa), sublimation/recondensation of volatile molecules in the nucleus, gas diffusion, gas released and trapped by crystallization and clathrate formation/dissociation processes, as well as gas and dust release and mantle formation at the surface. Applying this model to the comet 67P/Churyumov-Gerasimenko, results show different outgassing profiles of volatiles molecules from the nucleus depending on the water ice structure, the distribution of volatile molecules between the “trapped” and “condensed” states in the nucleus and the thermal inertia of its porous matrix. Conclusions. Given these results, we pretend that this model is able to constrain the water ice structure and chemical composition in comets from outgassing profiles of volatile molecules, and especially those of the target comet of the Rosetta mission.

Crystal structure of ammonia dihydrate II

We have used density-functional-theory (DFT) methods together with a structure searching algorithm to make an experimentally constrained prediction of the structure of ammonia dihydrate II (ADH-II). The DFT structure is in good agreement with neutron diffraction data and verifies the prediction. The structure consists of the same basic structural elements as ADH-I, with a modest alteration to the packing, but a considerable reduction in volume. The phase diagram of the known ADH and ammonia monohydrate + water-ice structures is calculated with the Perdew-Burke-Ernzerhof density functional, and the effects of a semi-empirical dispersion corrected functional are investigated. The results of our DFT calculations of the finite-pressure elastic constants of ADH-II are compared with the available experimental data for the elastic strain coefficients.

Isomorphism between ice and silica

Both ice and silica crystallize into solid-state structures composed of tetrahedral building units that are joined together to form an infinite four-connected net. Mathematical considerations suggest that there is a vast number of such nets and thus potential crystal structures. It is therefore perhaps surprising to discover that, despite the differences in the nature of interatomic interactions in these materials, a fair number of commonly observed ice and silica phases are based on common nets. Here we use computer simulation to investigate the origin of this symmetry between the structures formed for ice and silica and to attempt to understand why it is not complete. We start from a comparison of the dense phases and then move to the relationship between the different open (zeolitic and clathratic) structures formed for both materials. We show that there is a remarkably strong correlation between the energetics of isomorphic silica and water ice structures and that this correlation arises because of the strong link between the total energy of a material and its local geometric features. Finally, we discuss a number of as yet unsynthesized low-energy structures which include a phase of ice based on quartz, a silica based on the structure of ice VI, and an ice clathrate that is isomorphic to the silicate structure nonasil.

Vibrational dynamics of amorphous ice structures studied by high-resolution neutron spectroscopy

The dynamics of amorphous water ice structures of different densities have been studied by high-resolution neutron time-of-flight and backscattering spectroscopy. An accurate determination of the vibrational density of states $G(\ensuremath{\omega})$ in the energy range of phonons $\ensuremath{\hbar}\ensuremath{\omega}\ensuremath{\lesssim}40\text{ }\text{meV}$ of a many fold of structures comprising the low-density amorphous (LDA, $\ensuremath{\rho}\ensuremath{\approx}31\text{ }\text{molecules}/{\text{nm}}^{3}$), high-density amorphous (HDA, $\ensuremath{\rho}\ensuremath{\approx}39\text{ }\text{molecules}/{\text{nm}}^{3}$), very-high-density amorphous (vHDA, $\ensuremath{\rho}\ensuremath{\approx}41\text{ }\text{molecules}/{\text{nm}}^{3}$) and modifications of intermediate density in respect to HDA and vHDA has been achieved. Unlike the $G(\ensuremath{\omega})$ of high-density crystalline phases IX, V, and XII, which have been measured as reference systems, the $G(\ensuremath{\omega})$ of all high-density amorphous counterparts proves to be textureless except for a predominant peak at low energies. In vHDA this peak is centered at about 10 meV and redshifted upon density decrease to 7 meV in LDA. A concomitant upshift of the low-energy librational band edge from 34 to 45 meV is detected in deuterated samples. Mean-square displacement and Debye temperatures ${T}_{D}$ for vHDA, ${\mathrm{HDA}}^{\ensuremath{'}}$---a structure obtained as a transient product of the temperature induced vHDA to LDA transformation---and LDA are extracted from the highest resolution backscattering experiments. ${T}_{D}$ values indicate the absence of a dominant excess of low-energy modes in $G(\ensuremath{\omega})$, referred to as boson peak in the literature, being in agreement with the $G(\ensuremath{\omega})$ properties directly monitored by the time-of-flight technique. Having applied deuterated sample material we are able to display phase coherence effects within the phonon system in the second and third pseudo-Brillouin zone $(1\text{ }{\text{\AA{}}}^{\ensuremath{-}1}\ensuremath{\le}Q\ensuremath{\le}5\text{ }{\text{\AA{}}}^{\ensuremath{-}1})$ of the amorphous samples. A phase coherent signal from acoustic phonons can be followed up to energies of at least 15 meV.

Ultrafast electron crystallography of interfacial water.

We report direct determination of the structures and dynamics of interfacial water on a hydrophilic surface with atomic-scale resolution using ultrafast electron crystallography. On the nanometer scale, we observed the coexistence of ordered surface water and crystallite-like ice structures, evident in the superposition of Bragg spots and Debye-Scherrer rings. The structures were determined to be dominantly cubic, but each undergoes different dynamics after the ultrafast substrate temperature jump. From changes in local bond distances (OH.O and O.O) with time, we elucidated the structural changes in the far-from-equilibrium regime at short times and near-equilibration at long times.

Computer molecular dynamics of 2-d water (ice) structures under shock by

Abstract Computer molecular dynamics has been used to study the shock-front transition region for a series of two-dimensional hydrogen-bonded structures composed of water-vapor molecules. Two different structures were examined and different intermolecular potentials were considered. Sample sizes and running times were chosen to correspond to the predicted shock-front rise-time in real water. In this way, the effect of different potentials and initial structures on the equilibration associated with the shock-front transition in water could be investigated. In addition to studying the development and incipient relaxation of shock-polarization states, we have also considered the propagation and possible incipient relaxation of structural phase transitions occurring in two-dimensional structures. The results of these molecular dynamics calculations are compared with the experimental shock behavior of real water; in particular, comparisons are made with respect to intermolecular hydrogen-bond breaking, dissoci...