Diffusion of atomic oxygen relevant to water formation in amorphous interstellar ices.

High sensitivity temperature-programmed desorption mass spectrometry (TPDMS) was employed in order to investigate the desorption kinetics of CCl4 from thin (∼500 ML (ML: monolayer)) amorphous D2O ice films. TPDMS experiments demonstrate that at low coverages CCl4 is trapped in the pores near the surface of microscopically rough ice. Three distinct desorption features, μ-, δ-, and ε-CCl4, consistent with the release of trapped CCl4 were observed. The μ-, δ-, and ε-CCl4 desorption yields demonstrate high sensitivity to the temperature and rate of ice film deposition. We interpret these results as evidence of the existence of three metastable forms of microporous amorphous ice, Iμ, Iδ, and Iε. Measurements of the relative desorption yields from CCl4 species trapped at the surface of ice films prepared at different temperatures and deposition rates were used in order to estimate the barriers to the diffusion of D2O on the surface of Iδ (EDδ) and Iε (EDε). The values obtained were EDδ = 5 ± 1 kcal mol-1 and EDε = 9 ± 2 kcal mol-1. We suggest that Iμ, Iδ, and Iε can be characterized respectively by the relative abundances of two-, three-, and four-coordinated D2O molecules at the ice surface. A proposed phase diagram for thin D2O ice films is presented.

Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorphous phase due to the stabilising effect imparted by the presence of an extensive array of strong hydrogen bonds. These results have important consequences for the astrochemistry of interstellar ices and outer Solar System bodies, as they imply that the chemical products arising from the irradiation of amorphous ices (which may include prebiotic molecules relevant to biology) should be more abundant than those arising from similar irradiations of crystalline phases. In this present study, we have extended our work on this subject by performing comparative energetic electron irradiations of the amorphous and crystalline phases of the sulphur-bearing molecules H2S and SO2 at 20 K. We have found evidence for phase-dependent chemistry in both these species, with the radiation-induced exponential decay of amorphous H2S being more rapid than that of the crystalline phase, similar to the effect that has been previously observed for CH3OH. For SO2, two fluence regimes are apparent: a low-fluence regime in which the crystalline ice exhibits a rapid exponential decay while the amorphous ice possibly resists decay, and a high-fluence regime in which both phases undergo slow exponential-like decays. We have discussed our results in the contexts of interstellar and Solar System ice astrochemistry and the formation of sulphur allotropes and residues in these settings.

view Abstract Citations (157) References (75) Co-Reads Similar Papers Volume Content Graphics Metrics Export Citation NASA/ADS High-Density Amorphous Ice, the Frost on Interstellar Grains Jenniskens, P. ; Blake, D. F. ; Wilson, M. A. ; Pohorille, A. Abstract Most water ice in the universe is in a form which does not occur naturally on Earth and of which only minimal amounts have been made in the laboratory. We have encountered this "high-density amorphous ice" in electron diffraction experiments of low-temperature (T < 30 K) vapor-deposited water and have subsequently modeled its structure using molecular dynamics simulations. The characteristic feature of high-density amorphous ice is the presence of "interstitial" oxygen pair distances between 3 and 4 A. However, we find that the structure is best described as a collapsed lattice of the more familiar low-density amorphous form. These distortions are frozen in at temperatures below 38 K because, we propose, it requires the breaking of one hydrogen bond, on average, per molecule to relieve the strain and to restructure the lattice to that of low-density amorphous ice. Several features of astrophysical ice analogs studied in laboratory experiments are readily explained by the structural transition from high-density amorphous ice into low-density amorphous ice. Changes in the shape of the 3.07 microns water band, trapping efficiency of CO, CO loss, changes in the CO band structure, and the recombination of radicals induced by low-temperature UV photolysis all covary with structural changes that occur in the ice during this amorphous to amorphous transition. While the 3.07 microns ice band in various astronomical environments can be modeled with spectra of simple mixtures of amorphous and crystalline forms, the contribution of the high-density amorphous form nearly always dominates. Publication: The Astrophysical Journal Pub Date: January 1995 DOI: 10.1086/176585 Bibcode: 1995ApJ...455..389J Keywords: INFRARED: ISM: LINES AND BANDS; ISM: DUST; EXTINCTION; ISM: MOLECULES; LINE: PROFILES; MOLECULAR DATA; METHODS: LABORATORY; Density (Mass/Volume); Amorphous Materials; Ice; Frost; Interstellar Matter; Astronomy; Astrophysics; Cosmic Dust; Crystallinity; Electron Diffraction; Hydrogen Bonds; Molecular Dynamics; Radicals; Shapes; Trapping; Universe; Vapor Deposition; Water; Astrophysics full text sources ADS |

Based on several force fields (COMPASS, modified TIP3P and SPC/E) high-density amorphous ice is simulated by use of isothermal-isobaric molecular dynamics at a pressure of p approximately 0.3 GPa in the temperature range from 70 to 300 K. Starting at low temperature a large number of heating/cooling cycles are performed and several characteristic properties (density, total energy, and mobility) are traced as functions of temperature. While the first cycles are showing irreversible structural relaxation effects data points from further cycles are reproducible and give clear evidence for the existence of a glass-to-liquid transition. Although, the observed transition temperatures T(g) are dependent on the actual force field used and slightly dependent on the method adopted the results indicate that high-density amorphous ices may indeed be low-temperature structural proxies of ultraviscous high-density liquids.

Electronic structures of hexagonal ice (ice Ih), high-density amorphous ice (HDA), and very high-density amorphous ice (VHDA) are investigated using ab initio density functional theory (DFT) at 77 K under a pressure of 0.1 MPa, focusing on band structure, density of states (DOS), partial density of states (PDOS), and electron density. It is found that the integration intensity of the O-2p bonding band in HDA is 1.53 eV wider than that in the VHDA. Because more 2p electrons in HDA participate the 2p-1s hybridization of O-H. The classical molecular dynamics (MD) method has further been carried out to analyze the hydrogen bond network of HDA and VHDA with larger numbers of water molecules under the same temperature, pressure, and boundary conditions used as those during the DFT calculation. MD results show that there exists some water molecules with five hydrogen bonds in both HDA (4.1 +/- 0.1%) and VHDA (2.8 +/- 0.1%), as compared with the LDA, being consistent with the integration intensity results of PDOS. This result can be used to interpret the physical nature of the similar transition temperature of HDA and VHDA to LDA with different heating rates.

Amorphous solid water (ASW) is of great importance in astrochemistry as it has been detected in star forming regions, comets, and cold solar-system objects. A key property of ASW is its porous nature (with the extent of porosity reflecting the formation and growth conditions) and the subsequent pore collapse when the ice is heated. If interstellar ices are porous there are huge implications to both the process of planet formation and the budgets of molecular gas in the solid and gas phases. It is therefore vital to understand ASW porosity over astronomically relevant conditions in order to effectively model its potential effects on these processes.

The low-energy, electron-stimulated production of molecular oxygen from thin amorphous solid water (ASW) films adsorbed on Pt(111) is investigated. For ASW coverages less than approximately 60 ML, the O(2) electron-stimulated desorption (ESD) yield depends on coverage in a manner that is very similar to the H(2) ESD yield. In particular, both the O(2) and H(2) ESD yields have a pronounced maximum at approximately 20 ML due to reactions at the Pt/water interface. The O(2) yield is dose dependent and several precursors (OH, H(2)O(2), and HO(2)) are involved in the O(2) production. Layered films of H(2) (16)O and H(2) (18)O are used to profile the spatial distribution of the electron-stimulated reactions leading to oxygen within the water films. Independent of the ASW film thickness, the final reactions leading to O(2) occur at or near the ASW/vacuum interface. However, for ASW coverages less than approximately 40 ML, the results indicate that dissociation of water molecules at the ASW/Pt interface contributes to the O(2) production at the ASW/vacuum interface presumably via the generation of OH radicals near the Pt substrate. The OH (or possibly OH(-)) segregates to the vacuum interface where it contributes to the reactions at that interface. The electron-stimulated migration of precursors to the vacuum interface occurs via transport through the hydrogen bond network of the ASW without motion of the oxygen atoms. A simple kinetic model of the nonthermal reactions leading to O(2), which was previously used to account for reactions in thick ASW films, is modified to account for the electron-stimulated migration of precursors.

With the purpose of clarifying a number of points raised in the experimental literature, we investigate by molecular dynamics simulation the thermodynamics, the structure and the vibrational properties of vapor-deposited amorphous ice (ASW) as well as the phase transformations experienced by crystalline and vitreous ice under ion bombardment. Concerning ASW, we have shown that by changing the conditions of the deposition process, it is possible to form either a nonmicroporous amorphous deposit whose density (approximately 1.0 g/cm3) is essentially invariant with the temperature of deposition, or a microporous sample whose density varies drastically upon temperature annealing. We find that ASW is energetically different from glassy water except at the glass transition temperature and above. Moreover, the molecular dynamics simulation shows no evidence for the formation of a high-density phase when depositing water molecules at very low temperature. In order to model the processing of interstellar ices by cosmic ray protons and heavy ions coming from the magnetospheric radiation environment around the giant planets, we bombarded samples of vitreous ice and cubic ice with 35 eV water molecules. After irradiation the recovered samples were found to be densified, the lower the temperature, the higher the density of the recovered sample. The analysis of the structure and vibrational properties of this new high-density phase of amorphous ice shows a close relationship with those of high-density amorphous ice obtained by pressure-induced amorphization.

The interaction of methanol (MeOH) with amorphous solid water (ASW) composed of D2O molecules, prepared at 125 K on a polycrystalline Ag substrate, was studied with metastable-impact-electron spectroscopy, reflection-absorption infrared spectroscopy, and temperature-programmed desorption mass spectroscopy. In connection with the experiments, classical molecular dynamics (MD) simulations have been performed on a single CH3OH molecule adsorbed at the ice surface (T=190 K), providing further insights into the binding and adsorption properties of the molecule at the ice surface. Consistently with the experimental deductions and previous studies, MeOH is found to adsorb with the hydroxyl group pointing toward dangling bonds of the ice surface, the CH3 group being oriented upwards, slightly tilted with respect to the surface normal. It forms the toplayer up to the onset of the simultaneous desorption of D2O and MeOH. At low coverage the adsorption is dominated by the formation of two strong hydrogen bonds as evidenced by the MD results. During the buildup of the first methanol layer on top of an ASW film the MeOH-MeOH interaction via hydrogen-bond formation becomes of importance as well. The interaction of D2O with solid methanol films and the codeposition of MeOH and D2O were also investigated experimentally; these experiments showed that D2O molecules supplied to a solid methanol film become embedded into the film.

From crystalline tetrahydrofuran clathrate hydrate, THF-CH (THF·17H2O, cubic structure II), three distinct polyamorphs can be derived. First, THF-CH undergoes pressure-induced amorphization when pressurized to 1.3 GPa in the temperature range 77-140 K to a form which, in analogy to pure ice, may be called high-density amorphous (HDA). Second, HDA can be converted to a densified form, VHDA, upon heat-cycling at 1.8 GPa to 180 K. Decompression of VHDA to atmospheric pressure below 130 K produces the third form, recovered amorphous (RA). Results from neutron scattering experiments and molecular dynamics simulations provide a generalized picture of the structure of amorphous THF hydrates with respect to crystalline THF-CH and liquid THF·17H2O solution (∼2.5 M). Although fully amorphous, HDA is heterogeneous with two length scales for water-water correlations (less dense local water structure) and guest-water correlations (denser THF hydration structure). The hydration structure of THF is influenced by guest-host hydrogen bonding. THF molecules maintain a quasiregular array, reminiscent of the crystalline state, and their hydration structure (out to 5 Å) constitutes ∼23H2O. The local water structure in HDA is reminiscent of pure HDA-ice featuring 5-coordinated H2O. In VHDA, the hydration structure of HDA is maintained but the local water structure is densified and resembles pure VHDA-ice with 6-coordinated H2O. The hydration structure of THF in RA constitutes ∼18 H2O molecules and the water structure corresponds to a strictly 4-coordinated network, as in the liquid. Both VHDA and RA can be considered as homogeneous.

Biological samples are successfully preserved for indefinite periods after vitrification, providing ice formation is avoided. Glass is difficult to characterize, especially at the extremely low temperatures required for biological tissues vitrification. Glass transition is traditionally observed by differential scanning calorimetry (DSC), in spite of its reduced sensitivity and lack of spatial information. In this work, a novel procedure, based on low-temperature scanning electron microscopy (cryo-SEM), is explored to locate vitrified areas and ice crystals in tissues and cells. Cryo-SEM observation of biological samples requires an etching phase to create contrast: a temperature rise, allowing ice partial sublimation. Glassy water, differently from crystallized water (ice), has a neglectable sublimation rate. Consequently, while the dark image of sublimated crystals and the resulting structural details can be observed in ice-containing samples, vitrified tissues show a smooth landscape, without dark areas or visible structure elements.

The structure of amorphous ice under pressure has been studied by molecular dynamics at 160 K. The starting low-density phase undergoes significant changes as the density increases, and at rho=1.51 g/cm(3) our calculated g(OO)(r) is in excellent agreement with in situ neutron diffraction data obtained at 1.8 GPa and 100 K on very high density amorphous ice made at 150 K. As the system is further compressed, in the theoretical simulations, up to rho=1.90 g/cm(3), the structural modifications are continuous up to the highest density. The analysis of orientational distributions reveals that dense amorphous ice is characterized by major distortions of the tetrahedral geometry, and that the pressure structural changes, already observed experimentally at lower densities, can be interpreted as a trend towards a disordered closed-packed structure.

Supercooled liquids in the Y(2)O(3)-Al(2)O(3) system undergo a liquid-liquid phase transition between a high-temperature, high-density amorphous (HDA) polymorph form and one with lower density (LDA form) that is stable at lower temperature. The two amorphous polymorphs have the same chemical composition, but they differ in their density (ca. 4% difference) and in their heat content (enthalpy) and entropy determined by calorimetry. Here we present new results of structural studies using neutron and high-energy X-ray diffraction to study the structural differences between HDA and LDA polyamorphs. The combined datasets show no large differences in the average nearest-neighbour Al-O or Y-O bond lengths or coordination numbers between the low- and high-density liquids. However, the data indicate that substantial changes occur among the packing geometries and clustering of the Al-O and Y-O coordination polyhedra, i.e. within the second-nearest-neighbour shell defined by the metal-metal (i.e. Y-Y, Y-Al, Al-Al) interactions. Polarizable ion model molecular dynamics simulations of Y(2)O(3)-Al(2)O(3) liquids are used to help interpret the pair-correlation functions obtained from X-ray and neutron scattering data. Unexpectedly large density fluctuations are observed to occur during the simulation of nominally equilibrated systems. These are interpreted as being due to dynamic sampling of high- and low-density configurations within the single-phase liquid at temperatures above the critical point or phase transition line. Calculated partial radial distribution functions indicate that the primary differences between HDA and LDA configurations occur among the Y-Y correlations.

Introduction There are 12 crystalline forms of ice. At ordinary pressures the stable phase is termed ice I, terminology that followed Tammann's (1900) discovery of high-pressure phases. There are two closely related low-pressure variants: hexagonal ice, denoted Ih, and cubic ice, Ic. Ice Ih is termed ordinary ice whose hexagonal crystal symmetry is reflected in the shape of snow-flakes. Ice Ic is made by depositing water vapor at temperatures lower than about −130 ℃. High-pressure ices are of little interest in relation to geophysical processes on Earth, but constitute the primary materials from which many extra-terrestrial bodies are made. We describe their structure and creep properties in Chapter 8. In addition to the 12 crystalline forms, there are two amorphous forms. One is termed low-density ice (940 kg m −3 at −196 ℃ at 1 atmosphere) and the other, high-density ice (1170 kg m −3 , same conditions). The density of ice Ih is 933 kg m −3 at the same temperature and pressure (Hobbs, 1974). Amorphous ices can be made at low temperatures in five ways (see review by Mishima and Stanley, 1998): by condensing vapor below −160 ℃; by quenching liquid; by compressing ice Ih at −196 ℃; by electron irradiation; and through transformation upon warming from one amorphous state to another. Although once thought to be a nanocrystalline material, amorphous ice is now considered to be truly glassy water. Its mechanical behavior remains to be explored. In this chapter we address the structure of ice Ih.

Spectroscopic and volumetric characterization of a non-microporous amorphous ice