Water Ice Surface Research Articles

A computational study on the structures of methylamine–carbon dioxide–water clusters: evidence for the barrier free formation of the methylcarbamic acid zwitterion (CH3NH2+COO−) in interstellar water ices

We investigated theoretically the interaction between methylamine (CH(3)NH(2)) and carbon dioxide (CO(2)) in the presence of water (H(2)O) molecules thus simulating the geometries of various methylamine-carbon dioxide complexes (CH(3)NH(2)/CO(2)) relevant to the chemical processing of icy grains in the interstellar medium (ISM). Two approaches were followed. In the amorphous water phase approach, structures of methylamine-carbon dioxide-water [CH(3)NH(2)/CO(2)/(H(2)O)(n)] clusters (n = 0-20) were studied using density functional theory (DFT). In the crystalline water approach, we simulated methylamine and carbon dioxide interactions on a fragment of the crystalline water ice surface in the presence of additional water molecules in the CH(3)NH(2)/CO(2) environment using DFT and effective fragment potentials (EFP). Both the geometry optimization and vibrational frequency analysis results obtained from these two approaches suggested that the surrounding water molecules which form hydrogen bonds with the CH(3)NH(2)/CO(2) complex draw the carbon dioxide closer to the methylamine. This enables, when two or more water molecules are present, an electron transfer from methylamine to carbon dioxide to form the methylcarbamic acid zwitterion, CH(3)NH(2)(+)CO(2)(-), in which the carbon dioxide is bent. Our calculations show that the zwitterion is formed without involving any electronic excitation on the ground state surface; this structure is only stable in the presence of water, i.e. in a methyl amine-carbon dioxide-water ice. Notably, in the vibrational frequency calculations on the methylcarbamic acid zwitterion and two water molecules we find the carbon dioxide asymmetric stretch is drastically red shifted by 435 cm(-1) to 1989 cm(-1) and the carbon dioxide symmetric stretch becomes strongly infrared active. We discuss how the methylcarbamic acid zwitterion CH(3)NH(2)(+)CO(2)(-) might be experimentally and astronomically identified by its asymmetric CO(2) stretching mode using infrared spectroscopy.

An overview of current issues in the uptake of atmospheric trace gases by aerosols and clouds

Abstract. A workshop was held in the framework of the ACCENT (Atmospheric Composition Change – a European Network) Joint Research Programme on "Aerosols" and the Programme on "Access to Laboratory Data". The aim of the workshop was to hold "Gordon Conference" type discussion covering accommodation and reactive uptake of water vapour and trace pollutant gases on condensed phase atmospheric materials. The scope was to review and define the current state of knowledge of accommodation coefficients for water vapour on water droplet and ice surfaces, and uptake of trace gas species on a variety of different surfaces characteristic of the atmospheric condensed phase particulate matter and cloud droplets. Twenty-six scientists participated in this meeting through presentations, discussions and the development of a consensus review. In this review we present an analysis of the state of knowledge on the thermal and mass accommodation coefficient for water vapour on aqueous droplets and ice and a survey of current state-of the-art of reactive uptake of trace gases on a range of liquid and solid atmospheric droplets and particles. The review recommends consistent definitions of the various parameters that are needed for quantitative representation of the range of gas/condensed surface kinetic processes important for the atmosphere and identifies topics that require additional research.

Gas temperature dependent sticking of hydrogen on cold amorphous water ice surfaces of interstellar interest

Using the King and Wells method, we present experimental data on the dependence of the sticking of molecular hydrogen and deuterium on the beam temperature onto nonporous amorphous solid water ice surfaces of interstellar interest. A statistical model that explains the isotopic effect and the beam temperature behavior of our data is proposed. This model gives an understanding of the discrepancy between all known experimental results on the sticking of molecular hydrogen. Moreover, it is able to fit the theoretical results of Buch et al. [Astrophys. J. 379, 647 (1991)] on atomic hydrogen and deuterium. For astrophysical applications, an analytical formula for the sticking coefficients of H, D, H(2), D(2), and HD in the case of a gas phase at thermal equilibrium is also provided at the end of the article.

Radar Signal Propagation and Detection Through Ice

In this paper we describe the existing and planned radar measurements of the planetary bodies. The dielectric properties of water ice and other potential surface and subsurface materials are discussed, as well as their dependency on temperature and structure. We then evaluate the performance of subsurface sounding radars using these parameters. Finally we describe some laboratory technique to help interpret the radar data, presenting some results obtained using dielectric spectroscopy methods.

Desorption of ionic species from ice/graphite by femtosecond XUV free-electron laserpulses

We report results of laser desorption from water ice surfaces using XUV pulsesfrom the free-electron laser in Hamburg (FLASH). This XUV to soft x-ray FELprovides femtosecond pulses at 20–200 eV photon energy with pulse energies up to100 µJ. The interaction of this intense soft x-ray radiation with ice (H2O,D2O)adsorbed on highly oriented pyrolytic graphite (HOPG) yields the desorption of various ions, particularlyH + (D + ),O + ,O2 + and others.For H + and O + ions linear desorption yields are observed, while forO2 + a highly nonlineardesorption yield with n = (2.5 ± 0.2) is found. Kinetic energies of 1.8 eV, 559 meV and 390 meV forH + ,O + , andO2 + , respectively, account for only a small part of the available excess energy.

Saturn’s icy satellites investigated by Cassini–VIMS: II. Results at the end of nominal mission

We report the detailed analysis of the spectrophotometric properties of Saturn’s icy satellites as derived by full-disk observations obtained by visual and infrared mapping spectrometer (VIMS) experiment aboard Cassini. In this paper, we have extended the coverage until the end of the Cassini’s nominal mission (June 1st 2008), while a previous paper ( Filacchione, G., and 28 colleagues [2007]. Icarus 186, 259–290, hereby referred to as Paper I) reported the preliminary results of this study. During the four years of nominal mission, VIMS has observed the entire population of Saturn’s icy satellites allowing us to make a comparative analysis of the VIS–NIR spectral properties of the major satellites (Mimas, Enceladus, Tethys, Dione, Rhea, Hyperion, Iapetus) and irregular moons (Atlas, Prometheus, Pandora, Janus, Epimetheus, Telesto, Calypso, Phoebe). The results we discuss here are derived from the entire dataset available at June 2008 which consists of 1417 full-disk observations acquired from a variety of distances and inclinations from the equatorial plane, with different phase angles and hemispheric coverage. The most important spectrophotometric indicators (as defined in Paper I: I/ F continua at 0.55 μm, 1.822 μm and 3.547 μm, visible spectral slopes, water and carbon dioxide bands depths and positions) are calculated for each observation in order to investigate the disk-integrated composition of the satellites, the distribution of water ice respect to “contaminants” abundances and typical regolith grain properties. These quantities vary from the almost pure water ice surfaces of Enceladus and Calypso to the organic and carbon dioxide rich Hyperion, Iapetus and Phoebe. Janus visible colors are intermediate between these two classes having a slightly positive spectral slope. These results could help to decipher the origins and evolutionary history of the minor moons of the Saturn’s system. We introduce a polar representation of the spectrophotometric parameters as function of the solar phase angle (along radial distance) and of the effective longitude interval illuminated by the Sun and covered by VIMS during the observation (in azimuth) to better investigate the spatial distribution of the spectrophotometric quantities across the regular satellites hemispheres. Finally, we report the observed spectral positions of the 4.26 μm band of the carbon dioxide present in the surface material of three outermost moons Hyperion, Iapetus and Phoebe.

Identification of hydrogen and deuterium at the surface of water ice by reflection electron energy loss spectroscopy

A nondestructive method to distinguish between hydrogen (H) and deuterium (D) at surfaces by reflection electron energy loss spectroscopy is presented. It is based on the analysis of the energy distributions of electrons elastically backscattered from surfaces containing H or D. We consider standard and deuterated water ices as test surfaces. The recoil energy of the backscattered electrons depends on the atomic mass of the targets, and the contributions of H, D, and O to the measured spectra can be easily separated. The results of Monte Carlo simulations corroborate the experimental findings.

Photoelectric emission from the alkali metal doped vacuum-ice interface

The photoelectron photoemission spectra and thresholds for low coverages of Li and K adsorbed on water-ice have been measured, compared with photoionization spectra of the gas-phase atoms, and modeled by quantum chemical calculations. For both alkali metals the threshold for photoemission is dramatically decreased and the cross section increased on adsorption to the water-ice surface. Quantum chemical calculations suggest that the initial state is formed by the metal atoms adsorbed into the water-ice surface, forming a state with a delocalized electron distribution. This state is metastable and decays on the hundreds of seconds time scale at 92 K. The decay is markedly faster for Li than for K, probably due to diffusion into the ice film.

MARSIS surface reflectivity of the south residual cap of Mars

The south residual cap of Mars is commonly described as a thin and bright layer of CO 2-ice. The Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) is a low-frequency radar on board Mars Express operating at the wavelength between 55 and 230 m in vacuum. The reflection of the radar wave on a stratified medium like the residual cap can generate interferences, causing weaker surface reflections compared to reflections from a pure water ice surface. In order to understand this anomalous low reflectivity, we propose a stratified medium model, which allows us to estimate both the thickness and the dielectric constant of the optically thin slab. First, we consider the residual cap as single unit and show that the decrease in the reflected echo strength is well explained by a mean thickness of 11 m and a mean dielectric constant of 2.2. This value of dielectric constant is close to the experimental value 2.12 for pure CO 2-ice. Second, we study the spatial variability of the radar surface reflectivity. We observe that the reflectivity is not homogeneous over the residual cap. This heterogeneity can be modeled either by variable thickness or variable dielectric constant. The surface reflectivity shows that two different units comprise the residual cap, one central unit with high reflectivity and surrounding, less reflective units.

Facilitation of Applicability in Ice Chromatography by Mechanistic Considerations and by Preparation of Fine Water-Ice Stationary Phase

We have, in previous papers, demonstrated that some solute is adsorbed on the ice surface at temperatures below -5 degrees C by the hydrogen-bond formation between the polar groups in the solute and the dangling bonds on the water-ice surface. However, the separation efficiency of this method, named ice chromatography, was seriously restricted principally due to the large sizes of water-ice particles used as a stationary phase. We have devised a convenient method to prepare finer ice particles with diameters of approximately 10 microm. This stationary phase has provided much larger theoretical plate numbers (N = 1500) than that prepared in the previous way (N = 250) and has allowed various applications such as separation of amino acid derivatives, poly(oxyethylene) oligomers, and estrogen. The improved separation performance allows us to discuss retention mechanisms in more detail and to see subtle differences in the retentivity between solutes.

Trace constituents of Europa's atmosphere

Europa is bombarded by intense radiation that erodes the surface, launching molecules into a thin “atmosphere” representative of surface composition. In addition to atoms and molecules created in the mostly water ice surface such as H 2O, O 2, H 2, the atmosphere is known to have species representative of trace surface materials. These trace species are carried off with the 10–10 4 H 2O molecules ejected by each energetic heavy ion, a process we have simulated using molecular dynamics. Using the results of those simulations, we found that a neutral mass spectrometer orbiting ∼100 km above the surface could detect species with surface concentrations above ∼0.03%. We have also modeled the atmospheric spatial structure of the volatile species CO 2 and SO 2 under a variety of assumptions. Detections of these species with moderate time and space resolution would allow us to constrain surface composition, chemistry and to study space weathering processes.

Mobility of D atoms on porous amorphous water ice surfaces under interstellar conditions

Aims. The mobility of H atoms on the surface of interstellar dust grains at low temperature is still a matter of debate. In dense clouds, the hydrogenation of adsorbed species (i.e., CO), as well as the subsequent deuteration of the accreted molecules depend on the mobility of H atoms on water ice. Astrochemical models widely assume that H atoms are mobile on the surface of dust grains even if controversy still exists. We present here direct experimental evidence of the mobility of H atoms on porous water ice surfaces at 10 K. Methods. In a UHV chamber, O2 is deposited on a porous amorphous water ice substrate. Then D atoms are deposited onto the surface held at 10 K. Temperature-Programmed Desorption (TPD) is used and desorptions of O2 and D2 are simultaneously monitored. Results. We find that the amount of O2 that desorb during the TPD diminishes if we increase the deposition time of D atoms. O2 is thus destroyed by D atoms even though these molecules have previously diffused inside the pores of thick water ice. Our results can be easily interpreted if D is mobile at 10 K on the water ice surface. A simple rate equation model fits our experimental data and best fit curves were obtained for a D atoms diffusion barrier of 22(+-)2 meV. Therefore hydrogenation can take place efficiently on interstellar dust grains. These experimental results are in line with most calculations and validate the hypothesis used in several models.

Direct Observation of OH Radicals Ejected from Water Ice Surface in the Photoirradiation of Nitrate Adsorbed on Ice at 100 K

Production of gaseous OH radicals in the 248-350 nm photoirradiation of NO3(-) doped on amorphous ice at 100 K was monitored directly by using resonance-enhanced multiphoton ionization. The translational energy distribution of the OH product was represented by a Maxwell-Boltzmann energy distribution with the translational temperature of 3250 +/- 250 K. The rotational temperature was estimated to be 175 +/- 25 K. We have confirmed that the OH production should be attributed to the secondary photolysis of H2O2 produced on ice surface on the basis of the results of controlled photolysis experiments for H2O2 doped on ice surface.

Hydrogen peroxide formation following the vacuum ultraviolet photodissociation of water ice films at 90K

The production of gaseous OH radicals from the 300-350 nm photodissociation of H(2)O(2) that was photolytically produced on a water ice surface following the 157 nm photolysis of water ice at 90 K was directly monitored using resonance-enhanced multiphoton ionization. The translational energy distribution estimated by the time-of-flight spectrum of the OH products is represented by a Maxwell-Boltzmann energy distribution with a translational temperature of 3750+/-250 K. The rotational temperature was estimated by a spectral simulation to be 225+/-25 K. Surface defects produced by HCl deposition on the water ice contributed to the higher production rate of H(2)O(2) in the 157 nm photoirradiation of water ice while surface coverage caused by CD(3)OH deposition decreased the H(2)O(2) production rate.

Chandrayaan-1 mission to the Moon

Chandrayaan-1 is the first Indian planetary exploration mission that will perform remote sensing observation of the Moon to further our understanding about its origin and evolution. Hyper-spectral studies in the 0.4– 3 μ m region using three different imaging spectrometers, coupled with a low energy X-ray spectrometer, a sub-keV atom analyzer, a 3D terrain mapping camera and a laser ranging instrument will provide data on mineralogical and chemical composition and topography of the lunar surface at high spatial resolution. A low energy gamma ray spectrometer and a miniature imaging radar will investigate volatile transport on lunar surface and possible presence of water ice in the polar region. A radiation dose monitor will provide an estimation of energetic particle flux en route to the Moon as well as in lunar orbit. An impact probe carrying a mass spectrometer will also be a part of the spacecraft. The 1 ton class spacecraft will be launched by using a variant of flight proven indigenous Polar Satellite Launch Vehicle (PSLV-XL). The spacecraft will be finally placed in a 100 km circular polar orbit around the Moon with a planned mission life of two years.

Measurement of the Adsorption Energy Difference betweenOrtho- andPara-D2on an Amorphous Ice Surface

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

The composition of Europa's near-surface atmosphere

AbstractThe presence of an undersurface ocean renders Europa as one of the few planetary bodies in our Solar System that has been conjectured to have possibly harbored life. Some of the organic and inorganic species present in the ocean underneath are expected to transport upwards through the relatively thin ice crust and manifest themselves as impurities of the water ice surface. For this reason, together with its unique dynamic atmosphere and geological features, Europa has attracted strong scientific interests in past decades.Europa is imbedded inside the Jovian magnetosphere, and, therefore, is constantly subjected to the immerse surrounding radiations, similar to the other three Galilean satellites. The magnetosphere-atmosphere-surface interactions form a complex system that provides a multitude of interesting geophysical phenomenon that is unique in the Solar System. The atmosphere of Europa is thought to have created by, mostly, charged particles sputtering of surface materials. Consequently, the study of Europa's atmosphere can be used as a tool to infer the surface composition. In this paper, we will discuss our recent model studies of Europa's near-surface atmosphere. In particular, the abundances and distributions of the dominant O2 and H2O species, and of other organic and inorganic minor species will be addressed.

Comet Knudsen Layers

This paper reviews some important results about Knudsen layers obtained in theoretical gas kinetics research in the last few decades, focusing on the weak and strong evaporation problems in two-surface, half-space, and spherical geometries. Furthermore, the application of such results in cometary science is reviewed. In order to illustrate some properties of the half-space evaporation problem for water ice surfaces at temperatures relevant for active comets, a number of numerical Direct Simulation Monte Carlo calculations are presented.

Interaction of atomic and molecular deuterium with a nonporous amorphous water ice surface between 8 and 30K

Molecular and atomic interactions of hydrogen on dust grains covered with ice at low temperatures are key mechanisms for star formation and chemistry in dark interstellar clouds. We have experimentally studied the interaction of atomic and molecular deuterium on nonporous amorphous water ice surfaces between 8 and 30 K, in conditions compatible with an extrapolation to an astrophysical context. The adsorption energy of D(2) presents a wide distribution, as already observed on porous water ice surfaces. At low coverage, the sticking coefficient of D(2) increases linearly with the number of deuterium molecules already adsorbed on the surface. Recombination of atomic D occurs via a prompt reaction that releases molecules into the gas phase. Part of the newly formed molecules are in vibrationally excited states (v=1-7). The atomic recombination efficiency increases with the presence of D(2) molecules already adsorbed on the water ice, probably because these increase the sticking coefficient of the atoms, as in the case of incident D(2). We have measured the atomic recombination efficiency in the presence of already absorbed D(2), as it is expected to occur in the interstellar medium. The recombination efficiency decreases rapidly with increasing temperature and is zero at 13 K. This allows us to estimate an upper limit to the value of the atom adsorption energy E(a) approximately 29 meV, in agreement with previous calculations.

Ice chromatography: Modification of solute retention on water–ice stationary phase

Ice chromatography, in which water–ice particles are used as the stationary phase, has high potential as a separation tool, and is an efficient approach to probe the molecular interaction occurring on the water–ice surface. In the present paper, to modify solute retention, several methods are proposed, that is, changing the mobile phase composition, the surface modification of water–ice, and the implantation of functional molecules into water–ice. The retention mechanism of ice chromatography is discussed through these retention modifications.