Infrared and electronic absorption spectra of formaldehyde in gas phase and astrophysical H<Subscript>2</Subscript>O ice

This work reports theoretical infrared and electronic absorption spectra of formaldehyde and its ions in gas phase and H₂O ice at different levels of theory. The vibrational frequencies from this work at B3LYP/6-311++G^** level are in agreement with the experimental determinations. The gas phase dipole moment of neutral formaldehyde 2.4 D is in excellent agreement with the experimental value of 2.33 D. An influence of ice on vibrational frequencies of neutral formaldehyde molecule was obtained using Self Consistence Isodensity Polarizable Continuum Model (SCI-PCM) with dielectric constant 78.5. Significant shift in vibrational frequencies for neutral formaldehyde molecule when studied in H₂O ice and upon ionization is observed. All the vibrational modes in cation and anion of formaldehyde in gas phase are red shifted than the corresponding modes in neutral formaldehyde. Two vibrational modes are blue shifted and all other modes are red shifted for neutral formaldehyde in H₂O ice. Time dependent density functional theory (TDDFT) is used to study electronic absorption spectrum of neutral formaldehyde and its charged states. It is found that like neutral formaldehyde, its cation and anion also display strong σ→σ ^∗ electronic transitions in vacuum and far UV regions. This study should help in detecting formaldehyde molecule and its ions in gas phase and in H₂O ice in different astronomical environment.     

Models of the Internal Structure of Callisto

Models of the internal structure of Callisto were constructed and the extent of its differentiation was determined based on geophysical information from the Galileo spacecraft (the mass, the radius, the mean density, and the moment of inertia), geochemical data (the chemical composition of meteorites), and the equations of state of water, ices, and meteoritic material. The thickness and the phase state of the water-ice shell were defined as well as the ice concentrations in the rock-ice mantle and the bulk concentration of H₂O. The constraints on the density distribution in the mantle and the size of the rock-iron core were derived. We considered models of the internal structure of Callisto in which the presence of a continuous ice shell was assumed (models without ocean) and models with an internal ocean. We demonstrated that it is possible to apply three-layer models with an icy shell up to 320 km in thickness and a rock-iron core in different combinations with a rock-ice mantle. These models do not reject a two-layer structure of Callisto (an ice lithosphere plus a rock-ice mantle or a rock-ice mantle plus a rock-iron core) and a one-layer model of the satellite composed only of a rock-ice mantle with an ice concentration that is variable in depth. Taking into account the chemically bound water, the bulk content of H₂O in the satellite is found to be 49–55 wt %. For the model with an internal ocean, the geophysically allowed thickness of the water-ice shell of Callisto was estimated to be 270–315 km with thicknesses of the icy crust and the underlying water layer of 135–150 and 120–180 km, respectively. The results of reconstruction of the composition and structure of the regular satellites of Jupiter allow us to conclude that they were possibly formed from material whose composition was close to ordinary L/LL chondrites at relatively low temperatures, lower than the temperature of evaporation of iron and Fe-Mg silicates.__________Translated from Astronomicheskii Vestnik, Vol. 39, No. 4, 2005, pp. 321–341.Original Russian Text Copyright © 2005 by Kuskov, Kronrod.     

Deuterium enrichment of the interstellar medium

Despite the low elemental abundance of atomic deuterium in the interstellar medium (ISM), observational evidence suggests that several species, both in the gas phase and in ices, could be heavily fractionated. We explore various aspects of deuterium enrichment by constructing a chemical evolution model in both gaseous and granular phases. Depending on various physical parameters, gases and grains are allowed to interact with each other through the exchange of their chemical species. It is known that HCO⁺ and N₂H⁺ are two abundant gas phase ions in the ISM and, their deuterium fractionation is generally used to predict the degree of ionization in the various regions of a molecular cloud. For a more accurate estimation, we consider the density profile of a collapsing cloud. The radial distributions of important interstellar molecules, along with their deuterated isotopomers, are presented. Quantum chemical simulations are computed to study the effects of isotopic substitution on the spectral properties of these interstellar species. We calculate the vibrational (harmonic) frequencies of the most important deuterated species (neutral and ions). The rotational and distortional constants of these molecules are also computed in order to predict the rotational transitions of these species. We compare vibrational (harmonic) and rotational transitions as computed by us with existing experimental and theoretical results. It is hope that our results will assist observers in detecting several hitherto unobserved deuterated species.     

Water-ice clouds and dust in the north polar region of Mars using MGS TES data

Water-ice and dust optical depths in Mars’ north polar region are mapped as function of season, latitude and longitude, and their characteristics and variability on a geographic, seasonal, and interannual basis are discussed. We use water-ice and dust optical depth data provided by the Mars Global Surveyor (MGS) Thermal Emission Spectrometer (TES), covering nearly three northern spring and summer periods. We find that interannual variability exists in both the water ice and dust behavior, although there are trends that repeat year to year as well. The optical thickness of the north polar hood (NPH) exhibits interannually varying longitudinal structure, both during springtime recession and late-summer onset. We define the characteristics associated with the transition to and from the NPH and find that the disappearance occurs near L_s=75° and the reappearance near L_s=160-165°. We find that the late spring to early summer time frame is characterized by very low water-ice optical depths and enhanced dust activity, with a preference for lower water-ice and higher dust optical depths in the 0-90°W quadrant. We see possible evidence for stationary wavenumber 2 systems in a few of the maps examined.     

The evolution of icy satellite interiors and surfaces

The satellites of the outer solar system planets are thought to be mixtures of ices and rocky material, in which decay of radioactive nuclides can lead to internal melting and solid-state convection. Time-dependent models indicate that melting will reach its maximum extent approximately 2.0 GYr after formation; bodies of radius <500 km will never melt, and those <750 km in radius will be totally refrozen by present. Surface water flows are not expected for bodies of <1500-km radius. However, even small (100 km) bodies may be unstable against solid-state convection, and their surfaces may show signs of tectonism. Other processes altering the surfaces include sublimation and photolysis of ices. Sublimation likely explains the absence of CH₄ ices on any Saturnian satellite except Titan; photolysis explains the absence of NH₃ ices on these bodies, and possibly the absence of water ice on the surface of Callisto. The photolysis rate of CH₄ also implies a crustal reservoir of CH₄ on Titan.     

Internal structure of Europa and Callisto

Models of the internal structure of completely differentiated Europa and partially differentiated Callisto have been constructed on the basis of Galileo gravity measurements, geochemical constraints on composition of ordinary and carbonaceous chondrites, and thermodynamic data on the equations of state of water, high-pressure ices, and meteoritic material. We assume thermal and mechanical equilibrium for the interiors of the satellites. A geophysically and geochemically permissible thickness of Europa's outer water-ice shell lies between 105 and 160 km (6.2-9.2% of total mass). Our results show that the bulk composition of the rock-iron core of Europa may be described by material approaching the L/LL-type chondrites in composition, but cannot be correlated either with the material of CI chondrites or H chondrites. For Europa's L/LL-chondritic models, core radii are estimated to be 470-640 km (5.3-12.5% of total mass). The allowed thickness of Europa's H₂O layer ranges from 115±10 km for a differentiated L/LL-type chondritic mantle with a crust to 135±10 km for an undifferentiated mantle. We show that Callisto must only be partially differentiated into an outer ice-I layer, a water ocean, a rock-ice mantle, and a rock-iron core (mixture of anhydrous silicates and/or hydrous silicates + FeFeS alloy). We accept that the composition of the rock-iron material of Callisto is similar to the bulk composition of L/LL-type chondritic material containing up to 10-15% of iron and iron sulfide. Assuming conductive heat transfer through the ice-I crust [Ruiz, 2001. The stability against freezing of an internal liquid-water ocean on Gallisto. Nature, 412, 409-411], heat flows were estimated and the possibility of the existence of a water ocean in Callisto was evaluated. The liquid phase is stable (not freezing) beneath the ice crust, if the heat flow is between 3.3 and 3.7 mW m⁻², which corresponds to the heat flow from radiogenic sources. The thickness of the ice-I crust is 135-150 km, and that of the underlying water layer, 120-180 km. The results of modeling support the hypothesis that Callisto may have an internal liquid-water ocean. The allowed total (maximum) thickness of the outer water-ice shell is up to 270-315 km. Rock-iron core radii, depending on the presence or absence of hydrous silicates, do not exceed 500-700 km, the thickness of an intermediate ice-rock mantle is not less than 1400 km, and its density is in the range of 1960-2500 kg m⁻³. The surface temperature of Callisto is expected to be 100-112 K. The total amount of H₂O in Callisto is found to be 49-55 wt%. The correspondence between the density and moment of inertia values for bulk ice-free Io, rock-iron core of ice-poor Europa, and rock-iron cores of Ganymede and Callisto shows that their bulk compositions may be, in general, similar and may be described by the composition close to a material of the L/LL-type chondrites with the (Fe_tot/Si) weight ratios ranging from 0.9 to 1.3. Planetesimals composed of these types of ordinary chondrites could be considered as analogues of building material for the rock-iron cores of the Galilean satellites. Similarity of bulk composition of the rock-iron cores of the inner and outer satellites implies the absence of iron-silicon fractionation in the protojovian nebula.     

An improved model of radiative transfer for the NLTE problem in the NIR bands of CO<Subscript>2</Subscript> and CO molecules in the daytime atmosphere of Mars. 2. Population of vibrational states

The near-infrared (NIR) emission of the Martian atmosphere in the CO2 bands at 4.3, 2.7, 2.0, 1.6, 1.4, 1.3, 1.2, and 1.05 µm and in the CO bands at 4.7, 2.3, 1.6, and 1.2 µm is mainly generated under nonlocal thermodynamic equilibrium (NLTE) conditions for vibrational states, the transitions from which form the specified bands. The paper presents the results of simulations of the population of these states under NLTE for daytime conditions. In the cold high-latitude troposphere, the NLTE takes place much lower than in the troposphere under typical temperature conditions. If the NIR-radiation reflection from the surface is ignored, the population of high vibrational states substantially decreases, at least, in some layer of the lower atmosphere. However, inelastic collisions of CO₂ and CO molecules with O atoms produce no considerable influence on the values of populations. The population of vibrational states, the transitions from which form NIR bands, is also almost insensitive to possible large values of the quenching-in-collision rate constants of vibrational states higher than CO₂(00⁰1). However, very large errors in the estimates of the population of vibrational states of the CO₂ molecule (rather than the CO molecule!) can be caused by the uncertainty in the values of the rate constant of exchange between CO² molecules by the energy quantum of the asymmetric stretching vibrational mode. For this intermolecular exchange, we recommend a possible way to restrict the vibrational excitation degree of the molecule that is a collision partner and to maintain simultaneously a sufficiently high accuracy in the population estimate.     

Ozone photochemistry in the condensed phase

Recent results about the ozone photochemistry in solid matrices (O₂, Ar, N₂) and water ices are reported. Several areas are reviewed: photochemistry in the visible and UV of ozone monomer, photochemistry of ozone involved in weak complexes, reactivity of atomic oxygen with various partners in nearest neighbour.Although reactions occurring in matrices are not the same as in gas phase, pathways displayed in matrices can bring information for gas phase modelling.     

A quantum chemical study on the formation of ethanimine (CH<Subscript>3</Subscript>CHNH) in the interstellar ice

Ethanimine (CH₃CHNH) is an important prebiotic molecule since it is a precursor of amino acid \(\alpha \)-alanine in Strecker synthesis. Two isomers (E and Z) of ethanimine were detected in the molecular cloud Sagittarius B2 north during GBT-PRIMOS survey. A possible radical-molecule reaction pathway has been proposed for the formation of ethanimine in the interstellar medium (ISM) from some previously detected interstellar molecules like methylene (both triplet CH₂ (³B₁) and singlet CH₂ (¹A₁)) and methyenimine (CH₂NH). The mechanism has been studied in the gas phase and in water ice with the help of density functional theory at B2PLYPD/6-311++G (2d, p) level of theory. It is observed that E-ethanimine forms efficiently in gas phase but ice reactions are favorable only in the hot core of molecular clouds. Same is true for the formation of Z-ethanimine which forms only at the surface of water cluster as the height of entrance barrier for formation of Z-ethanimine is similar to that of E-ethanimine. Isomerization from E to Z form is also studied and found to be forbidden due to large entrance barrier. Out of the two reaction system CH₂ (³B₁) + CH₂NH and CH₂ (¹A₁) + CH₂NH, later is more favorable then the former one due to the small entrance barrier. Still, much of the detected abundance of ethanimine comes from the reaction of CH₂ (³B₁) with CH₂NH as since CH₂ (¹A₁) has very low abundance compared to the CH₂ (³B₁) in ISM. The proposed pathway seems to be a promising candidate for the ethanimine formation in ISM.     

Solid co spectroscopy: embedded ysos in taurus-auriga

Infrared spectra of the 4.67µm solid CO feature were obtained for YSOs in Taurus. A first attempt is made to analyse the likely composition of the CO ices. Column densities are derived from the spectra, and compared with the ones predicted for a low mass protostar. The strengths of the CO- and water-ice features towards those objects are compared.TCT supported by grant BD/2095/92-RM from JNICT- Programa CIENCIA, Portugal     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

Laboratory set-up for studying ices at the MIR and FIR region

H₂O, CO and CO₂ ices are condensed on carbonaceous and silicate dust grains in dense interstellar clouds and circumstellar environments. The presence of these ices is inferred by analysing their infrared (IR) spectra. The upcoming Herschel space observatory (HERSCHEL) and ground-based astronomy project (ALMA) will provide new spectral data in the unexplored far infrared (FIR) and sub-millimetre range. In our laboratory we are developing instrumentation to study ices at IR region. One of the key components of our laboratory is a silicon composite bolometer in our IFS. This detector allows us to obtain spectra with a sensitivity much greater than that obtained with a standard deuterated triglycine sulphate (DTGS) detector working at room temperature and under vacuum conditions. We plan to collect mid infrared (MIR) and FIR spectra of simple ices and their mixtures and compare these with observational data. It is also planned to do a systematic laboratory study of the effects that ultraviolet (UV) photolysis and thermal annealing have on the ice band profiles and their structure.     

H<Stack><Subscript>2</Subscript><Superscript>16</Superscript></Stack>O and H<Stack><Subscript>2</Subscript><Superscript>18</Superscript></Stack>O maser emission from gas-dust clouds

The collisional pumping of H₂¹⁶O and H₂¹⁸O masers in hot dense gas-dust clouds has been simulated numerically. New data on the rate coefficients for collisional transitions from Faure et al. (2007) were used in the calculations. The possibility of detecting H₂¹⁸O emission in 22.2-GHz H₂¹⁶O maser sources is investigated. The medium is shown to become optically thick in the H₂¹⁸O lines for which an inverted level population is observed at H₂O column densities of ∼1019–1020 cm⁻². A simultaneous observation of H₂¹⁸O emission and H₂¹⁶O maser emission in the same source will allow the physical conditions in the gas-dust cloud to be refined.     

Limits on the trapping of atmospheric CH4 in martian polar ice analogs

Recent detection of methane (CH₄) on Mars has generated interest in possible biological or geological sources, but the factors responsible for the reported variability are not understood. Here we explore one potential sink that might affect the seasonal cycling of CH₄ on Mars - trapping in ices deposited on the surface. Our apparatus consisted of a high-vacuum chamber in which three different Mars ice analogs (water, carbon dioxide, and carbon dioxide clathrate hydrates) were deposited in the presence of CH₄ gas. The ices were monitored for spectroscopic evidence of CH₄ trapping using transmission Fourier-Transform Infrared (FT-IR) spectroscopy, and during subsequent sublimation of the ice films the vapor composition was measured using mass spectrometry (MS). Trapping of CH₄ in water ice was confirmed at deposition temperatures <100 K which is consistent with previous work, thus validating the experimental methods. However, no trapping of CH₄ was observed in the ice analogs studied at warmer temperatures (140 K for H₂O and CO₂ clathrate, 90 K for CO₂ snow) with approximately 10 mTorr CH₄ in the chamber. From experimental detection limits these results provide an upper limit of 0.02 for the atmosphere/ice trapping ratio of CH₄. If it is assumed that the trapping mechanism is linear with CH₄ partial pressure and can be extrapolated to Mars, this upper limit would indicate that less than 1% is expected to be trapped from the largest reported CH₄ plume, and therefore does not represent a significant sink for CH₄.     

Photometric and spectral analysis of the distribution of crystalline and amorphous ices on Enceladus as seen by Cassini

Photometric and spectral analysis of data from the Cassini Visual and Infrared Mapping Spectrometer (VIMS) has yielded significant results regarding the properties and composition of the surface of Saturn's satellite Enceladus. We have obtained spectral cubes of this satellite, containing both spatial and spectral information, with a wavelength distribution in the infrared far more extensive than from any previous observations and at much higher spatial resolution. Using a composite mosaic of the satellite, we map the distribution of crystalline and amorphous ices on the surface of Enceladus according to a “crystallinity factor” and also the depth of the temperature- and structure-dependent 1.65 micron water-ice band. These maps show the surface of Enceladus to be mostly crystalline, with a higher degree of crystallinity at the “tiger-stripe” cracks and a larger amorphous signature between these stripes. These results suggest recent geological activity at the “tiger stripe” cracks and an intriguing atmospheric environment over the south pole where amorphous ice is produced either through intense radiative bombardment, flash-freezing of cryovolcanic liquid, or rapid condensation of water vapor particles on icy microspherules or on the surface of Enceladus.     

Ionization chemistry in H<Subscript>2</Subscript>O-dominated atmospheres of icy moons

The processes of the formation and dynamics of tenuous gaseous envelopes of icy moons in giant-planet systems are considered. Tenuous exospheres with relatively dense surface layers are likely to form around more massive icy satellites, such as, for example, the Galilean satellites Europa and Ganymede in the Jovian system. Escaping exospheres are formed in the case of low-mass icy moons, as happens for the icy satellite Enceladus in the Saturnian system. The main parent component of such gaseous envelopes is water vapor, which enters into the atmosphere as a result of thermal degassing processes, nonthermal radiolysis, and other active processes and phenomena on the icy surface of a satellite. A numerical kinetic model has been developed to study on a molecular level the processes of the formation, chemical evolution, and dynamics of tenuous gaseous envelopes dominated mainly by H₂O. The ionization processes in such tenuous gaseous envelopes are caused by solar ultraviolet (UV) radiation and solar-wind and/or magnetospheric plasma. The primary processes when ultraviolet solar photons and plasma electrons affect the tenuous gas of the H₂O-dominated atmosphere are responsible for the chemical diversity of the gaseous envelopes of icy moons. Ionization chemistry, including ion-molecular reactions, dissociative recombination of molecular ions, and the reactions of the charge exchange with magnetospheric ions, is important for the formation of chemical diversity in gaseous envelopes of icy satellites. The model considered in the study was used to numerically simulate the formation and development of chemical diversity in the tenuous gaseous envelope of Enceladus. The numerical results were compared to the direct Cassini measurements during its close flyby near Enceladus.     

Stability of hydrous minerals on the martian surface

The presence of water-bearing minerals on Mars has long been discussed, but little or no data exist showing that minerals such as smectites and zeolites may be present on the surface in a hydrated state (i.e., that they could contain H₂O molecules in their interlayer or extra-framework sites, respectively). We have analyzed experimental thermodynamic and X-ray powder diffraction data for smectite and the most common terrestrial zeolite, clinoptilolite, to evaluate the state of hydration of these minerals under martian surface conditions. Thermodynamic data for clinoptilolite show that water molecules in its extra-framework sites are held very strongly, with enthalpies of dehydration for Ca-clinoptilolite up to three times greater than that for liquid water. Using these data, we calculated the Gibbs free energy of hydration of clinoptilolite and smectite as a function of temperature and pressure. The calculations demonstrate that these minerals would indeed be hydrated under the very low-P (H₂O) conditions existing on Mars, a reflection of their high affinities for H₂O. These calculations assuming the partial pressure of H₂O and the temperature range expected on Mars suggest that, if present on the surface, zeolites and Ca-smectites could also play a role in affecting the diurnal variations in martian atmospheric H₂O because their calculated water contents vary considerably over daily martian temperature ranges. The open crystal structure of clinoptilolite and existing hydration and kinetic data suggest that hydration/dehydration are not kinetically limited. Based on these calculations, it is possible that hydrated zeolites and clay minerals may explain some of the recent observations of significant amounts of hydrogen not attributable to water ice at martian mid-latitudes.     

Comparison between polar regions of Mars from HEND/Odyssey data

In this paper, we have analyzed neutron spectroscopy data gathered by the High Energy Neutron Detector (HEND) instrument onboard Mars Odyssey for comparison of polar regions. It is known that observation of the neutron albedo of Mars provides important information about the distribution of water-ice in subsurface layers and about peculiarities of the CO₂ seasonal cycle. It was found that there are large water-rich permafrost areas with contents of up to ∼50% water by mass fraction at both the north and south Mars polar regions. The water-ice layers at high northern latitudes are placed close to the surface, but in the south they are covered by a dry and relatively thick (10-20 cm) layer of soil. Analysis of temporal variations of neutron flux between summer and winter seasons allowed the estimation of the masses of the CO₂ deposits which seasonally condense at the polar regions. The total mass of the southern seasonal deposition was estimated as 6.3×¹⁰¹⁵ kg, which is larger than the total mass of the seasonal deposition at the north by 40-50%. These results are in good agreement with predictions from the NASA Ames Research Center General Circulation Model (GCM). But, the dynamics of the condensation and sublimation processes are not quite as consistent with these models: the peak accumulation of the condensed mass of CO₂ occurred 10-15 degrees of Ls later than is predicted by the GCM.     

CO clathrate hydrate: Near to mid-IR spectroscopic signatures

Carbon monoxide is the second most abundant molecule after H₂ in the molecular universe, and as such an abundant constituent of interstellar and Solar System ices. To trace the possibility of this molecule to be found in a clathrate hydrate inclusion compound, its pure phase FTIR spectrum is investigated. We confirm the formation of a type I clathrate structure whereas simple guest size estimates would favour a type II clathrate hydrate, revealing interactions of this molecule with its water network during clathrate formation. The observed cage vibrational downshift with respect to pure CO ice is within 5 cm⁻¹. The temperature dependent wavenumber separation between the two enclathrated CO vibrational transitions in the two distinct type I clathrate cages is less than a wavenumber below 140 K, implying that the spectral simplification for detailed spectroscopic analysis of the individual profiles is a difficult task. The dynamics of the CO molecules in its cage change considerably from 5 K to 140 K. At temperatures above 30 K, the molecule is extremely mobile in the cages, as revealed by the infrared profile, significantly different from CO entrapped in water ice and different from observed profiles in astrophysical objects.     

Numerical simulation of seasonal dynamics of water vapor in the Martian atmosphere

The seasonal evolution of the H₂O snow in the Martian polar caps and the dynamics of water vapor in the Martian atmosphere are studied. It is concluded that the variations of the H₂O mass in the polar caps of Mars are determined by the soil thermal regime in the polar regions of the planet. The atmosphere affects water condensation and evaporation in the polar caps mainly by transferring water between the polar caps. The stability of the system implies the presence of a source of water vapor that compensates for the removal of water from the atmosphere due to permanent vapor condensation in the polar residual caps. The evaporation of the water ice that is present in the surface soil layers in the polar regions of the planet is considered as such a source. The annual growth of the water-ice mass in the residual polar caps is estimated. The latitudinal pattern of the seasonal distribution of water vapor in the atmosphere is obtained for the stable regime.Translated from Astronomicheskii Vestnik, Vol. 38, No. 6, 2004, pp. 497–503.Original Russian Text Copyright © 2004 by Aleshin.