Studies of proton-irradiated cometary-type ice mixtures

Radiation synthesis has been proposed as a mechanism for changing the nature of the outer few meters of ice in a comet stored 4.6 billion years in the Oort cloud and may explain some of the differences observed between new and more evolved comets. Cometary-type ice mixtures were studied in a laboratory experiment designed to approximately simulate the expected temperature, pressure, and radiation environment of the interstellar Oort cloud region. The 2.5- to 15-μm infrared absorption features of thin ice films were analyzed near 20°K before and after 1 MeV proton irradiation. Various ice mixtures included the molecules H₂O, NH₃, CH₄, N₂, C₃H₈, CO, and CO₂. All experiments confirm the synthesis of new molecular species in solid phase mixtures at 20°K. The synthesized molecules, identified by their infrared signatures, are C₂H₆, CO₂, CO, N₂O, NO, and CH₄ (weak). Synthesized molecules, identified by gas chromatographic (GC) analysis of the volatile fraction of the warmed irradiated ice mixture, are C₂H₄ or C₂H₆, and C₃H₈. When CH₄ is present in the irradiated ice mixture, long-chained volatile hydrocarbons and CO₂ are synthesized along with high-molecular-weight carbon compounds present in the room temperature residue. Irradiated mixtures containing CO and H₂O synthesize CO₂ and those CO₂ and H₂O synthesize CO. Due to radiation synthesis, ～1% of the ice was converted into a nonvolatile residue containing complicated carbon compounds not present in blank samples. These results suggest that irrespective of the composition of newly accreted comets, initial molecular abundances can be altered and new species created as a result of radiation synthesis. Irradiated mixtures exhibited thermoluminescence and pressure enhancements during warming; these phenomena suggest irradiation synthesis of reactive species. Ourbursts in new comets resulting from similar radiation induced exothermic activity would be expected to occur beginning at distances of the order of 100 AU.     

Photochemistry of minor constituents in the troposphere

Altitude profiles for the number densities of NO, NO₂, NO₃, N₂O₅, HNO₂, CH₃O, CH₃O₂, H₂CO, OH, and HO₂ are calculated as a function of time of day with a steady-state photochemical model in which the altitude profiles for the number densities of H₂O, CH₄, H₂, CO, O₃, and the sum of NO and NO₂ are fixed at values appropriate to a summer latitude of 34°. Average daily profiles are calculated for the long-lived species, HNO₃, H₂O₂, and CH₃O₂H.The major nitrogen compound HNO₃ may have a number density approaching 5 × 10¹¹ molecules cm^?3 at the surface, although an effective loss path due to collisions with particulates could greatly reduce this value.The number density of OH remains relatively unchanged in the first 6 km and reaches 1 × 10⁷ molecules cm^?3 at noon, while the number density of HO₂ decreases throughout the lower troposphere from its noontime value of 8 × 10⁸ molecules cm^?3 at the surface.H₂O₂ and H₂CO both have number densities in the ppb range in the lower troposphere.Owing to decreasing temperature and water concentration, the production of radicals and their steady-state number densities decrease with altitude, reaching a noontime minimum of 1 × 10⁸ molecules cm^?3 for OH and 3 × 10⁷ molecules cm^?3 for HO₂ at the tropopause. The related minor species show even sharper decreases with increasing altitude.The primary path for interconverting OH and HO₂ serves as the major sink for CO and leads to a tropospheric lifetime for CO of ~0.1 yr.Another reaction cycle, the oxidation of CH₄, is quite important in the lower troposphere and leads to the production of H₂CO along with the destruction of CH₄ for which a tropospheric lifetime of ~2 yr is estimated.The destruction of H₂CO that was produced in the CH₄ oxidation cycle provides the major source of CO and H₂ in the atmosphere.     

Monte Carlo modeling of neutral gas and dust in the coma of Comet 1P/Halley

The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer and the Dust Impact Detection System onboard the Giotto spacecraft taken during the fly-by at Comet 1P/Halley in 1986. We also show that our model is in good agreement with contemporaneous measurements obtained by the International Ultraviolet Explorer, sounding rocket experiments, and various ground based observations.The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique (Tenishev, V., Combi, M., Davidsson, B. [2008]. Astrophys. J. 685, 659-677) by tracking trajectories of gas molecules and dust grains under the influence of the comet’s weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H₂O, CO, H₂CO, CO₂, CH₃OH, C₂H₆, C₂H₄, C₂H₂, HCN, NH₃, and CH₄) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H₂, O, OH, C, CH, CH₂, CH₃, N, NH, NH₂, C₂, C₂H, C₂H₅, CN, and HCO) from the comet’s surface all the way out to 10⁶ km.As a result we are able to further constrain cometary the gas production rates of CO (13%), CO₂ (2.5%), and H₂CO (1.5%) relative to water without invoking unknown extended sources.     

Spectroscopy of Comet Hale-Bopp in the infrared

High resolution infrared spectra of Comet C/1995 O1 (Hale-Bopp) were obtained during 2-5 March 1997 UT from the NASA Infrared Telescope Facility on Mauna Kea, Hawaii, when the comet was at r≈1.0 AU from the Sun pre-perihelion. Emission lines of CH₄, C₂H₆, HCN, C₂H₂, CH₃OH, H₂O, CO, and OH were detected. The rotational temperature of CH₄ in the inner coma was T_rot=110±20 K. Spatial profiles of CH₄, C₂H₆, and H₂O were consistent with release solely from the nucleus. The centroid of the CO emission was offset from that of the dust continuum and H₂O. Spatial profiles of the CO lines were much broader than those of the other molecules and asymmetric. We estimate the CO production rate using a simplified outflow model: constant, symmetric outflow from the peak position. A model of the excitation of CO that includes optical depth effects using an escape probability method is presented. Optical depth effects are not sufficient to explain the broad spatial extent. Using a parent+extended-source model, the broad extent of the CO lines can be explained by CO being produced mostly (∼90% on 5 March) from an extended source in the coma. The CO rotational temperature was near 100 K. Abundances relative to H₂O (in percent) were 1.1±0.3 (CH₄), 0.39±0.10 (C₂H₆), 0.18±0.04 (HCN), 0.17±0.04 (C₂H₂), 1.7±0.5 (CH₃OH), and 37-41 (CO, parent+extended source). These are roughly comparable to those obtained for other long-period comets also observed in the infrared, though CO appears to vary.     

Reflectance and transmittance spectra (2.2-2.4 μm) of ion irradiated frozen methanol

We present near-IR (2.2-2.4 μm) reflectance and transmittance spectra of frozen (16 and 77 K) methanol (CH₃OH) and water-methanol (1:1) mixtures before and after irradiation with 30 keV He⁺ and 200 keV H⁺ ions. Spectra of other simple hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆) and CO have also been obtained both to help in the identification of the new molecules formed after ion irradiation of methanol-rich ices, and to get insight into the question of the presence of simple frozen hydrocarbons on the surface of some objects in the outer Solar System. The results confirm what obtained by studies performed in different spectral ranges, namely the ion-induced formation of CO and CH₄, and, for the first time, evidence a strong decrease of the intensity of the methanol band at about 2.34 μm in comparison with that at 2.27 μm. The results are discussed in view of their relevance for icy objects in the Solar System (namely comets, Centaurs, and Kuiper belt objects) where CH₃OH has been observed or suggested to be present.     

Injection of molecules from the surfaces of grains into the gas phase chemistry of an expanding cloud

We present model results for the chemistry in an expanding cloud or clump in which molecules are injected into the gas phase from grain surfaces when the clump reaches a certain visual extinction A _v during the expansion. We consider separately injection at two different values of A _v, and include a representative large hydrocarbon, C₆H, and sulphur-bearing molecule, H₂SO₄, as well as H₂O and CO. We examine the abundances of certain molecules which have been observed in diffuse and translucent clouds, and compare the results obtained for these abundances with and without an injection during expansion. We also compare our results withpublished observations, and conclude that in most clouds an injection of molecules has occurred.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Global atmospheric monitoring with SCIAMACHY

SCIAMACHY (SCanning Imaging Absorption spectrometer for Atmospheric CHartographY) is a space based spectrometer designed to measure sunlight transmitted, reflected and scattered by the Earth atmosphere or surface. It is a contribution to the Envisat-1 satellite to be launched in late 1999.SCIAMACHY measurements will provide amounts and distribution of 0₃, BrO, OCl0, ClO, S0₂, H₂CO, N0₂, CO, CO₂, CH₄, H₂O, N₂0, pressure, temperature, aerosol, radiation, cloud cover and cloud top height from atmospheric measurements in nadir, limb and occultation geometry.By the combination of the near simultaneous limb and nadir observations SCIAMACHY is one of a limited number of instruments which is able to detect tropospheric column amounts of 0₃, N0₂, CO, CH₄, H₂O, N₂0, S0₂, H₂CO, and BrO down to the planetary boundary layer under cloud free conditions.     

Infrared Spectroscopy of Comet Hale-Bopp

High resolution (λ/δλ ∼ 20,000) spectra of comet C/1995 O1 (Hale-Bopp) in the 2–5 μm region were obtained during UT 2–5 March 1997 using CSHELL at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea. The heliocentric and geocentric distances of the comet were ∼1.1 AU and ∼1.5 AU,respectively. We detected emission lines of the gas-phase molecules H₂O, ₄, C₂H₆, C₂H₂, HCN, and CO and derived absolute production rates and relative abundances for all species. We also used the 2-dimensional nature of the CSHELL data to investigate the spatial distribution of the molecules and find evidence that CO was derived at least partly from an extended source in the coma. This revised version was published online in July 2006 with corrections to the Cover Date.     

Shock waves and the chemical structure of interstellar clouds

In this paper we study the effect of shock waves on the chemical structure of the interstellar clouds. A model of molecular cloud has been assumed. The chemistry is investigated in a time dependent model. Our chemical network contains 56 species in 251 reactions to including molecules of the elements H, O, C, N, S, and Si.The results indicate that the calculated fractional abundance of the molecules NS, H₂O, CN, NH, CO, and SO agrees well with the observations. The molecules OH, H₂S, CS, H₂CS, HS, NO, SiO, CH, CH₂, CH₃, HCO, C₂, and HCN reach high post-shock abundances.     

Theoretical investigation of interstellar C–C–O and C–O–C bonding backbone molecules

There are numerous complex organic molecules containing carbon and oxygen atoms which show either C–C–O or C–O–C bonding backbone. This paper examines altogether 51 C–C–O and C–O–C bonding backbone molecules from ten different isomeric groups (C₂H₂O, C₃H₂O, C₂H₄O, C₂H₄O₂, C₃H₄O, C₂H₆O, C₂H₆O₂, C₃H₆O, C₃H₆O₂, C₃H₈O) to summarize the present astronomical status of these molecules. Accurate calculations of enthalpy of formation of these molecules show that the isomers with C–C–O backbone are more stable than the C–O–C backbone. Interestingly, a detailed analysis of relevant astromolecules indicates that most of the observed astromolecules have the C–C–O backbone. As a matter of fact, of all the molecules examined in this study, 80% of the astronomically observed species have the C–C–O backbone while only 20% have the C–O–C backbone. In general, interstellar abundance of a molecule is controlled by some factors such as kinetics, formation and destruction pathways,thermodynamics etc. A proper consideration of these factors could explain the observed abundances of these molecules. All these possible key factors are discussed in this paper.     

Infrared measurements of the chemical composition of C/2006 P1 McNaught

C/2006 P1 McNaught is a dynamically new comet from the Oort cloud that passed very close to the Sun, driving overall volatile production rates up to about 10³¹ molecules s⁻¹. Post-perihelion observations were obtained in a target-of-opportunity campaign using the CSHELL instrument at the NASA Infrared Telescope Facility atop Mauna Kea, Hawaii, on UT 2007 January 27 and 28. Eight parent volatiles (H₂O, CH₄, C₂H₂, C₂H₆, HCN, CO, NH₃, H₂CO) and two daughter fragments (OH and NH₂) were detected, enabling the determination of a rotational temperature and production rate for H₂O on UT January 27 and absolute and relative production rates for all the detected parent species on UT January 28. The chemical composition measured in the coma suggests that this close perihelion passage stripped off processed outer surface layers, likely exposing relatively fresh primordial material during these observations. The post-perihelion abundances we measure for CO and CH₄ (relative to H₂O) are slightly depleted while C₂H₂, NH₂ and possibly NH₃ are enhanced when compared to the overall comet population. Measured abundances for other detected molecular species were within the range typically observed in comets.     

The composition of the Martian atmosphere: Minor constituents

The Mariner 6 and 7 infrared spectrometers provided data which, in principle, determine upper limits on the possible atmospheric abundance of every gaseous substance that was undetected but which has recognized absorptions in the accessible spectral region, 1.9 to 14.4 μ. Through supporting laboratory determinations of curves of growth under pressure broadening conditions appropriate to Mars, upper limits can be specified (expressed first in cm-atm, STP, for a vertical column and then in parts per million) for the following gases: NO₂ (<0.0016, 0.23); NH₃ (<0.0031, 0.44); C₃O₂ (<0.0032, 0.45); SO₂ (?0.0037, 0.52); OCS (<0.0040, 0.56); NO (<0.0050, 0.70); O₃ (<0.0061, 0.86); CH₄ (<0.026, 3.7); N₂O (<0.13, 18); HCl (<3.7, 520); HBr (?8.2, 1150); H₂S (<27, 3800). In addition, considerations of band contours, moments of inertia, and experimental absorption coefficients permit us to place useful upper limits on twenty-seven additional substances that were not detected and for which curves of growth have not been measured: less than 1.0ppm (or, <0.0071cm-atm); SF₆, NF₃, Cl₂CO, CF₄, CHF₃, Br₂CO, SiF₄; less than 6.0ppm (or, <0.035 cm-atm); C₂F₆, CO₃, F₂CO, C₂H₄, BF₃, CS₂, CHCl₃, C₂H₆, H₂CO, CH₃F, C₆H₆, CH₂I₂; less than 50ppm (or, <0.35 cm-atm): C₂H₂, HCN, CH₂Br₂, CH₂Cl₂, CH₃Br, PH₃, CH₃I, and CH₃Cl. These upper limits are compared to earlier limits based upon terrestrial measurements. The present limits placed upon the possible atmospheric content of the molecules C₃O₂ and CO₃ are of particular interest because of their relevance to the photochemistry of the Martian atmosphere.     

Reaction between H2, CO,and H2S over Fe,Ni metal in the solar nebula: Experimental evidence for the formation of sulfur‐bearing organic molecules and sulfides

Abstract— Detailed laboratory studies have been carried out in order to simulate the interaction between nanometer‐sized kamacite metal particles and different gas mixtures consisting of H₂:H₂S (250:0.1), H₂:CO (250:1), and H₂:CO:H₂S (250:1:0.1) under nebular‐type conditions (5 × 10^?4 atm and 473 K). Reaction of H₂ + H₂S with kamacite particles for 1000 h leads to the formation of pyrrhotite. Incorporation of CO into the gaseous reactant mixture results in the formation of both sulfide and carbide phases. At the same time, amorphous C is deposited onto the metal particles and organic molecules are evolved, namely hydrocarbons and thiols in the C₁‐C₅ and C₁‐C₂ range, respectively. Carbon deposition and production of organics are enhanced with respect to experiments performed with H₂ + CO, where a carbide phase is formed. There is no evidence for the existence of S‐poisoning effects on the metal‐catalysed hydrogenation of CO through Fischer‐Tropsch‐type reactions in nebular environments. In fact, it is experimentally demonstrated that S‐containing organic species could be synthesized by such reactions from nebular gas.     

The status of spectroscopic data for the exoplanet characterisation missions

The status of laboratory spectroscopic data for exoplanet characterisation missions such as EChO is reviewed. For many molecules (eg H ₂O, CO, CO ₂, H\(_{3}^{+}\), O ₂, O ₃) the data are already available. For the other species work is actively in progress constructing this data. Much of the is work is being undertaken by ExoMol project (www.?exomol.?com). This information can be used to construct a mission-specific spectroscopic database.     

The organic composition of Comet C/2001 A2 (LINEAR): I. Evidence for an unusual organic chemistry

We used the NIRSPEC instrument on the Keck-2 telescope atop Mauna Kea, HI to observe Comet C/2001 A2 (LINEAR) in a Target of Opportunity campaign on UT 2001 July 9.5, 10.5 August 4.4, 10.5. We measured seven organic parent volatiles (C₂H₆, C₂H₂, HCN, CH₄, CO, CH₃OH, H₂CO) simultaneously with H₂O. We obtained absolute production rates and relative abundances for parent volatiles, and also measured rotational temperatures for several of these species. The chemical composition of C/2001 A2 differs substantially from any comet we have observed to date. The abundances we measure (relative to H₂O) for C₂H₆, C₂H₂, HCN, and CH₃OH are enriched by a factor of ∼2 to 3 in C/2001 A2 compared with most comets in our database. Other molecular species were detected within the typical range of measured abundances. C/2001 A2 presented a unique opportunity to study the chemistry of a fragmenting comet where pristine areas are exposed to the Sun.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.     

The influence of grain mantles on the formation of hydrogen molecules on grain surfaces

The physical adsorption energy,E, of hydrogen molecules on various substrates at temperatures between 5 and 30 K and at the lowest practicable gas densities has been measured. Values ofE/k are for condensed CO 340 K, CO₂ 800 K, H₂O 850 K and for ‘dirty’ graphite 980 K and ‘dirty’ copper 800 K. From these measurements temperature ranges in which H atoms might combine on the surface to form H₂ molecules are estimated. Duley has discussed the formation and composition of condensed gas mantles on interstellar grains. The effects of such mantles in promoting and poisoning hydrogen molecule formation are discussed.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Cosmic ray synthesis of organic molecules in Titan's atmosphere

We have studied the possible synthesis of organic molecules by the absorption of galactic cosmic rays in an N₂CH₄H₂ Titan model atmosphere. The cosmic-ray-induced ionization results in peak electron densities of 2 × 10³ cm^?3, with NH₄⁺, C₃H₉⁺, and C₄H₉⁺ being among the important positive ions. Details of the ion and neutral chemistry relevant to the production of organic molecules are discussed. The potential importance of $\text{N}\text{(}{}^2\text{D)}$ reactions with CH₄ and H₂ is also demonstrated. Although the integrated production rate of organic matter due to the absorption of the cosmic ray cascade is much less than that by solar ultraviolet radiation, the production of nitrogen-bearing organic molecules by cosmic rays may be greater.