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.     

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH₃CN, CH₃CH₂CN, CH₂CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH₃)₂CHCN and (CH₃)₃CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH₃CN, CH₃CH₂CN, and (CH₃)₂CHCN also formed ketenimines. In the presence of H₂O, no isonitriles were detected but rather the cyanate ion (OCN⁻) was seen in all cases. Although isonitriles, ketenimines, and OCN⁻ were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.     

Formation and photochemistry of Methylamine in Jupiter's atmosphere

The formation of methylamine (CH₃NH₂) in the upper troposphere and lower stratosphere of Jupiter is investigated. Translationally hot hydrogen atoms are produced in the photolysis of ammonia, phosphine, and acetylene which react with methane to produce methyl (CH₃) radicals; the latter recombine with NH₂ to form CH₃NH₂. Also, methane is catalytically dissociated to CH₃ + H by the species C₂ and C₂H produced in the photolysis of acetylene. It is shown that the combined production of CH₃NH₂ and subsequent photolysis to HCN is unlikely to account for the HCN observed near Jupiter's tropopause. Recombination of NH₂ and C₂H₅N followed by photolysis to HCN is the preferred path. Production of C₂H₆ by these two processes is negligible in comparison to the downward flux of C₂H₆ from the Lyman α photolysis region of CH₄. An upper limit column density on CH₃PH₂ is estimated to be ～10¹³ cm^?2 as compared to 10¹⁵ cm^?2 for CH₃NH₂. Hot H atoms account for a negligible fraction of the total ortho-para conversion by the reaction H + H₂     

The absence of endogenic methane on Titan and its implications for the origin of atmospheric nitrogen

We calculate the D/H ratio of CH₄ from serpentinization on Titan to determine whether Titan’s atmospheric CH₄ was originally produced inside the giant satellite. This is done by performing equilibrium isotopic fractionation calculations in the CH₄-H₂O-H₂ system, with the assumption that the bulk D/H ratio of the system is equivalent to that of the H₂O in the plume of Enceladus. These calculations show that the D/H ratio of hydrothermally produced CH₄ would be markedly higher than that of atmospheric CH₄ on Titan. The implication is that Titan’s CH₄ is a primordial chemical species that was accreted by the moon during its formation. There are two evolutionary scenarios that are consistent with the apparent absence of endogenic CH₄ in Titan’s atmosphere. The first is that hydrothermal systems capable of making CH₄ never existed on Titan because Titan’s interior has always been too cold. The second is that hydrothermal systems on Titan were sufficiently oxidized so that C existed in them predominately in the form of CO₂. The latter scenario naturally predicts the formation of endogenic N₂, providing a new hypothesis for the origin of Titan’s atmospheric N₂: the hydrothermal oxidation of ¹⁵N-enriched NH₃. A primordial origin for CH₄ and an endogenic origin for N₂ are self-consistent, but both hypotheses need to be tested further by acquiring isotopic data, especially the D/H ratio of CH₄ in comets, and the ¹⁵N/¹⁴N ratio of NH₃ in comets and that of N₂ in one of Enceladus’ plumes.     

Ion composition and chemistry in the coma of Comet 1P/Halley—A comparison between Giotto's Ion Mass Spectrometer and our ion-chemical network

In order to understand the cometary plasma environment it is important to track the closely linked chemical reactions that dominate ion evolution. We used a coupled MHD ion-chemistry model to analyze previously unpublished Giotto High Intensity Ion Mass Spectrometer (HIS-IMS) data. In this way we study the major species, but we also try to match some minor species like the CH_x and the NH_x groups. Crucial for this match is the model used for the electrons since they are important for ion-electron recombination. To further improve our results we included an enhanced density of supersonic electrons in the ion pile-up region which increases the local electron impact ionization. In this paper we discuss the results for the following important ions: C⁺, CH⁺, CH⁺₂, CH⁺₃, N⁺, NH⁺, NH⁺₂, NH⁺₃, NH⁺₄, O⁺, OH⁺, H₂O⁺, H₃O⁺, CO⁺, HCO⁺, H₃CO⁺, and CH₃OH⁺₂. We also address the inner shock which is very distinctive in our MHD model as well as in the IMS data. It is located just inside the contact surface at approximately 4550 km. Comparisons of the ion bulk flow directions and velocities from our MHD model with the data measured by the HIS-IMS give indication for a solar wind magnetic field direction different from the standard Parker angle at Halley's position. Our ion-chemical network model results are in a good agreement with the experimental data. In order to achieve the presented results we included an additional short lived inner source for the C⁺, CH⁺, and CH⁺₂ ions. Furthermore we performed our simulations with two different production rates to better match the measurements which is an indication for a change and/or an asymmetric pattern (e.g. jets) in the production rate during Giotto's fly-by at Halley's comet.     

Evidence of N2-ice on the surface of the icy dwarf Planet 136472 (2005 FY9)

We present high signal precision optical reflectance spectra of 2005 FY9 taken with the Red Channel Spectrograph and the 6.5-m MMT telescope on 2006 March 4 UT (5000-9500 Å; 6.33 Å pixel⁻¹) and 2007 February 12 UT (6600-8500 Å; 1.93 Å pixel⁻¹). From cross-correlation experiments between the 2006 March 4 spectrum and a pure CH₄-ice Hapke model, we find the CH₄-ice bands in the MMT spectrum are blueshifted by 3 ± 4 Å relative to bands in the pure CH₄-ice Hapke spectrum. The higher resolution MMT spectrum of 2007 February 12 UT enabled us to measure shifts of individual CH₄-ice bands. We find the 7296, 7862, and 7993 Å CH₄-ice bands are blueshifted by 4 ± 2, 4 ± 4, and 6 ± 5 Å. From four measurements we report here and one of our previously published measurements, we find the CH₄-ice bands are shifted by 4 ± 1 Å. This small shift is important because it suggest the presence of another ice component on the surface of 2005 FY9. Laboratory experiments show that CH₄-ice bands in spectra of CH₄ mixed with other ices are blueshifted relative to bands in spectra of pure CH₄-ice. A likely candidate for the other component is N₂-ice because its weak 2.15 μm band and blueshifted CH₄ bands are seen in spectra of Triton and Pluto. Assuming the shift is due to the presence of N₂, spectra taken on two consecutive nights show no difference in CH₄/N₂. In addition, we find no measurable difference in CH₄/N₂ at different depths into the surface of 2005 FY9.     

The upper ionosphere of Titan

Photoionization of the upper atmosphere of Titan by sunlight is expected to produce a substantial ionospheric layer. We have solved one-dimensional forms of the mass, momentum, and energy conservation equations for ions and electrons and have obtained electron number densities of about 10³ cm^?3, using various model atmospheres. The significant ions in a CH₄H₂ atmosphere are H⁺, H₃⁺, CH₅⁺, CH₅⁺, CH₃⁺, and C₂H₅⁺. Electron temperatures may be as high as 1000°K, depending on the abundance of hydrogen in the high atmosphere. Interaction of the solar wind with the ionosphere is also discussed.     

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.     

Infrared study of ion-irradiated N2-dominated ices relevant to Triton and Pluto: formation of HCN and HNC

Infrared spectra and radiation chemical behavior of N₂-dominated ices relevant to the surfaces of Triton and Pluto are presented. This is the first systematic IR study of proton-irradiated N₂-rich ices containing CH₄ and CO. Experiments at 12 K show that HCN, HNC, and diazomethane (CH₂N₂) form in the solid phase, along with several radicals. NH₃ is also identified in irradiated N₂ + CH₄ and N₂ + CH₄ + CO. We show that HCN and HNC are made in irradiated binary ice mixtures having initial N₂/CH₄ ratios from 100 to 4, and in three-component mixtures have an initial N₂/(CH₄ + CO) ratio of 50. HCN and HNC are not detected in N₂-dominated ices when CH₄ is replaced with C₂H₆, C₂H₂, or CH₃OH.The intrinsic band strengths of HCN and HNC are measured and used to calculate G(HCN) and G(HNC) in irradiated N₂ + CH₄ and N₂ + CH₄ + CO ices. In addition, the HNC/HCN ratio is calculated to be ∼1 in both icy mixtures. These radiolysis results reveal, for the first time, solid-phase synthesis of both HCN and HNC in N₂-rich ices containing CH₄.We examine the evolution of spectral features due to acid-base reactions (acids such as HCN, HNC, and HNCO and a base, NH₃) triggered by warming irradiated ices from 12 K to 30-35 K. We identify anions (OCN⁻, CN⁻, and N3−) in ices warmed to 35 K. These ions are expected to form and survive on the surfaces of Triton and Pluto. Our results have astrobiological implications since many of these products (HCN, HNC, HNCO, NH₃, NH₄OCN, and NH₄CN) are involved in the syntheses of biomolecules such as amino acids and polypeptides.     

A fast computation of the diurnal secondary ion production in the ionosphere of Titan

We propose an analytic model that allows rapid computation of the secondary ion production due to electron impact from the primary photo-production in the ionosphere of Titan. The model parameters are given for each of the 5 major ion productions (N⁺₂, CH⁺₄, N⁺, CH⁺₃, N⁺⁺₂) as well as for the electron production.     

Radioastronomical observations of comets IRAS-Araki-Alcock (1983d) and Sugano-Saigusa-Fujikawa (1983e)

Detections and upper limits to the continuum emission (1 ≤ λ ≤6 cm) and spectral line emission (OH, CO, CS, HCN, HCO⁺, CN, CH₃CN, CH₃C₂H, NH₃, H₂O, HC₃N, CH₃CH₂CN) are reported from radio observations of Comets 1983d and 1983e. Comparison is made with observations of CN at optical wavelengths. These results may be useful in planning future cometary observations.     

Early Mars serpentinization‐derived CH4 reservoirs,H2‐induced warming and paleopressure evolution

CH₄ has been observed on Mars both by remote sensing and in situ during the past 15 yr. It could have been produced by early Mars serpentinization processes that could also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH₄ as clathrates in stable form at depth. The maximum storage capacity of such a clathrate cryosphere has been recently estimated to be 2 × 10¹⁹ to 2 × 10²⁰ moles of methane. We estimate how large amounts of serpentinization‐derived CH₄ stored in the cryosphere have been released into the atmosphere during the Noachian and the early Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH₄ to H₂, these episodes of massive CH₄ release may have resulted in transient H₂‐rich atmospheres, at typical levels of 10–20% in a background 1–2 bar CO₂ atmosphere. The collision‐induced heating effect of H₂ present in such an atmosphere has been shown to raise the surface temperature above the water freezing point. We show how local and rapid destabilization of the cryosphere can be induced by large events (such as the Hellas Basin or Tharsis bulge formation) and lead to such releases. Our results show that the early Mars cryosphere had a sufficient CH₄ storage capacity to have maintained H₂‐rich transient atmospheres during a total time period up to several million years or tens of million years, having potentially contributed to the formation of valley networks during the Noachian/early Hesperian.     

Near-infrared spectra of laboratory H2O-CH4 ice mixtures

We present 1.25-19 μm infrared spectra of pure solid CH₄ and H₂O/CH₄=87, 20, and 3 solid mixtures at temperatures from 15 to 150 K. We compare and contrast the absorptions of CH₄ in solid H₂O with those of pure CH₄. Changes in selected peak positions, profiles, and relative strength with temperature are presented, and absolute strengths for absorptions of CH₄ in solid H₂O are estimated. Using the two largest (ν₃+ν₄) and (ν₁+ν₄) near-IR absorptions of CH₄ at 2.324 and 2.377 μm (4303 and 4207 cm⁻¹), respectively, as examples, we show that peaks of CH₄ in solid H₂O are at slightly shorter wavelength (higher frequency) and broader than those of pure solid CH₄. With increasing temperature, these peaks shift to higher frequency and become increasingly broad, but this trend is reversible on re-cooling, even though the phase transitions of H₂O are irreversible. It is to be hoped that these observations of changes in the positions, profiles, and relative intensities of CH₄ absorptions with concentration and temperature will be of use in understanding spectra of icy outer Solar System bodies.     

Flowing afterglow studies of temperature dependencies for electron dissociative recombination of HCNH, CH3CNH and CH3CH2CNH and their symmetrical proton-bound dimers

A study has been made using a variable temperature flowing afterglow Langmuir probe technique (VT-FALP) to determine the equilibrium temperature dependencies of the dissociative electron-ion recombination of the protonated cyanide ions (RCNH⁺, where R=H, CH₃ and C₂H₅) and their symmetrical proton-bound dimers (RCNH⁺NCR). The power law temperature dependencies of the recombination coefficients, α_e, over the temperature range 180 to 600 K for the protonated ions are α_e(T)(cm³ s⁻¹)=3.5±0.5×10⁻⁷ (300/T)^1.38 for HCNH⁺, α_e(T)=3.4±0.5×10⁻⁷ (300/T)^1.03 for CH₃CNH⁺, and α_e(T)=4.6±0.7×10⁻⁷ (300/T)^0.81 for CH₃CH₂CNH⁺. The equivalent values for the proton-bound dimers are α_e(T)(cm³ s⁻¹)=2.4±0.4×10⁻⁶(300/T)^0.5 for (HCN)₂H⁺ to α_e(T)=2.8±0.4×10⁻⁶(300/T)^0.5 for (CH₃CN)₂H⁺, and α_e(T)=2.3±0.3×10⁻⁶(300/T)^0.5 for (CH₃CH₂CN)₂H⁺. The relevance of these data to molecular synthesis in the interstellar medium and the Titan ionosphere are discussed.     

Organic astrochemistry: observations of interstellar ketene

We have observed emission from both ortho and para spin states of ketene (CH₂CO) towards several deeply-embedded protostars. The low CH₂CO fractional abundances (∼10⁻¹⁰) and the rotation temperatures (∼20 K) are consistent with emission from the cooler envelope. We compare our results with previous studies and discuss possible production pathways to interstellar ketene. We suggest that, if low observed excitation temperatures of CH₂CO, CH₃CHO and H₂CO are indicative of their absence from the hot core region, then this may be due to the extensive hydrogenation of pre-existing grain mantles prior to evaporation into the inner envelope, leading to lower abundances of these compounds and to mantles rich in alcohols.     

Chemical effects of H2 formation excitation

The effects of the production on dust grain surfaces of molecular hydrogen in excited states have been investigated. On the assumption that all of the H₂ formed on the surface of grains has a sufficient level of excitation too vercome the energy barriers in the formation reactions for the important OH and CH⁺ radicals, we consider the likely abundances of excited H₂ (H₂ ^*), OH and CH⁺ in various situations. Two different models are employed; the first links the H₂ ^* abundance directly to that of H₂ using a steady-state approximation, whilst the second considers the time-dependence of H₂ ^*. The second model is applied to gas that has been subjected to a strong isothermal shock (specifically, the shock-induced collapse of a diffuse cloud), which results in an extreme (high density, high atomic hydrogen abundance) environment. In general, it is found that the presence of the excited H₂ has only marginal effects on the chemistry of interstellar clouds. However, in the isothermal shock model, the abundances of CH⁺ are significantly enhanced, but only on short timescales, whilst the effects on the OH abundances are smaller, but last longer. We conclude that other than in such exceptional environments there are no obvious chemical signatures of the formation of H₂ ^*. This revised version was published online in July 2006 with corrections to the Cover Date.     

A study of the 3ν3CH4 region in a high-resolution spectrum of Jupiter recorded by Fourier transform spectroscopy

A spectrum of Jupiter between 6000 and 12 000 cm^? at high resolution (0.05 cm^?) was recorded with a Michelson interferometer at Palomar Mountain in October 1974. An analysis of the R branch of the 3ν₃CH₄ band with the reflecting-layer model, taking into account the H₂ absorption which occurs in the same spectral range, leads to a Lorentzian half-width of 0.09 ± 0.02 cm^?1, a rotational temperature of 175 ± 10° K, and a CH₄ abundance of order 52m atm. Five lines of the ¹³CH₄3ν₃ band have been identified; a comparison with new laboratory spectra indicates that the ¹³CH₄/¹²CH₄ ratio in the Jupiter atmosphere is close to the terrestrial ratio.     

The lower ionosphere of Titan

Ionization of the atmosphere of Titan by galactic cosmic rays is a very significant process throughout the altitude range of 100 to 400 km. An approximate form of the Boltzmann equation for cosmic ray transport has been used to obtain local ionization rates. Models of both ion and neutral chemistry have been employed to compute electron and ion density profiles for three different values of the H₂/CH₄ abundance ratio. The peak electron density is of the order 10³ cm^?3. The most abundant positive ions are C₂H₉⁺ and C₃H₉⁺, while the predicted densities of the negative ions H^? and CH₃^? are very small (<10^?4 that of the positive ions). It is suggested that inclusion of the ion chemistry is important in the computation of the H and CH₃ density profiles in the lower ionosphere.     

Ion-ion mutual neutralization and ion-neutral switching reactions of some stratospheric ions

Following the recent mass spectrometric observations of the ambient stratospheric positive and negative ions we have carried out co-ordinated laboratory experiments using a selected ion flow tube apparatus and a flowing afterglow apparatus for the following purposes: (i) to consider whether CH₃CN is a viable candidate molecule for the species X in the observed stratospheric ion series H⁺ (H₂O_n (X)_m and (ii) to determine the binary mutual neutralization rate coefficients α_i for the reactions ofH⁺ (H₂O₄ and H⁺(H₂O)(CH₃CN)₃ with several of the negative ion species observed in the stratosphere. We conclude from (i) that CH₃CN is indeed a viable candidate for X and from (ii) that the α_i for stratospheric ions are within the limited range (5–6) × 10^?8 cm³ s^?1.     

The spectra of Uranus and Neptune at 8–14 and 17–23 μm

An array spectrometer was used on the nights of 1985 May 30–June 1 to observe the disks of Uranus and Neptune in the spectral regions 7–14 and 17–23 μm with effective resolution elements ranging from 0.23 to 0.87 μm. In the long-wavelength region, the spectra are relatively smooth with the broad S(1) H₂ collision-induced rotation line showing strong emission for Neptune. In the short-wavelength spectrum of Uranus, an emission feature attributable to C₂H₂ with a maximum stratospheric mixing ratio of 9 × 10⁻⁹ is apparent. An upper limit of 2 × 10⁻⁸ is placed on the maximum stratospheric mixing ratio of C₂H₆. The spectrum of Uranus is otherwise smooth and quantitatively consistent with the opacity provided by H₂ collision-induced absorption and spectrally continuous stratospheric emission, as would be produced by aerosols. Upper limits to detecting the planet near 8 μm indicate a CH₄ stratospheric mixing ratio of 1 × 10⁻⁵ or less, below a value consistent with saturation equilibrium at the temperature minimum. In the short-wavelength spectrum of Neptune, strong emission features of CH₄ and C₂H₆ are evident and are consistent with local saturation equilibrium with maximum stratospheric mixing ratios of 0.02 and 6 × 10⁻⁶, respectively. Emission at 8–10 μm is most consistent with a [CH₃D]/[CH₄] volume abundance ratio of 5 × 10⁻⁵. The spectrum of Neptune near 13.5 μm is consistent with emission by stratospheric C₂H₂ in local saturation equilibrium and a maximum mixing ratio of 9 × 10⁻⁷. Radiance detected near 10.5 μm could be attributed to stratospheric C₂H₄ emission for a maximum mixing ratio of approximately 3 × 10⁻⁹. Quantitative results are considered preliminary, as some absolute radiance differences are noted with respect to earlier observations with discrete filters.