CARBONIC ACID AS A RESERVE OF CARBON DIOXIDE ON ICY MOONS: THE FORMATION OF CARBON DIOXIDE (CO2) IN A POLAR ENVIRONMENT

Carbon dioxide (CO{sub 2}) has been detected on the surface of several icy moons of Jupiter and Saturn via observation of the ν{sub 3} band with the Near-Infrared Mapping Spectrometer on board the Galileo spacecraft and the Visible-Infrared Mapping Spectrometer on board the Cassini spacecraft. Interestingly, the CO{sub 2} band for several of these moons exhibits a blueshift along with a broader profile than that seen in laboratory studies and other astrophysical environments. As such, numerous attempts have been made in order to clarify this abnormal behavior; however, it currently lacks an acceptable physical or chemical explanation. We present a rather surprising result pertaining to the synthesis of carbon dioxide in a polar environment. Here, carbonic acid was synthesized in a water (H{sub 2}O)-carbon dioxide (CO{sub 2}) (1:5) ice mixture exposed to ionizing radiation in the form of 5 keV electrons. The irradiated ice mixture was then annealed, producing pure carbonic acid which was then subsequently irradiated, recycling water and carbon dioxide. However, the observed carbon dioxide ν{sub 3} band matches almost exactly with that observed on Callisto; subsequent temperature program desorption studies reveal that carbon dioxide synthesized under these conditions remains in solid form until 160 K, i.e., themore » sublimation temperature of water. Consequently, our results suggest that carbon dioxide on Callisto as well as other icy moons is indeed complexed with water rationalizing the shift in peak frequency, broad profile, and the solid state existence on these relatively warm moons.« les

Cosmic-ray-mediated Formation of Benzene on the Surface of Saturn's Moon Titan

The aromatic benzene molecule (C_6H_6)—a central building block of polycyclic aromatic hydrocarbon molecules—is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C_2H_2) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two orders of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene

Preparation of methanediamine (CH2(NH2)2)—A precursor to nucleobases in the interstellar medium

Although methanediamine (CH2(NH2)2) has historically been the subject of theoretical scrutiny, it has never been isolated to date. Here, we report the preparation of methanediamine (CH2(NH2)2)—the simplest diamine. Low-temperature interstellar analog ices composed of ammonia and methylamine were exposed to energetic electrons which act as proxies for secondary electrons produced in the track of galactic cosmic rays. These experimental conditions, which simulate the conditions within cold molecular clouds, . result in radical formation and initiate aminomethyl (ĊH2NH2) and amino (NH2) radical chemistry. Exploiting tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReToF-MS) to make isomer-specific assignments, methanediamine was identified in the gas phase upon sublimation, while its isomer methylhydrazine (CH3NHNH2) was not observed. The molecular formula was confirmed to be CH6N2 through the use of isotopically labeled reactants. Methanediamine is the simplest molecule to contain the NCN moiety and could be a vital intermediate in the abiotic formation of heterocyclic and aromatic systems such as nucleobases, which all contain the NCN moiety

NEUTRAL-NEUTRAL REACTIONS IN THE INTERSTELLAR MEDIUM. I. FORMATION OF CARBON HYDRIDE RADICALS VIA REACTION OF CARBON ATOMS WITH UNSATURATED HYDROCARBONS

The reactions of ground-state atomic carbon with acetylene, C2H2 (1), methylacetylene, CH3CCH (2), ethylene, C2H4 (3), and propylene, C3H6 (4), are investigated at relative collision energies between 8.8 and 45 kJ mol-1 in crossed-beam experiments to elucidate the reaction products and chemical dynamics of atom-neutral encounters relevant to the formation of carbon-bearing molecules in the interstellar medium (ISM). Reactive scattering signal is found for C3H (1), as well as the hitherto unobserved interstellar radicals C4H3 (2), C3H3 (3), and C4H5 (4). All reactions proceed on the triplet surface via addition of the carbon atom to the molecular π-bond. The initial collision complexes undergo hydrogen migration (1/2) or ring opening (3/4) and decompose via C-H-bond rupture to l/c-C3H (1), n-C4H3 (2), propargyl (3), and methylpropargyl (4). The explicit identification of the carbon-hydrogen exchange channel under single collision conditions identifies this class of reaction as a potential pathway to carbon-bearing species in the ISM. Especially, the formation of l/c-C3H correlates with actual astronomical observations and explains a higher [c-C3H]/[l-C3H] ratio in the dark cloud TMC-1 as compared to the carbon star IRC +10216. Our findings strongly demand the incorporation of distinct structural isomers in prospective chemical models of interstellar clouds, hot cores, and circumstellar envelopes around carbon stars

Perchlorate formation on Mars through surface radiolysis‐initiated atmospheric chemistry: A potential mechanism

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4–). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one‐dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 × 107 molecules cm–2 s–1 sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.Key PointsMechanism initiated by radiolysis in the surface can potentially account for observed Martian perchlorate concentrationsInjection of oxides of chlorine from the surface into the atmosphere is potentially an effective way of forming perchloric acidMartian perchlorate is an important oxidant but poorly characterizedPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/134196/1/jgre20553.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/134196/2/jgre20553_am.pd

Untangling the Formation of Methoxymethanol (CH\u3csub\u3e3\u3c/sub\u3eOCH\u3csub\u3e2\u3c/sub\u3eOH) and Dimethyl Peroxide (CH\u3csub\u3e3\u3c/sub\u3eOOCH\u3csub\u3e3\u3c/sub\u3e) in Star-forming Regions

© 2019. The American Astronomical Society. All rights reserved.. Methoxymethanol (CH3OCH2OH) was recently detected toward the MM1 core in the high-mass star-forming region NGC 6334I. However, the underlying formation mechanisms of this complex organic molecule (COM) as well as its structural isomers ethylene glycol (HOCH2CH2OH) and the hitherto unobserved dimethyl peroxide (CH3OOCH3) are still elusive. Here, we report the very first confirmed synthesis of dimethyl peroxide - at various deuteration levels within interstellar analogous ices of D3-methanol (CD3OH) exposed to ionizing radiation at ultralow temperatures of 5 K. The discrimination of specific isomers is achieved by exploiting reflectron time-of-flight mass spectrometry coupled with isomer-selective photoionization of the subliming molecules in the temperature programmed desorption phase of the experiment. Based on the distribution of the identified species at distinct mass-to-charge ratios, we reveal primary and secondary reaction pathways to methoxymethanol, ethylene glycol, and dimethyl peroxide involving radical-radical recombination of methoxy (CH3O) and hydroxymethyl (CH2OH). Our findings help to constrain the formation mechanism of COMs detected within star-forming regions (methoxymethanol, ethylene glycol) and propose that the hitherto elusive dimethyl peroxide isomer represents an excellent candidate for future astronomical searches

A Unified Mechanism on the Formation of Acenes, Helicenes, and Phenacenes in the Gas Phase.

A unified low-temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes-polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho-condensed arrangements of fused benzene rings-is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas-phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer-selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free-radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry

Experimental identification of aminomethanol (NH2CH2OH)—the key intermediate in the Strecker Synthesis

The Strecker Synthesis of (a)chiral α-amino acids from simple organic compounds, such as ammonia (NH3), aldehydes (RCHO), and hydrogen cyanide (HCN) has been recognized as a viable route to amino acids on primordial earth. However, preparation and isolation of the simplest hemiaminal intermediate – the aminomethanol (NH2CH2OH)– formed in the Strecker Synthesis to even the simplest amino acid glycine (H2NCH2COOH) has been elusive. Here, we report the identification of aminomethanol prepared in low-temperature methylamine (CH3NH2) – oxygen (O2) ices upon exposure to energetic electrons. Isomer-selective photoionization time-of-flight mass spectrometry (PI-ReTOF-MS) facilitated the gas phase detection of aminomethanol during the temperature program desorption (TPD) phase of the reaction products. The preparation and observation of the key transient aminomethanol changes our perception of the synthetic pathways to amino acids and the unexpected kinetic stability in extreme environments