Synthesis of complex organic molecules in simulated methane rich astrophysical ices.

It has been proposed that organic molecules required for life on earth may be formed by the radiation processing of molecular ices in space environments, e.g., within our solar system. Such processes can be studied in the laboratory with surface science analytical techniques and by using low-energy electron (LEE) irradiation to simulate the effects of the secondary electrons that are generated in great abundance whenever ionizing radiation interacts with matter. Here we present new measurements of 70 eV LEE irradiation of multilayer films of CH4, 18O2, and CH4/18O2 mixtures (3:1 ratio) at 22 K. The electron stimulated desorption (ESD) yields of cations and anions have been recorded as a function of electron fluence. At low fluence, the prompt desorption of more massive multi-carbon or C-O containing cationic fragments agrees with our earlier measurements. However, new anion ESD signals of C2-, C2H-, and C2H2- from CH4/18O2 mixtures increase with fluence, indicating the gradual synthesis (and subsequent electron-induced fragmentation) of new, more complex species containing several C and possibly O atoms. Comparisons between the temperature programed desorption (TPD) mass spectra of irradiated and unirradiated films show the electron-induced formation of new chemical species, the identities of which are confirmed by reference to the NIST database of electron impact mass spectra and by TPD measurements of films composed of the proposed products. New species observed in the TPD of irradiated mixture films include C3H6, C2H5OH, and C2H6. Furthermore, X-ray photoelectron spectroscopy of irradiated films confirms the formation of C-O, C=O, and O=C-O- bonds of newly formed molecules. Our experiments support the view that secondary LEEs produced by ionizing radiation drive the chemistry in irradiated ices in space, irrespective of the radiation type.

[1]  L. Sanche Transmission of 0–15 eV monoenergetic electrons through thin‐film molecular solids , 1979 .

[2]  A. Domaracka,et al.  Cosmic ray impact on astrophysical ices: laboratory studies on heavy ion irradiation of methane , 2011 .

[3]  David A. Williams,et al.  The molecular universe , 2002 .

[4]  D. Diesing,et al.  Thermal desorption spectroscopy from the surfaces of metal-oxide-semiconductor nanostructures. , 2014, The Review of scientific instruments.

[5]  M. Huels,et al.  Substrate dependence of electron‐stimulated O− yields from dissociative electron attachment to physisorbed O2 , 1994 .

[6]  M. Huels,et al.  Small steps on the slippery road to life , 2008 .

[7]  Theodore E. Madey,et al.  Electron-Stimulated Desorption as a Tool for Studies of Chemisorption: A Review , 1971 .

[8]  F. Dorman Negative Fragment Ions from Resonance Capture Processes , 1966 .

[9]  S. Pimblott,et al.  Production of low-energy electrons by ionizing radiation , 2007 .

[10]  P. Cloutier,et al.  Dissociative attachment reactions in electron stimulated desorption from condensed O2 and O2‐doped rare‐gas matrices , 1989 .

[11]  G. Bader,et al.  Elastic and inelastic mean-free-path determination in solid xenon from electron transmission experiments , 1982 .

[12]  K. Wilson,et al.  A Fast XPS study of the surface chemistry of ethanol over Pt{1 1 1} , 2004 .

[13]  M. Huels,et al.  Halogen anion formation in 5-halouracil films: X rays compared to subionization electrons. , 1999, Radiation research.

[14]  M. Allan,et al.  Electron-induced chemistry of alcohols , 2008 .

[15]  A. Burton,et al.  Understanding Prebiotic Chemistry Through the Analysis of Extraterrestrial Amino Acids and Nucleobases in Meteorites , 2012 .

[16]  John R. Spencer,et al.  Charge‐coupled device spectra of the Galilean satellites: Molecular oxygen on Ganymede , 1995 .

[17]  Neal J. Evans,et al.  Discovery of interstellar methane - Observations of gaseous and solid CH4 absorption toward young stars in molecular clouds , 1991 .

[18]  J. L. Franklin,et al.  Endoergic ion—molecule-collision processes of negative ions. III. Collisions of I− on O2, CO, and CO2 , 1976 .

[19]  R. Kaiser,et al.  Application of Re fl ectron Time-of-Flight Mass Spectroscopy in the Analysis of Astrophysically Relevant Ices Exposed to Ionization Radiation : Methane ( CH 4 ) and D 4-Methane ( CD 4 ) as a Case Study , 2013 .

[20]  M. Spaans,et al.  The evolution of organic matter in space , 2011, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[21]  Christopher R. Arumainayagam,et al.  The Role of Low-Energy (≤ 20 eV) Electrons in Astrochemistry , 2016 .

[22]  Methane clathrates in the solar system. , 2015, Astrobiology.

[23]  K. Öberg Photochemistry and Astrochemistry: Photochemical Pathways to Interstellar Complex Organic Molecules. , 2016, Chemical reviews.

[24]  R. Kaiser,et al.  Application of Reflectron Time-of-Flight Mass Spectroscopy in the Analysis of Astrophysically Relevant Ices Exposed to Ionization Radiation: Methane (CH4) and D4-Methane (CD4) as a Case Study. , 2013, The journal of physical chemistry letters.

[25]  M. Allan,et al.  Selective cleavage of the C-O bonds in alcohols and asymmetric ethers by dissociative electron attachment. , 2009, Physical chemistry chemical physics : PCCP.

[26]  S. Lunell,et al.  Manifestation of the paramagnetic splitting of physisorbed O2 in core and valence spectroscopies , 1996 .

[27]  M. Allan,et al.  Selective cleavage of the C-O bonds in alcohols and asymmetric ethers by dissociative electron attachment , 2009 .

[28]  I. Ipolyi,et al.  Thermal desorption spectrometry for identification of products formed by electron-induced reactions , 2008 .

[29]  T. Orlando,et al.  Space-weathering of solar system bodies: a laboratory perspective. , 2013, Chemical reviews.

[30]  W. Calvin,et al.  Condensed O2 on Europa and Callisto , 2002 .

[31]  Hsiao-lu D. Lee,et al.  Low-energy electron-induced reactions in condensed matter , 2010 .

[32]  T. Märk,et al.  Formation of long-lived CO−2, N2O−, and their dimer anions, by electron attachment to van der waals clusters , 1986 .

[33]  The molecular universe , 2013 .

[34]  J. Jay-Gerin,et al.  A mechanism for the production of hydrogen peroxide and the hydroperoxyl radical on icy satellites by low-energy electrons , 2004 .

[35]  T. Madey,et al.  Electron stimulated desorption of anionic fragments from films of pure and electron-irradiated thiophene. , 2006, The Journal of chemical physics.

[36]  Paul A. Rowntree,et al.  Anion yields produced by low-energy electron impact on condensed hydrocarbon films , 1991 .

[37]  Thomas M. Orlando,et al.  Far-out surface science: radiation-induced surface processes in the solar system , 2002 .

[38]  H. Abdoul-Carime,et al.  D−, O− and OD− desorption induced by low-energy (0–20 eV) electron impact on amorphous D2O films , 2005 .

[39]  P. Swiderek,et al.  Control of chemical reactions and synthesis by low-energy electrons. , 2013, Chemical Society reviews.

[40]  R. Kaiser,et al.  Laboratory Studies on the Irradiation of Methane in Interstellar, Cometary, and Solar System Ices , 2006 .

[41]  Arnaud Belloche,et al.  Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M) , 2013, 1308.5062.

[42]  Everett Shock,et al.  The organic composition of carbonaceous meteorites: the evolutionary story ahead of biochemistry. , 2010, Cold Spring Harbor perspectives in biology.

[43]  E. Krishnakumar,et al.  Low Energy Electron Induced C–H Activation Reactions in Methane Containing Ices , 2017 .

[44]  Pascale Ehrenfreund,et al.  A voyage from dark clouds to the early Earth , 2000 .

[45]  L. Sanche,et al.  Reactions induced by low energy electrons in cryogenic films (Review) , 2003 .

[46]  Holger S. P. Müller,et al.  The Cologne Database for Molecular Spectroscopy, CDMS: a useful tool for astronomers and spectroscopists , 2005 .

[47]  M. Huels,et al.  Reactive scattering of O− in organic films at subionization collision energies , 1998 .

[48]  G. Leto,et al.  A comparison of ion irradiation and UV photolysis of CH4 and CH3OH , 2002 .

[49]  F. Weik,et al.  The effects of temperature and morphology on electron transmission and stimulated desorption of H− from thin hydrocarbon films , 2000 .

[50]  P. Rowntree,et al.  Electron stimulated desorption via dissociative attachment in amorphous H2O , 1991 .

[51]  Y. Yıldırım,et al.  Electron stimulated desorption of anions and cations from condensed allyl glycidyl ether. , 2010, Physical chemistry chemical physics : PCCP.