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The investigation on low-temperature tunneling reactions and its application

Research Project

Project/Area Number 14204058
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionUniversity of Yamanashi

Principal Investigator

HIRAOKA Kenzo  University of Yamanashi, Clean Energy Research Center, Professor, クリーンエネルギー研究センター, 教授 (80107218)

Co-Investigator(Kenkyū-buntansha) SATO Tetsuya  University of Yamanashi, Clean Energy Research Center, Associate Professor, クリーンエネルギー研究センター, 助教授 (60252011)
WADA Akira  University of Yamanashi, Clean Energy Research Center, Researcher, クリーンエネルギー研究センター, 研究員 (70377604)
曾越 宣仁  山梨大学, クリーンエネルギー研究センター, 博士研究員
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥44,850,000 (Direct Cost: ¥34,500,000、Indirect Cost: ¥10,350,000)
Fiscal Year 2004: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2003: ¥15,600,000 (Direct Cost: ¥12,000,000、Indirect Cost: ¥3,600,000)
Fiscal Year 2002: ¥24,050,000 (Direct Cost: ¥18,500,000、Indirect Cost: ¥5,550,000)
Keywordslow-temperature tunneling reaction / methanol / formaldyhyde / dark cloud / chemical evolution / silicon / electron impact / 水素原子 / トンネル反応 / 薄膜半導体 / シリコン薄膜 / FT-IR
Research Abstract

Light essentially cannot penetrate dense interstellar clouds, and the temperature inside dark clouds is kept at about 10K. More than 120 interstellar molecules have been observed by millimeter and submillimeter spectroscopy in such dark clouds. It is becoming increasingly clear that gas-phase ion-molecule reactions-the dominant processes in diffuse interstellar clouds-are less important in dense clouds. Instead, chemical reactions on cosmic dust grains play an important role. Interstellar ices, which grow on solid dust particles in cold, dense clouds also become the substrates for various chemical reactions. Recently, Infrared Space Observatory (ISO) has provided much information about interstellar and cometary ices.
Unfortunately, direct observations of the solid-phase chemistry of dense clouds are difficult to come by. In the absence of direct evidence, we have to resort to laboratory studies. A wealth of data has been gathered on gas-phase ion-molecule reactions, but investigations o … More n solid-phase reactions of various molecules remain scarce, although there have been experimental studies of molecular hydrogen formation on the surface of comic dust analogs.
In this work, the simulation of the formation of interstellar molecules on cold dust grains at -10K has been made. Formaldehyde and methanol are among the most complex molecules for which the successive H-atom addition reactions have been proposed : CO→HCO→H_2CO→CH_3O→CH_3OH. In the reaction of H with solid CO film, we found a very small yield of H_2CO with no CH_3OH detected as a reaction product. This strongly suggests that there must be some another source for the formation of ubiquitous CH_3OH in the universe, e.g., cosmic ray, UV, etc. In order to solve the methanol paradox, the H_2O ice film containing a small amount of CH_4 was irradiated by 50-300 eV electron beam at 10K. It was found that methanol was formed at the very early stage of the electron irradiation as a major product with an exceptionally high yield. This result clearly indicates that the cosmic ray plays a very important role for the formation of interstellar molecules.
The reactions of H and D atoms with solid formaldehyde and methanol were also investigated in detail at -10K. From the reaction of H with solid H_2CO at 10K, CO, CH_3OH and paraformaldehyde (polyoxymethylene) were the major products with the yields of about 1% or less. The yields of these products decrease steeply with an increase of temperature and they become negligible at -25K. From the reaction of D with solid H_2CO at 10K, CO, HDCO, CH_2DOD, and paraformaldehyde were formed. The branching ratio of reaction [D+HCO→CO+HD] to [D+HCO→HDCO] was measured to be about 1:6. The ratio of the yield of CH_3OH from reaction [H+H_2CO] to that of CH_2DOD from reaction [D+H_2CO] is 7:1, i.e., a marked isotope effect on the addition reaction of H and D to H_2CO. In the reaction of H and D with CH_3OH, H_2CO was not detected as a reaction product. Less

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (29 results)

All 2005 2004 Other

All Journal Article (13 results) Book (2 results) Publications (14 results)

  • [Journal Article] The reactions of H and D atoms with the thin films of formaldehyde and methanol at cryogenic temperature2005

    • Author(s)
      K.Hiraoka, A.Wada, H.Kitagawa, M.Kamo, H.Unagiike, T.Ueno
    • Journal Title

      Astrophysical Journal 620

      Pages: 542-551

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] The effect of the presence of foreign salts on the formation of gaseous ions for electrospray and laser spray2004

    • Author(s)
      K.Hiraoka, Y.Asakawa, Y.Kawashima
    • Journal Title

      Rapid Commun.Mass Spectrom. 18

      Pages: 2437-2442

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Selective dissociation of non-covalent bonds in biological; molecules by laser spray2004

    • Author(s)
      A.Takamizawa, Y.Itoh, K.Hiraoka
    • Journal Title

      Journal of Mass Spectrometry 39

      Pages: 1053-1058

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Atmospheric-pressure Penning ionization mass spectrometry2004

    • Author(s)
      K.Hiraoka, S.Fujimaki, H.Furuya
    • Journal Title

      Rapid Commun.Mass Spectrom. 18

      Pages: 2323-2330

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Laser spray : electric field-assisted matrix-assisted laser desorpt ion/ionization2004

    • Author(s)
      K.Hiraoka
    • Journal Title

      Journal of Mass Spectrometry 39

      Pages: 341-350

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Thermochemical stabilities and structures of the gas-phase cluster ions of halide ions with OCS2004

    • Author(s)
      K.Hiraoka, K.Fujita, M.Ishida
    • Journal Title

      Chem.Phys.Lett. 387

      Pages: 76-80

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Selective dissociation of non-covalent bonds in biological ; molecules by laser spray2004

    • Author(s)
      A.Takamizawa, Y.Itoh, K.Hiraoka
    • Journal Title

      Journal of Mass Spectrometry 39

      Pages: 1053-1058

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Atmospheric-pressure Penning ionization mass spectrometry2004

    • Author(s)
      Hiraoka, S.Yujimaki, H.Furuya
    • Journal Title

      Rapid Commun.Mass Spectrom. 18

      Pages: 2323-2330

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Laser spray : electric field-assisted matrix-assisted laser desorntion/ionization2004

    • Author(s)
      K.Hiraoka
    • Journal Title

      Journal of Mass Spectrometry 39

      Pages: 341-350

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Production of interstekkar molecules and amorphous semiconductors by atom funneling reactions2004

    • Author(s)
      T.Miyazaki (K.Hiraoka)
    • Journal Title

      Atom Tunneling Phenomena in Physics, Chemistry and Biology (Springer) 313

      Pages: 173-199

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The effect of the presence of foreign salts on the formation of gaseous ions for electrospray and laser spray2004

    • Author(s)
      K.Hiraoka, Y.Asakawa, Y.Kawashima
    • Journal Title

      Rapid Commun. Mass Spectrom. 18

      Pages: 2437-2442

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Atmospheric-pressure Penning ionization mass spectrometry2004

    • Author(s)
      K.Hiraoka, S.Fujimaki, H.Furuya
    • Journal Title

      Rapid Commun. Mass Spectrom. 18

      Pages: 2323-2330

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Laser spray: electric field-assisted matrix-assisted laser desorption/ionization2004

    • Author(s)
      K.Hiraoka
    • Journal Title

      Journal of Mass Spectrometry 39

    • Related Report
      2004 Annual Research Report
  • [Book] Atom Tunneling Phenomena in Physics, Chemistry and Biology (Production of Interstellar Molecules and Amorphous Semiconductors by Atom Tunneling Reactions)2004

    • Author(s)
      T.Miyazaki, (K.Hiraoka)
    • Publisher
      Springer
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] Atom Tunneling Phenomena in Physics, Chemistry and Biology (Production of Interstellar Molecules and Amorphous Semiconductors by Atom Tunneling Reactions)2004

    • Author(s)
      T.Miyazaki, K.Hiraoka
    • Publisher
      Springer
    • Related Report
      2004 Annual Research Report
  • [Publications] K.Hiraoka, K.Takao, F.Nakagawa: "Thermochemical stabilities of the gas-phase cluster ions H_3C^+(N_2)_n"Int.J.Mass Spectrom.. 227. 391-399 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, T.Shoda, I.Kudaka: "Gas-phase study of the clustering reactions of C_2H_5^+, s-C_3H_7^+ and t-C_4H_9^+ with CO_2 and N_2O : isomeric structure of C_2H_5^+"J.Phys.Chem.A. 107. 775-781 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, T.Mizuno, D.Eguchi: "Gas-phase ion/molecule reactions in octafluorocyclobutane"J.Chem.Phys.. 116. 7574-7582 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, R.Hamamoto, K.Mori: "Secondary ions produced by 400eV He^+ ion impact on solid films composed of binary mixtures of Ar/Xe, Ar/N_2, and Ar/O_2 at 7 K"Int.J.Mass Spectrom.. 218. 173-180 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, S.Sato: "Formation of formaldehyde by the tunneling reaction of the H with solid CO at 10K revisited"Astrophysical J.. 577. 265-270 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, M.Watanabe: "Secondary ions produced by 400 eV He^+ ion impact on N_2 and O_2 thin films at 8 K"J.Chem.Phys.. 117. 6252-6258 (2002)

    • Related Report
      2003 Annual Research Report
  • [Publications] Kenzo Hiraoka: "Atom Tunneling Phenomena in Physics, Chemistry, and Biology"Springer. 27 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, S.Sato, N.Sogoshi: "Formation of formaldehyde by the tunneling reactions of H with solid CO at 10K revisited"Astrophysical Journal. 577. 265-270 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, S.Sato, N.Sogoshi: "Study on the tunneling reaction of H atoms with a sold thin film of C_3H_6 at 10K"Journal of Physical Chemistry B. 106. 4974-4978 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 平岡賢三: "宇宙における化学進化の謎を解く:低温ほど速く進むトンネル反応"化学と教育. 50. 9-13 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, S.Sato, S.Hishiki: "Formation of amorphous silicon by the low-temperature tunneling reaction of H atoms with solid the films SiH4 at 10K"Journal of Physical Chemistry B. 105. 6950-6955 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Hiraoka, T.Sato, T.Takayama: "Tunneling reactions in interstellar ices"Science. 292. 869-870 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] 平岡賢三: "極低温トンネル反応による薄膜半導体合成"放射線化学. 72. 19-24 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Hiraoka: "Atom Tunneling Phenomena in Physics, Chemistry, and Biology"Springer. 330 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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