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Fundamental processes of tunneling reaction

Research Project

Project/Area Number 08240105
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionNagoya University

Principal Investigator

MIYAZAKI Tetsuo  Nagoya Univ., School of Eng., Prof., 工学研究科, 教授 (90023126)

Co-Investigator(Kenkyū-buntansha) ARATONO Yasuyuki  Japan Atomic Energy Res. Inst., Senior Researcher, 先端基礎研究センター, 主任研究員
NAKAMURA Hiroki  Inst. Molecular Science, Prof., 分子科学研究所, 教授 (10010935)
SHIOTANI Masaru  Hiroshima Univ., School of Eng., Prof., 工学部, 教授 (80002137)
駒口 健治  広島大学, 工学部, 助手 (80291483)
長谷 博友  京都大学, 原子炉実験所, 教授 (20027460)
Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥69,800,000 (Direct Cost: ¥69,800,000)
Fiscal Year 1998: ¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 1997: ¥7,700,000 (Direct Cost: ¥7,700,000)
Fiscal Year 1996: ¥54,500,000 (Direct Cost: ¥54,500,000)
KeywordsTunneling reaction / Solid hydrogen / Tunneling displacement / Quantum effects / Nonadiabatic transition / Chemical reaction dynamics / Tritium / Reaction in cells / トンネル反応 / 固体水素 / 非断熱遷移 / 核スピン一回転状態結合 / 原子バブル / 銀ニ量体カチオン / ファンデルワールス錯体 / ビタミンC / 量子拡散 / ESR / 分子内トンネル / 多次元トンネル / トリチウム / 液体ヘリウム / トンネル効果 / 非断熱トンネル / 反応動力学
Research Abstract

The detailed mechanism of a tunneling reaction has not been studied previously. Here the several factors that control a tunneling reaction have been elucidated at ultralow temperature. The selective reaction caused by tunneling is presented in solid hydrocarbon. It is also shown that a tunneling reaction of vitamin C and long-1ived radicals in γ-irradiated cells is related to suppression of cancer.
The temperature dependent ESR spectra of partially deuteriated cyclohexane radical cations were successfully analyzed in terms of dynamical averaging due to a tunneling displacement among the Jahn-Teller distorted C2h structures with different zero-point vibration energies. Furthermore, quantum effects of nuclear spin-rotation coupling were demonstrated for selectively deuteriated methyl radicals in low temperature argon matrix.
Hydrogen atom transfer chemical reactions have been successfully conceptualized as vibrationally nonadiabatic transitions in the vicinity of potential ridge. New control scheme of molecular processes by time-dependent external fields has been proposed.
Tunneling abstraction reaction of tritium(T), which is the heaviest hydrogen isotope, with isotopic hydrogen molecules was observed for the first time. It was proposed that the recombination of T and H proceeds through their bubble states in the liquid helium, which is the typical quantum liquid.

Report

(4 results)
  • 1999 Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] T.Miyazaki et al.: "Quantum tunneling of D(H) atoms and H2- anions m solid hydrogen"J.Low Temp. Phys. 111. 453-461 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Miyazaki et al.: "Tunneling reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells"Radiat. Phys. Chem. 49. 547-551 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Shiotani et al.: "High resolution EPR and quantum effects on CH_3, CH_2D, CHD_2 and CD_3 radicals under argon-matrix isolation conditions"J.Phys. Chem. A. 103. 4823-4829 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Shiotani et al.: "Asymmetrically distorted structure, selective bond length alternation and reactions of radical cations of silacyclohexanes"J.Phys. Chem. A. 101. 6983-6990 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Nakamura et al.: "Cumulative reaction probability without absorbing potentials"Phys. Rev. Lett. 80. 41-44 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y.Aratono et al.: "Tunneling abstraction reactions o tritium atoms with HD in superfluid ^3He-^4He media at 1.3 K"

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Miyazaki et al.: "Quantum tunneling of D(H) atoms and HィイD3-(/)2ィエD3 anions in solid hydrogen"J. Low Temp. Phys.. 111. 453-461 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Miyazaki et al.: "Tunneling reaction of long-lived radicals and vitamin C in γ-irradiated mammalian cells"Radiat. Phys. Chem.. 49. 547-551 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Shiotani et al.: "High resolution EPR and quantum effects on CHィイD23ィエD2, CHィイD22ィエD2D, CHDィイD22ィエD2 and CDィイD23ィエD2 radicals under argon-matrix isolation conditions"J. Phys. Chem. A. 103. 4823-4829 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M. Shiotani et al.: "Asymmetrically distorted structure, selective bond length alternation and reactions of radical cations of silacyclohexanes"J. Phys. Chem. A. 101. 6983-6990 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Nakamura et al.: "Cumulative reaction probability without absorbing potential"Phys. Rev. Lett.. 80. 41-44 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Y. Aratono et al.: "Tunneling abstraction reactions of tritium atoms with HD in superfluid ィイD13ィエD1He-ィイD14ィエD1He media at 1.3 K"J. Phys. Chem. A. 102. 1501-1506 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Miyazaki: "Quantum tunneling of D(H)atoms and H_2 anions in solid hydrogen" J.Low Temp.Phys.111. 453-461 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] P.Wang: "Structure and dynamics of radical cations of selectively deuteriated cyclohexanes" Chem.Phys.Lett.292. 110-114 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Teranishi: "Control of time-dependent nonadiabatic processes by an external field" Phys.Rev.Lett.81. 2032-2035 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Miyatake: "Emission characteristics of silver atoms in irradiated organic solid solutions at 77 K" J.Phys.Chem.102. 8389-8394 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Komaguchi: "H atom-H_2 molecule van der Waals complexes in solid argon matrix by high-resolution ESR spectroscopy" Chem.Phys.Lett.300. 257-261 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] S.Koyama: "Radiation-induced long-lived radicals which cause mutation and transformation" Mutation Res.421. 45-54 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Kumada: "Decay Behaviors of H_2^- anions in solid parahydrogen" J.Phys.Chem.101. 1198-1201 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Miyazaki: "New temperature effect on tunneling reaction in hydrogen,alkane and ethanol in the solid phase" Radiat.Phys.Chem.50. 523-526 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Komaguchi: "An ESR study of trimethylenemethane radical cation" Chem.Phys.Letters. 265. 217-223 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Komaguchi: "Asymmetrically distorted structure,selective bond length alternation and reactions of radical cations of silacyclohexanes" J.Phys.Chem.101. 6983-6990 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] C.Zhu: "Semiclassical theory of multi-channel curve crossing problems:Nonadiabatic tunneling case" J.Chem.Phys.107. 7839-7848 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Aratono: "Tunneling abstraction reactions of tritium atoms with HD and with mixtures of H_2 and D_2 in ^3He-^4He media at 1.3K" J.Phys.Chem.102. 1501-1505 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Kumada: "A Remarkable Temperature Dependence of Rate Constant for Tunneling Reaction HD+D→H+D_2 at 2.6-6.5K" Chem.Phys.Letters. 261. 463-466 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Matsumoto: "Reaction of Long-lived Radicals and Vitamin C in Mammalian Cells.Tunneling Reaction in Biological System." Radiat.Phys.Chem.(in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Komaguchi: "An ESR Study of Trimethylenemethane Radical Cation" Chem.Phys.Letters. (in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] V.I.Osherov: "Quantum Mechanically Exact Analytical Solutions of a Two-state Exponential Model" J.Chem.Phys.105. 2770-2779 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Nobusada: "Quantum Dynamics of O(3P)+HCl+C1 : Effects of Reagent Rotational Excitation" Faraday Transaction. (in press). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] T.Kumada: "Time Evolution of Rate Constant for Tunneling Reaction H_2+D→H+HD in Solid Hydrogen" Chem.Phys.212. 177-182 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2019-02-15  

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