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Discovery of the radical cations of van der Waals complexes and their stepwise photoinduced reactions

Research Project

Project/Area Number 02453017
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 構造化学
Research InstitutionKyoto University

Principal Investigator

SHIDA T  Kyoto University, Department of Chemistry, Professor, 理学部, 教授 (60025484)

Co-Investigator(Kenkyū-buntansha) MOMOSE T  Kyoto University, Department of Chemistry, Assistant, 理学部, 助手 (10200354)
KATO T  Kyoto University, Department of Chemistry, Assistant, 理学部, 助手 (80175702)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥4,900,000 (Direct Cost: ¥4,900,000)
Keywordsvan der Waals complex / Radical ion / Photoisomerization / Benzene / Ethylene / Octatetraene / Freon / Multiphoton ionization / ビシクロオクタジエン / ガンマ-線照射 / 電荷移動
Research Abstract

Studies of molecular ions of van der waals (vdW) complexes in the gas phase are being developed with the advent of the free-jet expansion and the multiphoton ionization techniques. However, in condensed phase the corresponding study is scarce. In this research project some radical cations of vdW molecules in rigid solutions are newly found and their stepwise photoincduced reactions are studied. In particular, the system of benzene-ethylene in Freon matrices is studied extensively to find that the ionized binary complex exhibits a strong charge-transfer band at about 1-2eV. Photoexcitation of the ionized system leads to the valence isomerization to the radical cation of octatetraene. The result indicates that ionization of binary complexes enhances the chemical reactivity greatly. With the increase of the concentration of ethylene another product of the composition of C_<10>H_<14> is also found.
The present work should be regarded as a pilot study for the future study in the gas phase which is anticipated with the development of short wavelength laser technology.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (32 results)

All Other

All Publications (32 results)

  • [Publications] Tsujii,Y: "Studies of conformation and electronic structure of the radical cations of 2,4-di(N-carbazolyl)pentane・・・" J.Phys.Chem.95. 8635-8640 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Fujisaka,Y: "Novel photochemical reactions of C_8H_<10> radical cations" J.Phys.Chem.(1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Matsushita,M: "Novel organic ions of high-spin states.II.Determination of the spin multiplicity of the ground state and H-ENDOR study of the monoanion of PBPM" J.Amer.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Shinohara,H: "Encapsulation of scandium trimer in fullerenes" Nature.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kawashima,H: "Vibronic quantum beats in on-resonance pump-probe experiments" J.Chem.Phys.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Matsushita,M: "ESR studies of the radical cation of methane at 4-11K:Analysis of tunneling" J.Chem.Phys.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kuchitsu,K.,Ed.: "Dynamics of excited molecules" Elsevier Science Publishers, ca.300 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] 梶本 興亜編: "クラスタ-の化学" 培風館, 305 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsujii, Y: "Studies of conformation and electronic structure of the radical cations of 2, 4-di (N-carbazolyl) pentane." J. Phys. Chem. 95. 8635-8640 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Fujisaka, Y: "Novel photochemical reactions of C_8H_<10> radical cations" J. Phys. Chem.(1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Matsushita, M: "Novel organic ions of high-spin States. II. Determination of the spin multiplicity of ground state and H-ENDOR study of the monoanion of PBPM." J. Amer. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Shinohara, H: "Encapsulation of scandium trimer in fullerenes" Nature.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kawashima, H: "Vibronic quantum beats in on-resonance pump-probe experiments" J. Chem. Phys.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Matsushita, M: "ESR studies of the radical cation of methane at 4-11K : Analysis of tunneling" J. Chem. Phys.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kuchitsu, K., Ed.: "Elsevier Science Publishers" Dynamics of excited molecules. ca. 300. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Kazimoto, O., Ed.: "Chemistry of Clusters" Baifu-Kan.305. (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Tsujii,Y: "Studies of conformation and electronic structure of the radical cations of 2,4ーdi(Nーcarbazolyl)pentane…" J.Phys.Chem.95. 8635-8640 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Fujisaka,Y: "Novel photochemical reactions of C_8H_<10>radical cations" J.Phys.Chem.(1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] Matsushita,M: "Novel organic ions of highーspin states.II.Determination of the spin multiplicity of the ground state and HーENDOR study of the monoanion of PBPM" J.Amer.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] Shinohara,H: "Encapsulation of scandium trimer in fullerenes" Nature.

    • Related Report
      1991 Annual Research Report
  • [Publications] Kawashima,H: "Vibronic quantum beats in onーresonace pumpーprobe experiments" J.Chem.Phys.

    • Related Report
      1991 Annual Research Report
  • [Publications] Matsushita,M: "ESR studies of the radical cation of methane at 4ー11K:Analysis of tunneling" J.Chem.Phys.

    • Related Report
      1991 Annual Research Report
  • [Publications] Kuchitsu,K.,Ed.: "Dynamics of excited molecules" Elsevier Scienece Publishers, ca.300 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] 梶本 興亜編: "クラスタ-の化学" 培風館, 305 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] M.Yamaguchi: "Vibrational analysis and calculation of FranckーCondon factors for the vinoxy radical (CH_2CHO) X^^〜( ^2A^^¨) and B^^〜( ^2A^¨) states" J.Chem.Phys.93. 4211-4222 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Momose: "Calculation of hyperfine coupling cnstant by symmetry adapted cluster expansion cnfiguration interation theory.II.Anisotropic constants" J.Chem.phys.93. 7284-7292 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] L.B.Knight,Jr.: "Electron spin resenance studies of ^<12>CH_3F^+, ^<13>CH_3F^+ and ^<12>CH_2DF^+ in neon matrices at 4K;comparison with theoetial calculations" J.Chem.Phys.94. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Shida: "Photochemistry and spectroscory of organic ions and radicals" Annu.Rev.Phys.Chem.42. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Kato: "Electronic absorptin spectra of the radical ions of fullerenes;C_<60> and C_<70>" Chem.Phys.Lett. 何巻になるか目下不明. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Tsujii: "studies of cnfomation and electronic structure of the ralical cations of 2.4ーdi(Nーcarbazolyl)rentane and 1.3ーdinaphthalenes in fluids and in rigid matrices by optical spectroscopy and moleculas orbital analyses" J.Phys.Chem.何巻になるか目下不明.

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Shida: "Radical Ionic Systems" Kluwer Academic Publishers,Dordrecht, 496 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Shida: "Dynamics of Excited Molecules" Elsevier Science Publishers,Ams, 500 (1991)

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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