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Studies on Reaction Dynamics and Molecular Dynamics of Para magnetic Intermediates by Use of Pulsed FT-ESR Method

Research Project

Project/Area Number 02403003
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionOsaka University

Principal Investigator

KUWATA Keiji  Osaka University,Faculty of Science,Professor, 理学部, 教授 (50028099)

Co-Investigator(Kenkyū-buntansha) MURAI Hisao  Osaka University,Faculty of Science,Research Instructor, 理学部, 助手 (50142261)
KAMACHI Mikiharu  Osaka University,Faculty of Science,Professor, 理学部, 教授 (40028163)
笠井 俊夫  大阪大学, 理学部, 講師 (20152613)
Project Period (FY) 1990 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥20,000,000 (Direct Cost: ¥20,000,000)
Fiscal Year 1992: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥8,000,000 (Direct Cost: ¥8,000,000)
Fiscal Year 1990: ¥10,000,000 (Direct Cost: ¥10,000,000)
KeywordsPulsed FT-ESR / Para magnetic Intermediate / Process of Reaction Dynamics / Process of Molecular Dynamics / Short-Lived Reaction Intermediate / Electron Spin Relaxation / Dynamic Spin Polarization / ラジカル対 / パルスFTーESR / スピン分極の移動 / 短寿命中間体 / 励起三重項状態 / 磁場効果 / 電子スピン緩和時間 / CIDEP / 光化学反応中間体 / ラジカルイオン対 / 溶媒和電子 / 光解離反応中間体
Research Abstract

By use of a pulsed FT-ESR spectrometer, which has been built in 1990 for the studies on reaction dynamics and molecular dynamics of the short-lived free radical intermediates in chemical reaction, the intermediate states and the spin dynamics of photo reduction and photoxidation were investigated in 1992. And also studies on chemical kinetics of the initiation step of photo polymerization were carried out. 1) Time-resolved ESR studies of chemically induced electron spin polarization (CIDEP) in photosensitized reduction of maleic anhydride gave a new finding that the spin polarization is caused by ST-1 mixing in a geminate radical ion pair in the photoinduced electron transfer reaction. On the basis of the results of the studies on spin polarization in the systems with different donors and solvents reaction mechanisms were discussed in detail. 2) The structure and the reaction rates with vinyl monomers of the reactive fragments of several photoinitiators of polymerization were determine … More d. And the direct observation of the initiating radicals in photopolymerization was firstly succeeded. 3) A quasi-stable spin-correlated radical pair in an micellar system was investigated by time-resolved ESR spectroscopy. For the analysis of the external magnetic field effect on the decay rates of the radical pair stochastic Liouville calculation was carried out. 4) In the photoreaction of benzophenone in an alcoholic solution the electron spin relaxation processes of the short-lived intermediates in the reaction were investigated by pulsed FT-ESR spectroscopy. In this investigation new findings on the spin dynamics and reaction mechanisms were obtained. 5) The electron transfer reaction of the negative ions of p-quinone derivatives with neutral molecules and the electron spin exchange reaction between negative ions were investigated by pulsed FT-ESR spectroscopy in detail. The results of these investigations show the usefulness of pulsed FT-ESR spectroscopy for the investigation of molecular dynamics of short-lived reaction intermediates. Less

Report

(4 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • 1990 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] Hiasao Murai,Natsuo Ishiwata,Keiji Kuwata,Yoshio Sakaguchi,and Hisaharu Hayashi: "External Magnetic Field Effect Chemical Reactions of Quasi-Stable Radical Pairs in an SDS Micelle." Chemi.Phys.Letters.203. 482-486 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Natsuo Ishiwata,Hisao Murai,and Keiji Kuwata: "Time-Resolved ESR Study of Quasi-Stable Spin-Correlated Radical Pairs in SDS Micellar Systems." Res.Chem.Intermediates.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hisao Murai,Hidekatsu Honma,and Keiji Kuwata: "CIDEP Studies of Transient Radical-Ion Pair:Photooxidation of TMPD and Carbazoles" Zeit.Phys.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsushi Kajiwara,Yoshinari Konishi,Yotaro Morishima,Wolfram Schnabel,Keiji Kuwata,and Mikiharu Kamachi: "Time-Resolved Study on Radical Polymerization with 2,4,6-Trimethyl-benzoyl Diphenylphosphine Oxide(TMDPO)-Direct Estimation of Rate Constants for Addition Reactions of Diphentlphosohonyl Radical to Vinyl Monomers" Macromol.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hisao Murai,Hidekazu Honma,and Keiji Kuwata: "Novel Interactions in Radical-Ion Pairs:CIDEP Studies of Photo-Ionization and Photooxidation Reactions." Res.Chem.Intermediates.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hisao Murai, Natsuo Ishiwata, Keiji Kuwata, Yoshio Sakaguchi and Hisaharu Hayashi: "External Magnetic Field Effect upon Chemical Reactions of Quasi-Stable Radical Pairs in an SDS Micelle." Chemical Physics Letters. 203. 482-486 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Natsuo Ishiwata, Hisao Murai, and Keiji Kuwata: "Time-Resolved ESR Study of Quasi-Stable Spin Correlated Radical Pairs in SDS Micellar Systems." Res.Chem.Intermediates.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hisao Murai, Hidekatsu Honma, and Keiji Kuwata: "CIDEP Studies of Transient Radical-Ion Pair: Photooxidation of TMPD and Carbazoles." Zeit.Phys.Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Atsushi Kajiwara, Yoshinari Konishi,Yotaro Morishima, Wolfram Schnabel, Keiji Kuwata, and Mikiharu Kamachi: "Time-Resolved Study on Radical Polymerization with 2,4,6-Tri- methyl-benzoyl Diphenylphosephine Oxide (TMDPO) - Direct Estimation of Rate Constants for Addition Reactions of Diphenylphosphonyl Radical to Vinyl Monomers." Macromol.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hisao Murai, Hidekatsu Honma, and Keiji Kuwata: "Novel Interactions in radical-Ion Pairs: CIDEP Studies of Photo-Ionization and Photooxidation Reactions." Res.Chem.Intermediates.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Hiasao Murai,Natsuo Ishewata,Kenji Kuwata,Yoshio Sakaguchi,and Hisaharu Hayashi: "External Magnetic Field Effect upon Chemical Reactions of Quasi-Stable Radical Pairs in an SDS Micelle." Chemi.Phys.Letters.203. 482-486 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Natsuo Ishiwata,Hisao Murai,Keiji Kuwata: "Time-Resolved ESR Study of Quasi-Stable Spin-Correlated Radical Pairs in SDS Micellar Systems." Res.Chem.Intermediates.

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisao Murai,Hidekatsu Honma,and Keiji Kuwata: "CIDEP Studies of Transient Radical-Ion Pair:Photooxidation of TMPD and Carbazoles" Zeit.Phys.Chem.

    • Related Report
      1992 Annual Research Report
  • [Publications] Atsushi Kajiwara,Yoshinari Konishi,Yotaro Morishima,Wolfram Schnabel,Keiji Kuwata,and Mikiharu Kamachi: "Time-Resolved Study on Radical Polymerization with 2,4,6-Trimethylbenzoyl Diphenylphosphine Oxide(TMDPO)-Direct Estimation of Rate Constants for Addition Reactions of DiphentlPhosphonyl Radical to Vinyl Monomers" Macromol.

    • Related Report
      1992 Annual Research Report
  • [Publications] Hisao Murai,Hidekazu Honma,and Keiji Kueata: "Novel Interactions in Radical-Ion Pairs:CIDEP Studies of Photo-Ionization and Photooxidation Reactions." Res.Chem.Intermediates.

    • Related Report
      1992 Annual Research Report
  • [Publications] H.Murai: "CIDEP Study of Photreduction of Xanthone in Alcohols:Novel Irdirect Hydrogen Abstrction Steps." J.Phys.Chem.95. 6247-6248 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Tajima: "The Photolysis of Acylphosphine Oxides lV." Photochem.Photobiol.A:Chem.58. 239-251 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Ohara: "TimeーResolved ESR Studies on Photosensitized Reaction of Maleic Anhydride in Alcohols:Memory Transfer in SpinーAdduct Formation." Bull.Chem.Soc.Japan. 65. NO.6 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] A.Hanazaki: "Photosensitized Triplet State of 1,3ーcyclodienes Detected by a TimeーResolved ESR Method." Chem.Phys.Letters. (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] H.Honma: "CIDEP Study on Photooxidation of N,N,N^',N^'ーtetramethylーpーphenylenーdiamine by Maleic Anhydride." Chem.Phys.Letters.

    • Related Report
      1991 Annual Research Report
  • [Publications] Hidetada Tokioka: "Pulsed ESR Study on Electron Spin Relaxation of Intermediates in Photoreduction of 2,6ーdiーtertーbutylーpーbenzoーquinone." J.Phys.Chem.95. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Hidekazu Honma: "CIDEP Study on Photooxidation of N,N,N',N'ーtetramethylーpーphenylenediamine by Maleic Anhydride:Enhanced SーT_<ー1> Mixing in Radical Ion Pair System." J.Phys.Chem.95. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Hisao Murai: "CIDEP Study on PhotoーReduction of Xanthone in Alcohols:Novel Indirect Hydrogen Abstraction Steps." J.Phys.Chem.95. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yoshiya Konishi: "Timeーresolved ESR Study on Photodissociation of 2,4,6ーTrimethylbenzoyl Phosphine Oxide." J.Phys.Chem.95. (1991)

    • Related Report
      1990 Annual Research Report

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

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