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High-frequency time-resolved EPR Study on the Short-lived Paramagnetic Species

Research Project

Project/Area Number 07404040
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

TERO Shozo  Inst.for Chem.Reaction Science, Professor, 反応化学研究所, 教授 (80111318)

Co-Investigator(Kenkyū-buntansha) IKOMA Tadaaki  Inst.for Chem.Reaction Science, Research Associate, 反応化学研究所, 助手 (10212804)
AKIYAMA Kimio  Inst.for Chem.Reaction Science, Associate Professor, 反応化学研究所, 助教授 (10167851)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥30,200,000 (Direct Cost: ¥30,200,000)
Fiscal Year 1997: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1996: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 1995: ¥23,200,000 (Direct Cost: ¥23,200,000)
Keywordstime-resolved spectroscopy / spin dynamics / short-lived species / radical pairs / excited triplet states / spin-orbit interaction / exhange interaction / carbene / 短寿命常時性種
Research Abstract

We built a Q-band time-resolved EPR spectrometer, which works with a pulsed laser. We applied the system to verify the mechanism of the ClDEP spectra due to short-lived radicals and the broadening mechanism of the time-resolved EPR spectra due to short-lived excited triplet states.
1. Microwave frequency dependence of spin-polarized EPR spectra
(a) The CIDEP spectra involving triplet mechanism depends on significantly to the observed frequency.
(b) Time-resolved EPR measurements on the excited triplet states verified that the spectral broadening due to the g-anisotropy is clearly distinguished from the other mechanisms.
2. The sign of the exchange interaction in the radical ion pairs.
The present study verified that the exchange interaction is governed by charge transfer interaction rather than covalent bonding interactions, The level crossing between the potential surfaces of the radical ion pair state and ground state is a key factor.
3. Electronic structure of the excited state of diphenyl carben.
We successfully observed the short-lived excited state of diphenylmethylene and determined the zero-field splitting constants.
4. Structure of the dangling bonds in microcrystalline silicon.
Q-band EPR measurements verified the existence of three kinds of signals due to dangling bonds in microcrystalline silicon.
5. Eelctronic structure of the excited triplet states having unusually large zero-field splitting constants.

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (62 results)

All Other

All Publications (62 results)

  • [Publications] T.Ehara: "Effects of Geometry and Hydrogen Bonding on the Excited Triplet States of 4-Nitropyridine N-Oxide and Derivatives" J.Phys.Chem.99. 2292-2295 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] A.Katsuki: "Echo FT-EPR Study of the Photochemical Reduction and Oxidation Reactions of 2,5-Di-t-butyl-1,4-benzoquinone and 2,5-Di-t butylhydroquinone by Xanthene Dyes" Bull.Chem.Soc.Jpn.68. 3383-3389 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Origin of an Absorptive Electron Spin Polarization Observed in Photochemical Hydrogen Abstraction Reaction by Benzophenone Derivatives. CW and Pulsed EPR Studies" J.Phys.Chem.100(1). 180-183 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Time-Resolved and Fourier Transform EPR Studies of Type I Photochemical Reaction. Direct Determination of Kinetic Parameters of C-C Bond Cleavage" Res.Chem.Intermed.22(2). 103-113 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Nakagawa: "FT EPR Study of the Hydrated Electron Generated by Laser Excitation of Phenothiazine in Quinone-SDS Micellar Systems" J.Am.Chem.Soc.118(24). 5778-5782 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Tero-Kubota: "Coherent and Incoherent Hopping of Triplet Exciton in Quinoxaline-annelated and Naphthalene-annelated Dimers" Chem.Phys.Lett.249. 314-318 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Positive Exchange Interaction in the Radical Ion Pair of Benzophenone Anion and 1,4-Diazabicyclo[2,2,2]octane Cation Radicals Studied by FT-EPR Spectroscopy" Chem.Phys.Lett.263(1,2). 161-166 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sasaki: "Spin-Orbit Coupling Induced Electron Spin Polarization: Influence of Heavy Atom Position" J.Am.Chem.Soc.119(6). 1323-1327 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Effects of Lewis Acid on the Sign of Exchage Interaction of Photogenerated Radical Ion Pairs" J.Chem.Soc.,Perkin Trans.2. 1619-1620 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Shimokage: "Substituent and Matrix Effects on the Excited Triplet States of 1,4-Naphthoquinones" J.Phys.Chem.A.101(49). 9253-9256 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Electronic Structure of the Excited Triplet State of Nonphosphorescent Tropolone Studied by Time-Resolved EPR" J.Chem.Soc.,Faraday Trans.94(9). 1197-1201 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Marcus Free Energy Dependence of the Sign of Exchange Interactions in Radical Ion Pairs Generated by Photoinduced Electron Transfer Reactions" J.Am.Chem.Soc.120(6). 1325-1325 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Direct Detection of the Excited Triplet State of Diphenylmethylene by Time-Resolved EPR Spectroscopy" J.Am.Chem.Soc.120(32). 8269-8270 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Molecular and Electronic Structures of the Short-Lived Excited Triplet State of Tropone" J.Phys.Chem.A. 102. 446-451 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Nagano: "Time-Resolved and Pulsed EPR Studies on the Lowest Excited Triplet State of 1,4-Diphenylbutadiyne" J.Phys.Chem.A. 102(29). 5769-5774 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sasaki: "Intrinsic Enhancement Factors of the Spin-Orbit Coupling Mechanism Polarization in the Duroquinone-N,N-Dimethylaniline Derivative Systems" J.Phys.Chem.A. 102(42). 8078-8083 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Two-Dimensional EPR Spectroscopic Studies on the Radicals in Argonne Premium Coals" Energy Fuel. 12(5). 996-1000 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "HYSCORE Study on Coal Radicals" Energy & Fuels. 12(6). 1363-1368 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] I.Amada: "Hydrogen Atom Abstraction and Electron Transfer of Triplet 2,3-Dihalo-1,4-naphthoquinones Studied by CIDEP Techniques and Laser Flash Photolysis" Res.Chem.Intermed.24(1). 81-104 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Twist Conformational Effects on the Excited Triplet States of Aromatic Ketones Studied by Multifrequency TREPR and pulsed EPR Spectroscopy" Mol.Phys.in press.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 勝木 明夫: "「光化学」,21" 光化学協会誌, 8 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 手老 省三: "バイオサイエンスESR" 廣川書店, 17 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 秋山 公男: "フタロシアニン-化学と機能" アイシーピー出版, 9 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 手老 省三: "化学総説No.36「光化学の基礎と先端研究」" 日本化学会編、学会出版センター, 9 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ehara: "Effects of Geometry and Hydrogen Bonding on the Excited Triplet States of 4-Nitropyridine N-Oxide and Derivatives" J.Phys.Chem.99 (8). 2292-2295 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] A.Katsuki: "Echo FT-EPR Study of the Photochemical Reduction and Oxidation Reactions of 2,5-Di-t- butyl-1,4-benzoquinone and 2,5-Di-t butylhydroquinone by Xanthene Dyes" Bull.Chem.Soc.Jpn.68 (12). 3383-3389 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Origin of an Absorptive Elctron Spin Polarization Observed in Photochemical Hydrogen Abstraction Reaction by Benzophenone Derivatives. CW and Pulsed EPR Studies" J.Phys.Chem.100 (1). 180-183 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Time-Resolved and Fourier Transform EPR Studies of Type I Photochemical Reaction. Direct Determination of Kinetic Parameters of C-C Bond Cleavage" Res.Chem.Intermed.22 (2). 103-113 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Nakagawa: "Et EPR Study of the Hydrated Electron Generated by Laer Excitation of Phenothiazine in Quinone-SDS Micellar Systems" J.Am.Chem.Soc.118 (24). 5778-5782 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Tero-Kubota: "Coherent and Incoherent Hopping of Triplet Exciton in Quinoxaline-annelated and Naphthalene-annelated Dimers" Chem.Phys.Lett.249. 314-318 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Positive Exchange Interaction in the Radical Ion Pair of Benzophenone Anion and 1,4-Diazabicyclo [2,2,2] octane Cation Radicals Studied by FT-EPR Spectroscopy" Chem.Phys.Lett.263 (1,2). 161-166 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sasaki: "Spin-Orbit Coupling Induced Electron Spin Polarization : Influence of Heavy Atom Position" J.Am.Chem.Soc.119 (6). 1323-1327 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Effects of Lewis Acid on the Sign of Exchange Interaction of Photogenerated Radical Ion Pairs" J.Chem.Soc.Perkin Trans.2. 1619-1620 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Shimokage: "Substituent and Matrix Effects on the Excited Triplet States of 1,4-Naphthoquinones" J.Phys.Chem.A. 101 (49). 9253-9256 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Electronic Structure of the Excited Triplet State of Nonphosphorescent Tropolone Studied by Time-Resolved EPR" J.Chem.Soc., Faraday Trans.94 (9). 1197-1201 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Marcus Free Energy Dependence of the Sign of Exchange Interactions in Radical Ion Pairs Generated by Photoinduced Electron Transfer Reactions" J.Am.Chem.Soc.120 (6). 1325-1325 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Akiyama: "Direct Detection of the Excited Triplet State of Diphenylmethylene by Time-Resolved EPR Spectroscopy" J.Am.Chem.Soc.120 (32). 8269-5270 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Molecular and Electronic Structures of the Short-Lived Excited Triplet State of Tropone" J.Phys.Chem.A. 102 (2). 446-451 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Nagano: "Time-Resolved and Pulsed EPR Studies on the Lowest Excited Triplet State of 1,4-Diphenylbutadiyne" J.Phys.Chem.A. 102 (29). 5769-5774 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sasaki: "Intrinsic Enhancement Factors of the Spin-Orbit Coupling Mechanism Polarization in the Duroquinone-N,N-Dimethylaniline Derivative Systems" J.Phys.Chem.A. 102 (42). 8078-8083 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Two-Dimensional EPR Spectroscpic Studies on the Radicals in Argonne Premium Coals" Energy & Fuels. 12 (5). 996-1000 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "HYSCORE Study on Coal Radicals" Energy & Fuels. 12 (6). 1363-1368 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] I.Amada: "Hydrogen Atom Abstraction and Electron Transfer of Triplet 2,3-Dihalo-1,4-naphthoquinones Studied by CIDEP Techniques and Laser Flash Photolysis" Res.Chem.Intermed.24 (1). 81-104 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] T.Ikoma: "Twist Conformational Effects on the Excited Triplet States of Aromatic Ketones Studied by Multifrequency TREPR and pulsed EPR Spectroscopy" Mol.Phys.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Sekiguchi: "Marcus Free Energy Dependence of the Sign of Exchange Interactions in Radical Ion Pair Generated by Photoinduced Electron Transfer" J.Am.Chem.Soc.120(6). 1325-1326 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Shimokage: "Substituent and Matrix Effects on the Excited Triplet States of 1,4-Naphthoquinones" J.Phys.Chem. 101(49). 9253-9256 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Sekiguchi: "Effects of Lewis Acid on the Sign ofExchange Interaction of Photogenerated Radical Ion Paris" J.Chem.Soc.,Perkin Trans.2. 2. 1619-1620 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Sasaki: "Spin-Orbit Coupling Induced Electron Spin Polarization:Influence of Heavy Atom Position" J.Am.Chem.Soc.119(6). 1323-1327 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Sekiguchi: "Positive Exchange Interaction in the Radical Ion Pair of Benzophenone Anion and 1,4-Diazabicyclo[2,2,2]octane Cation Radicals Studied by FT-EPR Spectroscopy" Chem.Phys.Lett.263(2). 161-166 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Nakagawa: "FT EPR Study of the Hydrated Electron Generated by Laser Excitation of Phenothiazine in Quinone-SDS Micellar Systems" J.Am.Chem.Soc.118(24). 5778-5782 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] 池上 雄作: "物理化学II-熱理論学・速度論" (株)丸善, 203 (1996)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Akiyama: "Origin of an Absorptive Electron Spin Polarization Observed in Photochemical Hydrogen Abstraction Reaction by Benzophenone Derivatives. CW and Pulsed EPR Studies" J.Phys.Chem.100(1). 180-183 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Tero-Kubota: "Coherent and Incoherent Hopping of Triplet Exciton in Quinoxaline-annelated and Naphtalene-annelated Dimers" Chem.Phys.Lett.249(5,6). 314-318 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Akiyama: "Time-resolved and Fourier Transform EPR Studies of Type I Photochemical Reaction. Direct Determination of Kinetic Parameters of C-C Bond Cleavage" Res.Chem.Intermed.22(2). 103-113 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Nakagawa: "FT EPR Study of the Hydrated Electron Generated by Laser Excitation of Phenothiazine in Quinone-SDS Micellar Systems" J.Am.Chem.Soc.118(24). 5778-5782 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Sekiguchi: "Positive Exchange Interaction in the Radical Ion Pair of Benzophenone Anion and 1,4-Diazabicyclo [2, 2, 2] octane Cation Radicals Studied by FT-EPR Spectroscopy" Chem.Phys.Lett.263(1,2). 161-166 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Sasaki: "Spin-Orbit Coupling Induced Electron Spin Polarization : Influence of Heavy Atom Position" J.Am.Chem.Soc.119(6). 1323-1327 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Tero-Kubota: "Coherent and Incoherent Hopping of Triplet Exciton in Quinoxaline-annelated and Naphtalene-annelated Dimers" Chem.Phys.Lett.249(5,6). 314-318 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Akiyama: "Time-resolved and Fourier Transform EPR Studies of Type I Photochemical Reaction.Direct Determination of Kinetic Parameters of C-C Bond Cleavage" Res.Chem.Intermed.22(2). 103-113 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Akiyama: "Origin of an Absorptive Electron Spin Polarization Observed in Photochemical Hydrogen Abstraction Reaction by Benzophenone Derivatives.CW and Pulsed EPR Studies" J.Phys.Chem.100. (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Oshio: "Magnetic Interactions in Cu(I) and Ag(I)Iminonitroxides" Mol.Cryst.Liq.Cryst.273. 47-56 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Katsuki: "Echo FT-EPR Study of the Photochemical Redution and Oxidation Reactions of 2,5-Di-t-butyl-1,4-benzoquinone and 2,5-Di-t butylhydroquinone by Xanthene Dyes" Bull.Chem.Soc.Jpn.68. 3383-3389 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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