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Study on Excited State Interaction by Time-Resolved Spectroscopy

Research Project

Project/Area Number 03453019
Research Category

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

Allocation TypeSingle-year Grants
Research Field 構造化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

SHIBUYA Kazuhiko  Tokyo Institute of Technology Department of Chemistry Associate Professor, 理学部, 助教授 (30126320)

Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1992: ¥700,000 (Direct Cost: ¥700,000)
KeywordsOODR / spin-orbit interaction / treansient absortion / photothermal spectroscopy / nitrogen dioxide / naphtalene / fullerene / benzophenone / 光一光二重共鳴 / ジフェニルアミン
Research Abstract

The visible absorption bands of NO_2 in the 588-591-nm range have been proved to contan a vibronic transition to the dark C^2A_2 state by rotational analysis using the optical-optical double-resonance (OODR) techniques. The intermediate state is verified to be a mixed state of dark C^2A_2 and light A^2B_2 coupled by spin-orbit inter- action with the selection rules DELTAN=*1 and DELTAKa=0. Although the C^2A_2 state is dark in the v_1 transition from X^2A_1, it becomes a light state in the v_2 transition to 2^2B_2.
Transient absorption and time-resolved thermal lensing techniques have been used to study the photophysical behavior of C_<60> in benzene solution at room tempeature. The riplet state was the only transient species detectable with the 10 ns time- resolution. The triplet-triplet absorption spectrum with apparent band peaks at 330 and 745 nm covers the whole spectral range of 290-850 nm. The riplet lifetime in air-free benzene is 49*1 mus and essentially all the photon energy absorbed is released as heat, predominantly through the triplet state.
A time-resolved thermal lensing (TRTL) technique was applied to the determina- tion of the dissociation quantum yield of benzophenone in the highly-excited triplet state yielding two phenyl radicals and a carbon monoxide. The TRTL signals were simulated using a kinetic model inculuding the S_1*S_0 and T_n*T_1 absorptions of benzophenone and subsequent dissociation of the Tn molecule. The reaction quantum yield and the heat of reaction in benzene solution were determined to be 0.36 and 126 kcal mol^<-1>, respectively, based on the experiment and simulation.

Report

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

    (24 results)

All Other

All Publications (24 results)

  • [Publications] T.Suzuki,Y.Kajii,K.Shibuya,K.Obi: "Relaxation processes of highly excited naphthalene in solution studied by time-resolved thermal lensing technique" Chemical Physics. 161. 447-452 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Kajii,T.Suzuki,Y.Takatori,K.Shibuya,K.Obi: "Photodissociation of Highly-Excited Triplet State of Benzophenone Studied by a Time-Resolved Thermal Lensing Technique" Bull.Chem.Soc.Jpn.65. 1349-1355 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Takatori,T,Suzuki,Y.Kajii,K.Shibuya,K.Obi: "Highly excited triplet state dynamics of benzophenone studied by pump and probe time-resolved thermal lensing spectroscopy" Chemical Physics. 169. 291-296 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Kajii,H.Itabashi,K.Shibuya,K.Obi: "Complex Formation of Benzophenone Ketyl Radical and Triethylamine" J.Phys.Chem.96. 7244-7247 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] W.Sisk,H.Endo,K.Shibuya,K.Obi: "NO A^2Σ^+-X^2Π Chemiluminescence Produced from the Reaction of Excited NO_2 with Acetylene and Its Derivatives in Their Triplet States" J.Phys.Chem.96. 6668-6674 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y.Kajii,K.Takeda,K.Shibuya: "Photochemical reaction of C_<60> in the presence of triethylamine in toluene" Chem.Phys.Letters. 204. 283-286 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki, Y.Kajii, K.Shibuya, K. Obi: "Relaxation processes of highly excited naphthalene in solution studied by time-resolved thermal lensing technique" Chem. Phys.161. 447-452 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Kajii, T. Suzuki, Y. Takatori, K. Shibuya, K. Obi: "Photodissociation of Highly-Excited Triplet State of Benzophenone Studied by a Time-Resolved Thermal Lensing Technique" Bull. Chem. Soc. Jpn.65. 1349-1355 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Takatori, T. Suzuki, Y. Kajii, K. Shibuya, K. Obi: "Highly excited triplet state dynamics of benzophenone studied by pump and probe time-resolved termal lensing spectroscopy" Chem. Phys.169. 291-296 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. KAJII, H. Itabashi, K. Shibuya, K. Obi: "Complex Formation of Benzophenone Ketyl Radical and Triethy lamine" J. Phys. Chem.96. 7244-7247 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] W. Sisk, H. Endo, K. Shibuya, K. Obi: "NO A^2SIGMA^+-X^2PI Chemiluminescence Produced from the Reaction of Excited NO_2 with Acetyleme and Its Derivatives in Their Triplet States" J. Phys. Chem.96. 6668-6674 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Y. Kajii, K. Takeda, K. Shibuya: "Photochemical reaction of C_<60> in the presence of triethylamine in tolueme" Chem. Phys. Letters. 204. 283-286 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] T.Suzuki,Y.Kajii K.Shibuya,K.Obi: "Relaxation processes of highly excited naphthalene in solution srudied by time-resolved thermal lensing technique" Chemical Physics. 161. 447-452 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Kajii,T.Suzuki Y.Takatori,K.Shibuya,K.Obi: "Photodissication of Highly-Excited Triplet State of Benzophenone Studied by a Time-Resolved Thermal Lensing Technique" Bull.Chem.Soc.Jon.65. 1349-1355 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Takatori,T.Suzuki,Y.Kajii K.Shibuya,K.Obi: "Highly excited triplet state dynamics of benzophenone studied by pump and probe time-resolved thermal lensing spectroscopy" Chemical Physics. 169. 291-296 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Kajii,H.Itabashi K.Shibuya,K.Ob: "Complex Formation of Benzophenone Ketyl Radical and Triethylamine" J.Phys.Chem.96. 7244-7247 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] W.Sisk,H.Endo K.Shibuya,K.Obi: "NOA^2Σ^+-X^22 Chemiluminescence Produced from the Reaction of Excited NO_2 with Acetylene and Its Derivatives in Their Triplet States" J.Phys.Chem. 96. 6668-6674 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Kajii,K.Takeda K.Shibuya: "Photochemical reaction of C_<60> in the presence of triethylamine in toluene" Chem.Phys.Letters. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.Shibuya: "Possible rotationally resolved detection of NO_2 in the C^2A_2 state by opticalーoptical double resonance spectroscopy" J.Chem.Phys.95. 720-721 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Suzuki: "Calorimetric Standards for Photochemical Methods in Ultraviolet and Visible Spectral Regions" Rev.Chem.Intermedi.15. 261-270 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Kajii: "Transient absorption,lifetime and relaxation of C_<60> in the triplet state" Chem.Phys.Letters. 181. 100-104 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Suzuki: "Photocyclization of Diphenylamine Studied by TimeーResolved Thermal Lensing:Heat of Reactions,Energetics and Reactivety of Intermediates" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report
  • [Publications] T.Suzuki: "Relaxation Processes of HighlyーExcited Naphtalene in Solution Studied by TimeーResolved Thermal Lensing Technique" Chem.Phys.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Kajii: "Photodissociation of HighlyーExcited Triplet State of Benzophenone Studied by a TimeーResolved Thermal Lensing Technique" Bull.Chem.Soc.Jpn.

    • Related Report
      1991 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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