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STRUCTURE AND BEHAVIOR OF EXCITED SPECIES AND ION PAIRS IN SOLUTIONS STUDIED BY THE TIME-RESOLVED MICROWAVE DIELECTRIC ABSORPTION METHOD

Research Project

Project/Area Number 04640478
Research Category

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

Allocation TypeSingle-year Grants
Research Field 構造化学
Research InstitutionFUKUI UNIVERSITY OF TECHNOLOGY

Principal Investigator

SHIMAMORI Hiroshi  FUKUI UNIVERSITY OF TECHNOLOGY, PROFESSOR, 工学部, 教授 (80139815)

Co-Investigator(Kenkyū-buntansha) TATSUMI Yoshitsugu  FUKUI UNIVERSITY OF TECHNOLOGY, ASSISTANT, 工学部, 助手 (80217752)
Project Period (FY) 1992 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1993: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1992: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywordsmicrowave dielectric absorption / aniline-derivatives / dipole moment / excited triplet state / contact ion pair / electron transfer / benzil / flash photolysis / 芳香族アミン / 光イオン化 / ハロゲン化物
Research Abstract

Followings are the main results of experimental studies with the time-resolved microwave dielectric absorption method combined with laser flash photolysis :
1. For N, N, N', N'-tetramethyl-p-phenylenediamine and N, N, N', N'-tetramethyl-benzidine in the presence of halogen-containing compounds, long-lived contact-ion-pairs are formed efficiently, and the efficiency and mechanism of their formation cannot be reconciled with those of the conventional electron-transfer processes, but correlate well to the electron attachment ptocesses in the gas phase. These results have been confirmed by the ordinary time-resolved light-absorption measurements following to flash photolysis.
Dipole moments of excited triplet states have been determined for aniline, its N-substituted derivatives (dimethylaniline, diethylaniline, diphenylamine, and triphenylamine) and ring-substituted compounds (o-, m-, p-anisidine, p-chloro-, p-nitro-, and p-cyano-aniline). Values obtained by the semi-empirical calculations are generally in good agreement with the present experimental ones.
Species with dipole moments much larger than those for the excited triplet states are formed for dimethylaniline and diethylaniline dissolved in carbontetrachloride. They can be ascribed to formation of contact ion pairs as in aromatic diamines.
It has been shown that photolysis of benzil at 308 nm laser pulse, in contrast to 355 nm photolysis, caused dissociation of the molecule into benzoyl radicals with the quantum yield of about 0.3, and the rest leads to the formation of the excited triplet state of benzil.
It has been suggested that determination of the dipole moment of excited state at very low temperatures may need further improvement of the detection sensitivity as well as the method of calibration of the signal intensity.

Report

(3 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] Hiroshi Shimamori: "Rates and Efficiencies of Contact-Ion-Pair Formation in Photolyzed Mixtures of TMPD with Halogenated Compounds--" The Journal of Physical Chemistry. 97. 3545-3550 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Shimamori: "Contact Ion Pairs Formed from Photolyzed Solutions of N,N,N′,N′-Tetramethylbenzidine in CCl_4" The Journal of Physical Chemistry. 97. 9408-9412 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Shimamori: "Mechanism of Contact Ion Pair Formation in Photolyzed Mixtures of N,N,N′,N′-Tetramethylbenzidine----" The Journal of Physical Chemistry. 98. 2576-2581 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Shimamori: "Rates and Efficiencies of Contact-Ion-Pair Formation in Photoluyzed Mixtures of TMPD with Halogenated Compounds in Nonpolar Solvents" The Journal of Physical Chemistry. Vol.97. p.3545-3550 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Shimamori: "Contact Ion Pairs Formed from Photolyzed Solutions of N, N, N', N'-Tetramethylbenzidine in CCI_4" The Journal of Physical Chemistry. Vol.97. p.9408-9412 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] H.Shimamori: "Mechanismn of Contact Ion Pair Formation in Photolyzed Mixtures of N, N, N', N'- Tetramethylbenzidine with Halogen-Containing Compounds in Nonpolar Solvent" The Journal of Physical Chemistry. Vol.98. p.2576-2581 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Hiroshi Shimamori: "Rates and Efficienies of Contact-Ion-Pair Formation in Phololyzed Mixtures of TMPD with Halogenated Compounds in Nonpolar Solvents" The Journal of Physial Chemistry. 97. 3545-3550 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hiroshi Shimamori: "Contact Ion Pairs Formed from Photolyzed Solutions of N,N,N′,N′-Tetramethy lbenzidine in CCl_4" The Journal of Physical Chemistry. 97. 9408-9412 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hiroshi Shimamori: "Mechanism of Contact Ion Pair Formation in Photolyzed Mixtures of N,N,N′,N′-Tetramethylbenzidine with Halogen-Containing Compounds in…" The Journal of Physical Chemistry. 98. 2576-2581 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Hiroshi Shimamori: "Rates and Efficiencies of Contact-Ion-Pair Formation in Photolyzed Mixtures of TMPD with Halogenated Compounds in Nonpolar…" The Journal of Physical Chemistry. 97. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hiroshi Shimamori: "Progress in Photochemistry and Photophysics.Vol.VI.Chap2." CRC Press, 35 (1992)

    • Related Report
      1992 Annual Research Report

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

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