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1995 Fiscal Year Final Research Report Summary

Dynamics of internal rotation related to the intramolecular charge-t transfer reactions

Research Project

Project/Area Number 06453022
Research Category

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

Allocation TypeSingle-year Grants
Research Field Physical chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KAJIMOTO Okitsugu  Graduate School of Science, Kyoto University Professor, 大学院・理学研究科, 教授 (30029483)

Co-Investigator(Kenkyū-buntansha) FUJIMURA Yo  Graduate School of Science, Kyoto University Instructor, 大学院・理学研究科, 助手 (00222266)
YOSHIMURA Yosuke  Graduate School of Science, Kyoto University Instructor, 大学院・理学研究科, 助手 (10192428)
HARA Kimihiko  Graduate School of Science, Kyoto University Lecturer, 大学院・理学研究科, 講師 (80025436)
Project Period (FY) 1994 – 1995
KeywordsInternal rotation / Time-resolved fluorescence depletion / Intramolecular charge-transfer reactions / Solvation cluster / 9,9'-bianthryl / ビアントリル
Research Abstract

The aim of this project is to determine the internal rotation potentials of the compounds capable of forming an intramolecular charge-transfer (CT) state and then to observe the dynamics of the CT state formation on the twisting reaction coordinate. The following topics have been extensively studied
1. Determination of the potential energy surface of internal rotation
The potential energy surfaces for the internal rotation of 9,9'-bianthryl (BA) -rare gas and BA-Ar complexes were determined. In a He complex the small perturbation slightly splits the degenerate twisting levels whereas in Ar and O complexes the shape of the potential is drastically changed ; one well of the double well potential disappears.
2. The time-resolved fluorescence of BA complexes
The BA-Ar complex only emits the fluorescence from the excited S_1 state whereas the BA-H_2 O complex gives the fluorescence from both the S_1 and the CT states. The time profile of the BA-Ar fluorescence was found to be independent of the … More wavelength observed, which probably indicated the rapid IVR within the time resolution of the detecting system. On the other hand, the time profile of the BA-H_2O complex showed the wavelength dependence ; at the excitation wavelength 375 nm), it decayd very rapidly within 10 ps whereas at 380nm it increased first and then decreased with the time constant of 20 ps. The CT fluorescence increased with 20 ps rise time. This behavior indicates the presence of the intermediate state which probably be assignable to the vibarationally hot CT state
3. The observation of the relaxation processes with the time-resolved fluorescence depletion (TRFD) method
With the TRFD method, the rapid dephasing processes of the excited state of BA-Ar and BA-H_2O complexes have been observed. In the BA-Ar complexes, the observed dephasing of 10 ps corresponded to the intramolecular vibrational energy redistribution whereas in BA-H_2O complexes the observed 6 ps dephasing time could be attributed to both the IVR and CT state formation.
4. A simulation of the dynamic processes
The simultaneously occurring IVR and CT state formation in the BA-H2O complexes was simulated in terms of the time-evolution of the wavefunction prepared by the ps excitation. The observed behavior was well reproduced. Less

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Fujiwara,T.,Fujimura,Y.and Kajimoto,O.: "Rotational coherence spectroscopy of 9,9'-binathryl and its van der Waals complexes with Ar and H_2O" Chem.Phys.Letters.261. 201-207 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Lee,S.and Kajimoto,O.: "4-(9-Anthryl) aniline. 2. Two weakly coupled electronic states and their torsional potentials evaluated from the LIF spectra in a supersonic jet." J.Phys.Chem.101. 5232-5240 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Ishida,T.,Fujimura,Y.,Fujiwara, T. and Kajimoto,O.: "Excited state dynamics of 9,9'-bianthryl clusters with H_2O and Ar" Chem.Phys.Lett.288. 433-440 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Itoh,M.and Kajimoto,O.: "Excited-State Electron Donor-Acceptor Interaction of Jet- Cooled Organic Molecules Dynamics of Excited Molecules Series in Physical and Theoretical Chemistry,Vol.82," Elsevier Science Publishers (K.Kuchitsu Ed.)., 614 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Honma, K., Arita, K., Yamasaki, K., and kajimoto, O.: "Microscopic solvation of acetone to 9,9'-bianthryl studied in a free jet : Polar excited state formation." J.Chem.Phys. 94. 3496-3503 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Fujiwara, T., Fujimura, Y.and Kajimoto, O.: "Rotational coherence spectrocscopy of 9,9'-binathryl and its van der Waals complexes with Ar and H_2O" Chem.Phys.Letters.261. 201-207 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Lee, S., Arita, K.and Kajimoto, O.: "Laser-Induced fluorescence excitation spectrum of jet-cooled 4- (9-Anthryl) aniline : Observation of two weakly coupled electronic states" Chem.Phys.Letters. 265. 579-584 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kajimoto, O., Sekiguchi, K., Nayuki, T.and Kobayashi, T.: "Dynamics of charge-transfer state formation in supercritical fluid solvent." Ber.Bunsenges.Phys.Chem.101 (3). 600-605 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Lee, S., Arita, K., and Kajimoto, O.: "4- (9-Anthryl) aniline. 1. Intramolecular charge-transfer state formation in solution." J.Phys.Chem.101. 5228-5231 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Lee, S.and Kajimoto, O.: "4- (9-Anthryl) aniline. 2. Two weakly coupled electronic states and their torsional potentials evaluated from the LIF spectra in a supersonic jet." J.Phys.Chem.101. 5232-5240 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Ishida, T., Fujimura, Y., Fujiwara, T.and Kajimoto, O.: "Excited state dynamics of 9,9'-bianthryl clusters with H_2O and Ar." Chem.Phys.Lett.288. 433-440 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Itoh, M.and Kajimoto, O.: Excited-State Electron Donor-Acceptor Interaction of Jet-Cooled Organic Molecules Dynamics of Excited Molecules "Series in Physical and Theoretical Chemistry"Vol.82. Elsevier Science Publishers (K.Kuchitsu Ed.), (1994)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-16  

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