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An Approach to the microscopic features of liquid phase reactions using solvation clusters of known structure

Research Project

Project/Area Number 03403002
Research Category

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

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KAJIMOTO Okitsugu  Faculty of Science, Kyoto University Professor, 理学部, 教授 (30029483)

Co-Investigator(Kenkyū-buntansha) FUJIMURA Yo  Faculty of Science, Kyoto University Instructor, 理学部, 助手 (00222266)
YOSHIMURA Yosuke  Faculty of Science, Kyoto University Instructor, 理学部, 助手 (10192428)
HARA Kimihiko  Faculty of Science, Kyoto University Lecturer, 理学部, 講師 (80025436)
Project Period (FY) 1991 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥30,900,000 (Direct Cost: ¥30,900,000)
Fiscal Year 1993: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1992: ¥9,000,000 (Direct Cost: ¥9,000,000)
Fiscal Year 1991: ¥20,600,000 (Direct Cost: ¥20,600,000)
KeywordsSolvation cluster, / Rotational coherence spectroscopy / Intramolecular charge-transfer reactions / 9,9'-bianthryl / Internal rotation / 回転コヒーレンス法 / クラスター / 溶媒和 / 超音速ジェット / ファンデルワールス分子 / 電荷移動 / ファンデルクールス分子 / 回転コヒ-レンス法 / 液相反応 / クラスタ- / 溶媒効果 / フリ-ジェット / ファンデルワ-ルス分子
Research Abstract

The aim of this project is to determine the structure of solvation clusters by means of the rotational coherence spectroscopy and, based on the determined structure of the clusters, to understand the precise dynamics of cluster reactions. The following subjects have been intensively studied during the period of this project.
1. The development of the method for determining the structure of large solvation clusters
For the determination of the structure of large molecules like solvation clusters, the rotational coherence spectroscopy (RCS) is much more suitable than the ordinary high-resolution spectroscopy. RCS directly determines the rotational constants of a cluster by observing the rotational period in the time domain. We constructed an RCS system consisting of a Ti : Al_2O_3 ps laser and a molecular beam apparatus.
The RCS of 9,9'-bianthryl (BA)
The observation of RCS of 9,9'-bianthryl revealed that the RCS signal reflected the average rotational angle of each twisting vibrational leve … More l in its intensity and the coherence time.
3. The structure of 9,9'-bianthryl complexes
By using the hole-burning spectroscopy, the detailed spectra of BA complexes were obtained and the potentials for the internal rotation were determined for the complexes. In a He complexe the small perturbation slightly splits the degenerate twisting levels whereas in Ar and H_2O complexes the shape of the potential is drastically changed ; one well of the double well potential disappears.
The RCS of these complexes could not be obtained with the time-correlated single photon counting method which detected the coherence of the excited state. On the other hand the time-resolved fluorescence depletion method which detects both the ground and excited state coherence provided information of the rotational constants of BA-Ne, BA-Ar, and BA-H_2O complexes. With the aid of structure optimization based on the empirical atom-atom interaction potentials, the structure of these complexes were determined.
4. The internal rotation and the charge-transfer reaction of 4- (9-anthryl) aniline (AA)
An compound, 4- (9-anthryl) aniline(AA), whose behavior is essentially the same for the typical charge-transfer compounds 4- (9-anthryl) -N,N-dimethylaniline (ADMA), was first synthesized and studied under supersonic jet conditions. The potential for the internal rotation was determined and the presence of a new electronic state of CT character was proposed. Less

Report

(4 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • 1991 Annual Research Report
  • Research Products

    (31 results)

All Other

All Publications (31 results)

  • [Publications] Yokoyama,H.,Kajimoto,O.,Ohshima,Y.,and Endo,Y.: "The structure of 4-(N,N-dimethylamino) benzonitrile and its van der Waals complexes" Chem.Phys.Lett.,. 179. 455-459 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Honma,K.,and Kajimoto,O.: "Symmetry demand in polar excited state formation of 9,9'-bianthryl in clusters with some ketones." J.Chem.Phys.101. 1752-1754 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [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(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kajimoto,O.: "TICT molecules in a free jet Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena" Elsevier Science Publishers (N.Mataga,T.Okada,and H.Masuhara,Ed.), 567 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kajimoto, O., Hayami, S., and Shizuka, H.: "The LIF spectra and the structure of jet-cooled 4- (9-anthryl) -n, N-dimethylaniline (ADMA)." Chem.Phys.Lett.177. 219-222 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yokoyama, H., Kajimoto, O., Ohshima, Y., and Endo, Y.: "The structure of 4- (N,N-dimethylamino) benzonitrile and its van der Waals complexes." Chem.Phys.Lett.179. 455-459 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Honma, K.and Kajimoto, O.: "Symmetry demand in polar excited state formation of 9,9'-bianthryl in clusters with some ketones." J.Chem.Phys.101. 1752-1754 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [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
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kajimoto, O.: TICT molecules in a free jet "Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena". Elsevier Science Publishers (N.Mataga, T.Okada, and H.Masuhara, Ed.), 145-154 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Honma, K., and Kajimoto, O.: Microscopic solvation of 9.9'-bianthryl studied in its clusters with polar molecules "Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena". Elsevier Science Publishers (N.Mataga, T.Okada, and H.Masuhara, Eds.), 335-342 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [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". Elsevier Science Publishers (K.Kuchitsu Ed.) Vol.82, (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] O.Kajimoto: "Pico-second dynamics of the twisted intramolecular chargetransfer state formation of(N,N′-dimethylamino)benzonitrile in supercritical fruid solution." Chem.Phys.Lett.209. 357-360 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] K.Honma: "Symmetry demand in polar excited state formation of 9,9′-bianthryl in clusters with some ketones" J.Chem.Phys.100. (in press) (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] K,HONMA and O.Kajimoto: "Symmetry demand in polar excited state formation of 9,9'-bianthryl in clusters with some ketones" J.Chem.,Phys.(1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.NAOTOH,Y.Fujimura K.Honma & O.Kajimoto: "Photodissociation oh the NO dimer at 193 nm:the rotational alignment of the NO(A) fragments" Chem.Phys.Lett.(1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] H.ISHIKAWA & O.Kajimoto: "Photolysis of phenylsilane at 193 nm:Energy distribution od the fragments" J.Phys.Chem.(1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] O.KAJMOTO: "TICT molecules in a free jet" ¨Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena¨,(N.Mataga et al.Ed.),Elsevier. 145-154 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] K.HONMA & O.Kajimito: "Microscopic solvation of 9,9¨-bianthryl soudied in its clusters with polar molecules" ¨Dynamics and Mechanisms of Photoinduced Electron Transfer and Related Phenomena¨,(N.Mataga et al.Ed.),Elsevier. 335-342 (1992)

    • Related Report
      1992 Annual Research Report
  • [Publications] Y.Naito,Y.Fujimura,O.Kajimoto,K.Honma: "Photodissociation of the NO dimer:Rotational energy distribution and alignment of the NO(B^2)fragments" Chem.Phys.Lett.190. 135-138 (1992)

    • Related Report
      1991 Annual Research Report
  • [Publications] O.Kajimoto,H.Yokoyama,Y.Ooshima,Y.Endo: "Structure of ー4ー(N,Nーdimethylamino)benzonitrile and its van der Waals complexes" Chem.Phys.Lett.179. 455-459 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] O.Kajimoto,S.Hayami,H.Shizuka: "The LIF spectra and the structure of jetーcooled 4ー(9ーanthryl)ーN,Nーdimethylaniline(ADMA)" Chem.Phys.Lett.177. 219-222 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] K.Honma,K.Arita,K.Yamasaki,O.Kajimoto: "Microscopic solvation of acetone to 9,9^1ーbianthryl studied in a free jet:Polar excited state formation" J,Chem.Phys.94. 3496-3503 (1991)

    • Related Report
      1991 Annual Research Report
  • [Publications] 梶本 興亜(編・著): "クラスタ-の化学" 培風館, 305 (1992)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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