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A New Molecular Approach toward Liquid-phase Chemical Reactions

Research Project

Project/Area Number 63303001
Research Category

Grant-in-Aid for Co-operative Research (A)

Allocation TypeSingle-year Grants
Research Field 物理化学一般
Research InstitutionKyoto University (1989)
The University of Tokyo (1988)

Principal Investigator

KAJIMOTO Okitsugu  Kyoto U., Fac. Science Professor, 理学部, 教授 (30029483)

Co-Investigator(Kenkyū-buntansha) OGAWA Teiichiro  Kyusyu U., Fac. Sci. & Tech. Prof., 総合理工学研究所, 教授 (50028156)
KONDOW Tamotsu  U.Kyoto, Fac. Sci. Prof., 理学部, 教授 (10011610)
SHIDA Tadamasa  Kyoto U., Fac. Sci. Prof., 理学部, 教授 (60025484)
ITO Michiya  U.Kanazawa, Fac. Pharm. Prof., 薬学部, 教授 (30012610)
TSUCHIYA Soji  U.Tokyo, Fac. Gen, Educ. Prof., 教養学部, 教授 (40012322)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥9,400,000 (Direct Cost: ¥9,400,000)
Fiscal Year 1989: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1988: ¥5,500,000 (Direct Cost: ¥5,500,000)
Keywordsclusters / van der Waals complex / supercritical fluid / proton-transfer / charge-transfer / solvent effect / cluster ions / matrix / ファンデルク-ルス錯体 / クラスター / ファンデルクルース錯体 / 電荷移動錯体 / クラスターイオン / 液相化学反応 / 異性化反応
Research Abstract

The aim of this cooperative research is to understand the solvent effect on molecular basis as the interaction between a solute and solvent molecules. For this purpose the following approaches were adopted.
(1) Cluters as a model of solvated molecules Small van der Waals clusters can be served as a model of solute molecules solvated by a small number of solvent molecules. In this case, the structure of the cluster can be determined using spectroscopic measurement and hence the details of the molecular interaction can be discussed. In the case of large clusters, the structure can be estimated from the thermodynamic data and fragmentation pattern. Using such clusters of a given structure, intramolecular chemical reaction and energy transfer have been studied.
(2) Using Supetcritical fluid as solvent A polar molecules dissolved in supercritical fluid was found to be surrounded by solvent fluid molecules and served as an independently solvated molecule at room temperature. Isomerization and charge-transfer reactions were studied for this particular solvated molecules.
(3) fragmentation of liquid solution into vacuum Jet expansion of liquid solution was found to forms the molecular size fragments and these fragments were proved to reflect the real structure of solution phase especially in the case of hydrogen-bonded solvent.
(4) femt-second observation of the motion of solvent molecules The ultra-fast motion of solvent molecules were followed after photo-ionization and photo-induced charge-transfer reactions.
(5) Reactions in matrix Reactions of radical cations were studied in glassy matrix at 77K and the information of the effect of molecular interaction on chemical reactions can be inferred.
Two meetings were held this year on the topics and the development of the above five research fields and hot discussions there helped individual attendant to develop his research project both experimentally and theoretically.

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (63 results)

All Other

All Publications (63 results)

  • [Publications] M.Ito and A.Hayashi: "Exciplex formation in the jetーcooled van der Waals cluster of methylーsubstituted dienes with fluorene and 9ーethylfluorene" J.phys.Chem. 93. 7789-7792 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Ito and M.Sasaki: "The van der Waals complex and exciplex formation between methyl substituted 1ーcyanonaphthalenes and triethylamine in a supersonic free jet" J.Phys.Chem.in press. 94. (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Tanaka and I.Omine: "Potential energy surfaces for water dynamics:reaction coordinates,transtition states,and normal mode analysis" J.Chem.Phys.91. 6318-6327 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Aoyagi,I.Omine,B.Kohler: "The frequency increase if tge C=C Ag stretching mode of polyenes in the 2^1A_g state;abーinitio MCSCF study of butadiene,hexatriene and octatetraene" J.Phys.Chem.in press. 94. (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Yao,T.Okada and N.Mataga: "Solvation induced charge separation in the excited state of composite systems with identical halves and intramolecular excimer formation by recombination.Picosecond laser photolysis studies on l,2ーdianthrylーethanes" J.Phys.Chem.93. 7388-7394 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Y.Kimura,Y.Yoshimura and M.Nakahara: "Chemical equilibrium in argon:anomaly of density depwndence of dimerization reaction in the medium density region" J.Chem.Phys. 91. 2758-2759 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Ogawa,T.Matsumoto,H.Kawazumi,T.Magamura: "Laser photoionization detector for reversed phoas high performance liquid chromatography" Analytical Science. 4. 473-480 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Y.Ozaki and T.Fukuyama: "An anomalous drop in the intensity distribution of cluster ions Ar_nX,X=Xe,N_2,Co_2 and CH_3OH" Int.J.Mass Spectrom.Ion Processes. 88. 227-239 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Kondow,T.Nagata and K.Kuchitsu: "A mechanism of electron attachment to small clusters" Z.Phys.(D). 12. 291-298 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] F.Misaizu,K.Mitsuke,T.Kondow and K.Kuchitsu: "Formation of negative ions from pyridine clusters in collision with HighーRydberg rareーgas atoms and slow electrons" J.Phys.Chem. 93. 4263-4270 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Kawashima,T.Kato and T.Shida: "Resonance Raman study of the radical cation of naphthalene in a glassy matrix at 77K" Chem.Phys.lett.59. 165-168 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Ushida,T.Shida and K.Shimokoshi: "Photoinduced isomerization observed for ringーopened radical cations of methylーsubstituted ethylene oxides" J.Phys.Chem. 93. 5388-5392 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Honma and O.Kajimoto: "Crossed beam study of the reaction of van der Waals molecule.H+(NO)_2ー〉HNO^*+NO" J.Chem.Phys. 92. 1657-1660 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Tsuchizawa,K.Yamaniuchi and S.Tsuchiya: "Interatomic potentials of the Cl and D0^+ stated of XeNe,XeAr and XeKr as studied by tunable vacuum ultraviolet laser spectroscopy" J.Chem.Phys.in press. 90. (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Shinohara and N.Nishi: "Excited state lifetimes and appearance potentials of benzene dimer and trimer" J.Chem.Phys.91. 6743-6751 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Hiraoka and T.Mori: "Isotope effect and nature of bonding in the cluster ions H_3Ar_n and D_3Ar_n" J.Chem.Phys.91. 4821-4828 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Kawahigashi S.Hirayama: "Microscopic fluorescence decay measurements on thin liquid films and droplets of concentrated dye solutions" J.Lumin.43. 207-210 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K.Fuke and K.Kaya: "Dynamics of doubleーprotonーtransfer reaction in the excited state model hydrogenーbonded base paris" J.Phys.Chem.63. 93-98 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Honma and O. Kajimoto: "Crossed beam study of the reaction of van der Waals molecule. H + (NO)_2 -> HNO^* + NO" J. Chem. Phys.92. 1657-1660 ((1990))

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Tsuchizawa, K.Yamanouchi and S.Tsuchiya: "Interatomic potentials of the Cl and D0^+ states of XeNe, XeAr and XeKr as studied by tunable vacuum ultraviolet spectroscopy" J. Chem. Phys., 92, in press (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H.Shinohara and N.Nishi: "Excited state lifetimes and appearance potentials of benzene dimer and trimer" J. Chem. Phys. 91, 6743-6751 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Hiraoka and T. Mori: "Isotope effect and nature of bonding in the cluster ions H_3Ar_n and D_3Ar_n" J. Chem. Phys., 91, 4821-4828 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Kawahigashi and S. Hirayama: "Microscopic fluorescence decay measurements on thin liquid films and droplets of concentrated dye solutions" J. Lumin., 43, 207-210 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Fuke and K. Kaya: "Dynamics of double-proton-transfer reaction in the excited state model hydrogen-bonded base pair" J. Phys. Chem., 63, 93-98 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M. Ito and A. Hayashi: "Exciplex formation in the jet-cooled van der Waals cluster of methyl-substituted dienes with fluorene and 9-ethyl-fluorene" J. Phys. Chem., 93, 7789-7792 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H. Tanaka and I. Omine: "Potential energy surfaces for water dynamics: reaction coordinates, transition states, and normal mode analysis" J. Chem. Phys., 91, 6318-6327 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H. Yao, T. Okada and N. Mataga: "Solvent induced charge separation in the excited state of composite system with identical halves and intramolecular excimer formation by recombination." J. Phys. Chem., 93 7388-7394 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Y. Kimura, Y. Yoshimura and M. Nakahara: "Chemical equilibrium in argon: anomaly of density dependence of dimerization reaction in the medium density argon" J. Chem. Phys., 91, 2758-2759 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Ogawa, T. Matsumoto, H. Kawazumi and T. Ogawa: "Laser photoionization detector for reversed phase high performance liquid chromatography" Analytical Science, 4 473-480 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] Y. Ozaki and T. Fukuyama: "An anomalous drop in the intensity distribution of cluster ions Ar_nX, X=Xe, N_2, CO_2 and CH_3OH" Int. J. Mass Spectrom. Ion Processes, 88, 227-239 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Kondow, T. Nagata and K. Kuchitsu: "A mechanism of electron attachment to small clusters" Z. Phys. (D), 12, 291-298 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] H. Kawashima, T. Kato and T. Shida: "Resonance Raman study of the radical cation of naphthalene in a glassy matrix at 77K" Chem. Phys. Lett. 59, 165-168 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] K. Ushida, T. Shida and K. Shimokoshi: "Photoinduced isomerization observed for ring-opened radical cations of methyl-substituted ethylene oxides" J. Phys. Chem., 93 5388-5392 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] M.Ito and A.Hayashi: "Exciplex formation in the jet-cooled van der Waals cluster of methyl-substituted dienes with fluorene and 9-ethylfluorene" J.Phys.Chem.93. 7789-7792 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Ito and M.Sadaki: "The van der waals complex and exciplex formation between methyl substituted 1-cyanonaphthalenes and triethylamine in a supersonic free jet" J.Phys.chem.94. (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] H.Tanaka and I.Omine: "Potential energy surfaces for water dynamics:reaction coordinates,transition states,and normal mode analysis" J.Chem.Phys.91. 6318-6327 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Aoyagi,I.Omine,B.Kohler: "The frequency increase if tge C=C Ag stretching mode of polyenes in the 2^lA_g Dastate;ab-initio MCSCF study of butadiene,hexatriene and octatetraene" J.Phys.Chem.94. inpress (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] H.Yao,T.Okada and N.Mataga: "Solvation induced charge separation in the excited state of composite systems with identical halves and intramolecular excimer formation by recombination.Picosecond laser photolysis studies on 1,2-dianthryl-ethanes" J.Pyhs.Chem.93. 7388-7394 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Y.Kimura,Y.Yoshimura and M.Nakahara: "Chemical equilibrium in argon:anomaly of density depwndence of dimerizatin reaction in the medium density region" J.Chem.Phys.91. 2758-2759 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Ogawa,T.Matsumoto,H.Kawazumi,T.Magamura: "Laser Photoionization detector for reversed phoas high Performance liquid chromatography" Analytical Science. 4. 473-480 (1988)

    • Related Report
      1989 Annual Research Report
  • [Publications] Y.Ozaki and T.Fukuyama: "An anomalous drop in the intensity distribution of cluster ions Ar_nX,X=Xe,N_2,CO_2 and CH_3OH" Int.J.Mass Spectrom.Ion Processes. 88. 227-239 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Kondow,T.Nagata and K.Kuchitsu: "A mechanism of electron attachment to small clusters" Z.Phys.(D). 12. 291-298 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] F.Misaizu,K.Mitsuke.T.Kondow and K.Kuchitsu: "Formation of negative ions from pyridine clusters in collision with High-Rydberg rere-gas atoms and slow electrons" J.Phys.Chem.93. 4263-4270 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] H.Kawashima,T.Kato and T.shida: "Resonance Raman study of the radical cation of naphthalene in a glassy matrix at 77K" Chem.Phys.Lett.59. 165-168 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] K.Ushida,T.Shida and K.Shimokoshi: "Photoinduced isomerization observed for ring-opened radical cations of methyl-substituted ethylene oxides" J.Phys.Chem.93. 5388-5392 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] O.Kajimoto.: J.Phys.Chem.92. 1347-1352 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Honma.: J.Chem.Phys.88. 4739-4747 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] O.Kajimoto.: Faraday Discuss.Chem.Soc.85. (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] H.Ito.: J.Mol Spectrosc.127. 143-155 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Y.Ozaki.: Int.J.Mass Spectry.Ion Processes.

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Momose.: J.Chem.Phys.89. 4185-4192 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] I.Ohmine.: J.Chem.Phys. 89. (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Mikami.: J.Phys.Chem.92. 1858-1862 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] T.Maeyama.: J.Amer.Chem.Soc.110. (1989)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Hiraoka.: J.Chem.Phys.89. 3190-3194 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Hiraoka.: J.Phys.Chem.92. 3943-3952 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] M.Itoh.: J.Phys.Chem.88. 5693-5696 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] K.Nakatani.: Chem.Phys.121. 87-92 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] S.Hirayama.: Chem.Phys.Lett.(1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Nishi.: J.Amer.Chem.Soc.110. 5246-5250 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Y.Yoshimura.: Ber.Bunsenges.Phys.Chem.92. 46-60 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Y.Yoshimura.: Ber.Bunsenges.Phys.Chem.92. 51-55 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Y.Ozaki.: Chem.Phys.Lett.145. 461-465 (1988)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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