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金属・非金属境界に位置する金混合原子価錯体の電子状態の研究とその超伝導相の探索

Research Project

Project/Area Number 05452040
Research Category

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

Allocation TypeSingle-year Grants
Research Field 固体物性Ⅰ(光物性・半導体・誘電体)
Research InstitutionThe University of Tokyo (1994)
Kyoto University (1993)

Principal Investigator

KOJIMA Norimichi  The University of Tokyo, College of Arts and Sciences, Professor, 教養学部, 教授 (60149656)

Project Period (FY) 1993 – 1994
Project Status Completed (Fiscal Year 1994)
Budget Amount *help
¥6,700,000 (Direct Cost: ¥6,700,000)
Fiscal Year 1994: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1993: ¥4,100,000 (Direct Cost: ¥4,100,000)
KeywordsMixed valence / Valence transition / P-T phase diagram / Perovskite structure / Jahn-Teller distortion / 混合原子価錯体 / 電荷移動相互作用 / 電荷移動遷移 / 構造相転移 / 相図
Research Abstract

The crystal structure and electronic properties of Au mixed valence compounds M_2Au_2X_6 (M=Rb, Cs ; X=Cl, Br, I) have been investigated by means of X-ray diffraction measurement under high pressure, ^<197>Au and ^<129>I Mossbauer spectroscopic measurements, and single crystal polarized reflectivity measurement. The results are as follows : (1) Cs_2Au_2X_6 (X=Cl, Br, I) undergo a tetragonal (I) -to-tetragonal (II) transition driven by the Au^I*Au^<III> transition at 11,9, and 5.5 GPa, respectively. Above the critical pressure, the AuI_6 octahedra in Cs_2Au_2I_6 are elongated, contrary the AuX_6 ones in Cs_2Au_2X_6 (X=Cl and Br) are compressed. Reflecting the half-filled HOMO band, it is considered that Cs_2Au_2X_6 (X=Cl and Br) and Cs_2Au_2I_6 in the tetragonal (II) phase behave as one-dimensional and two-dimensional conductors, respectively. The cubic perovskite phase with Au^<II> valence state appears under high pressures and high temperatures for all three compounds, which could be obtained as a metastable state at room temperature and ambient pressure. (2) Three inter-valence charge transfer transition (IVCT) bands appear in the visible region for all the compounds M_2Au_2X_6. From the analysis of IVCT,the inter-valence charge transfer interaction between Au^I and Au^<III> is considered to be two-dimensional. (3) From the analysis of Au and I Mossbauer spectra, the nature of the chemical bond between Au and halogen has been investigated in detail.

Report

(3 results)
  • 1994 Annual Research Report   Final Research Report Summary
  • 1993 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] N.Kojima: "Optical Investigation of the Intervalence Charge-Transfer Interaction in the Three-Dimensional Au Mixed-Valeuce Compounds Cs_2Au_2X_6(X=Cl,Br,I)." J.Chem.Soc.Dalton Trans.327-331 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kojima: "P-T Phase Diagram and Gold Valence State of the Perovskite-Type Mixed-Valence Compounds Cs_2Au_2X_6(X=Cl,Br,I) under High Pressures." J.Am.Chem.Soc.116. 11368-11374 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] S.S.Hafner: "Divalent Gold in Perovskite Type CsAuI_3." Phys.Lett.A. 192. 385-388 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] T.Terashima: "Electrical Transport Properties of Incommensurate Layer Compounds (RES)xNbS_2(RE=Rare-Earth Metals;x=1,2,0.6)." J.Phys.Soc.Jpn.63. 658-673 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] H.Kitagawa: "Pressure-Induced Metallization and Band-Type Jahn-Teller Transition in Perovskite-Type Mixed-Valence Metal Halide CsAuI_3" Phys.Rev.B. 51(to be published). (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] 小島憲道: "超高圧下における混合原子価錯体の原子価転移と相図." 高圧力の科学と技術. 3. 368-374 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kojima et al.: "Optical Investigation of the Intervalence Charge-Transfer Interaction in the three-Dimensional Au Mixed-Valence Compounds Cs_2Au_2X_6 (X=Cl, Br, I)" J.Chem.Soc.Dalton Trans.327-331 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kojima et al.: "P-T Phase Diagram and Gold Valence State of the Perovskite-Type Mixed-Valence Compounds Cs_2Au_2X_6 (X=Cl, Br, I) under High Pressures." J.Am.Chem.Soc.116. 11368-11374 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] S.S.Hafner et al.: "Divalent Gold in Perovskite Type CsAuI_3." Phys.Lett.A 192. 385-388 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] T.Terashima et al.: "Electrical Transport Properties of Incommensurate Layr Compounds (RES) _xNbS_2 (RE=Rare-Earth Metals ; X=1.2,0.6)." J.Phys.Soc.Jpn.63. 658-673 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kitagawa et al.: "Pressure-Induced Metallization and Band-Type Jahn-Teller Transition in Perovskite-Type Mixed-Valence Metal Halide CsAuI_3." Phys.Rev.B51 (to be published.). (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kojima: "Valence Transition and Phase Diagram of Mixed-Valence Compounds under High Pressure. (in Japanese)" Kouatsuryoku no kagaku to Gijutsu.3. 368-374 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1994 Final Research Report Summary
  • [Publications] N.Kojima: "Optical Investigation of the Intervalence Charge-Transfer Interaction in the Three-Dimensional Au Mixed-Valence Compounds Cs_2Au_2X_6(X=Cl,Br and I)" J.Chem.Soc.Dalton Trans.327-331 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] N.Kojima: "P-T Phase Diagram and Gold Valence State of the Perovskite-Type Mixed-Valence Compounds Cs_2Au_2X_6(X=Cl,Br, and I)under High Pressures" J.Am.Chem.Soc.116. 11368-11374 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] S.S.Hafner: "Divalent Gold in Perovskite Type CsAuI_3" Phys.Lett.A. 192. 385-388 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] T.Terashima: "Electrical Transport Properties of Incommensurate Layer Compounds (RES)_xNbS_2(RE=Rare-Earth Metals;x=1.2,0・6)" J.Phys.Soc.Jpn.63. 658-673 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] M.Hangyo: "Staging and Interlayer Interaction in the Misfit-Layer Compounds (RS)_nNbS_2(R=La,Ce;n=0.6,1.2)Studies by Raman and Infrared Spectroscopies." Phys.Rev.B. 50. 12033-12043 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 小島憲道: "超高圧下における混合原子価錯体の原子価転移と相図" 高圧力の科学と技術. 3. 368-374 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Kitagawa: "Electrical Conductivity and Its Anisotropy of the Mixed-Valence Compound Cs_2Au_2I_6 under High Pressure and Low Temperature" Synthetic Metals. 56. 1726-1729 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Sato: "Study on Carriers and Charge-Density Wave Transitions of Two-Dimensional Metals(K_<1-X>Rb_X)_3Cu_8S_6,K_3Cu_8(S_<1-X>Se_X)_6 and Rb_3Cu_8(S_<1-X>Se_X)_6" Synthetic Metals. 56. 2731-2736 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kojima: "Phase Diagram of the Three-Dimensional Halogen-Bridged Mixed-Valence Compounds M_2Au_2X_6(M=Rb,Csi X=Cl,Br,I) under High Pressure." Jpn.J.Appl.Phys.32-1. 51-53 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kojima: "^<197>Au Mossbauer Spectroscopy of the Cubic Phase in the Halogen Bridged Mixed Valence Complex Cs_2Au_2I_6." Nuclear Instruments and Methods in Physics Research. B76. 321-322 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kojima: "^<197>Au Mossbauer Spectroscopic Study on the Three-Dimensional Halogen Bridged Mixed Valence Complexes M_2Au_2X_6(M=Rb,Csi X=Br,I)" Nuclear Instruments and Methods in Physics Research. B76. 366-367 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Sato: "Effects of Alkali Substitution and Pressure on the Charge-Density Wave Transitions of Two-Dimensional Metals K_3Cu_8S_6 and Rb_3Cu_8S_6." J.Phys.Soc.Jpn.62. 647-658 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] H.Sato: "Structural Phase Transitions of the Quasi Two-Dimensional Metal (K_<1-X>Rb_X)_3Cu_8S_6:X-ray Scattering Studies." J.Phys.Soc.Jpn.62. 2051-2061 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kojima: "Optical Investigation of the Intervalence Charge-Transfer Interaction in the Three-Dimensional Au Mixed-Valence Compounds Cs_2Au_2X_6(X=Cl,Br and I)." J.Chem.Soc.Dalton Trans.327-331 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] N.Kojima: "P-T Phase Diagram and Au Valence State of the Perovskite-type Au Mixed-Valence Compounds Cs_2Au_2X_6(X=Cl,Br and I) under High Pressures." J.Am.Chem.Soc.(1994). (発表予定).

    • Related Report
      1993 Annual Research Report

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Published: 1993-04-01   Modified: 2020-05-15  

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