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Photophysics of molecular transition metal compounds studied by inner-shell excitation

Research Project

Project/Area Number 11440209
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionOkazaki National Research Institutes

Principal Investigator

KOSUGI Nobuhiro  Institute for Molecular Science Professor, 分子科学研究所, 教授 (20153546)

Co-Investigator(Kenkyū-buntansha) HATSUI Takai  Institute for Molecular Science,Research Associate, 分子科学研究所, 助手 (40332176)
高田 恭孝  岡崎国立共同研究機構, 分子科学研究所, 助手 (90261122)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 2001: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2000: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1999: ¥4,500,000 (Direct Cost: ¥4,500,000)
KeywordsPolarized x-ray Absorption / Resonant Photoelectron / Resonant x-ray emission / Back dionation bondby / Charge Tramsfer Transition / Inne-shell excitation / 内殻励起 / 共鳴X線発光 / 電子相関 / 共有結合
Research Abstract

There are several planar complexes with two-dimensional structures in the transition metal compounds showing various physical properties. Details of photophysics, especially, inner-shell excitation and decay dynamics, of molecular transition metal compounds have not yet been revealed. In this work, we have been establishing fundamentals of the inner-shell spectroscopy applied to reveal photophysics of the molecular transition metal compound, by using 2p core spectroscopy of transition metals involving polarized photoabsorption and resonant photoelectron and soft x-ray emission since three years ago. The followings are new results from this work : 1) Electron correlation is reduced in the molecular transition metal compound, due to the covalent bond between the metal and ligand molecule. 2) Extraordinarily stronger satellite bands are observed according to stronger covalent bonds, and are assigned to the excitation from the metal to ligand unoccupied orbital. Polarized spectra have clearly shown that the ligand unoccupied orbital has 兀 * character. 3) We can evaluate the strength of the covalent bond by using the relative intensity of the satellite bands. 4) It is for the first time found that the kinetic energy of the photoelectron decreases as the photon energy increases in the satellite region. This means that the satellite bands arise from the single, or excitonic, excitation but does not from the electron correlation. The photon energy dependence of the electron kinetic energy is dependent on the molecular interaction among molecular transition metal compounds in the solid. Metallic systems show no dependence. 5) The high-spin molecular transition metal compounds do not show such dependence. This is due to the electron correlation, which becomes important in the high-spin compound. 6) It is revealed for the first time that resonant soft x-ray emission of molecular transition metal compounds show metal-to-ligand charge transfer bands.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] Lars G.M.Pettersson: "Ni 2p-3d photoabsorption and strong charge transfer satellites in divalent Ni complexes with molecular ligands"Chemical Physics Letters. 311. 299-305 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Takata: "Mg and Al K-edge XAFS measurements with a KTP crystal monochromator"Journal of Synchrotron Radiation. 8. 351-353 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Takata: "Resonant X-ray emission spectra of K_2Ni(CN)_4 at the Ni K-edge"Journal of Synchrotron Radiation. 8. 404-406 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] N.Kosugi: "Molecular field and spin-orbit splittings in the 2p ionization of second-row elements"Chemical Physics Letters. 329. 138-144 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Takata: "Valence excitations observed in resonant soft X-ray emission spectra of K_2Ni(CN)_4"Journal of Electron Spectroscopy. 114. 909-913 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] L.G.M. Pettersson, T. Hatsui, N. Kosugi: "Ni 2p-3d photoabsorption and strong charge transfer satellites in divalent Ni complexes with molecular ligands. Evaluation of π-back donation based on the DFT approach"Chem. Phys, Lett. Vol.311. 229-305 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y Takata, T. Iwazumi, N. Kosugi: "Resonant x-ray emission spectra of K2Ni(CN)_4 ? H_2O at the Ni K-edge"J. Synchrotron Rad,. Vol.8. 404-406 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y Takata, E. Shigemasa, N. Kosugi: "Mg and Al K-edge XAFS measurements with a KTP crystal monochromator"J. Synchrotron Rad. Vol.8. 351-353 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] N. Kosugi, T. Ishida: "Molecular field and spin-orbit splitting in the 2p ionization of second-row elements"Chem. Phys. Lett. Vol. 329. 138-144 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y Takata X Hatsui, N. Kosugi, A. Agui, M.Magnuson, C. Sathe, J.-E. Rubensspn, J. Nordgren: "Wence excitations observed in resonant soft X-ray emission spectra of K2Ni(CN)_4 H_2O at the Ni 2p edge"J Electron Spectrosc. Vol. 114. 909-913 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Y.Takata: "Valence excitations observed in resonant soft X-rayemission spectra of K_2N_i(CN)_4"Journal of Electron Spectroscopy. 114. 909-913 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Takata: "Mg and Al K-edge XAFS measurements with a KTP monochromator"Journal of Synchrotron Radiation. 8. 351-353 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Y.Takata: "Resonant X-ray emission spectra of K_2Ni (CN)_4・H_2O at the Ni K-edge"Journal of Synchrotron Radiation. 8. 404-406 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] N.Kosugi: "Molecular field and spin-orbit splitting in the 2p ionization of second-row-elements"Chemical Physics Letters. 329. 138-144 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Laws G.M. Pettersson: "Ni 2p-3d photoabsorption and strong charge transfer satellites in divalent Ni complexes with molecular ligands"Chemical Physics Letters. 311. 299-305 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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