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Elucidating Solvation Structures of Metal Ions by Infrared Spectroscopy and Quantum Chemical Calculations of Gas-phase Clusters

Research Project

Project/Area Number 17550014
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKYUSHU UNIVERCITY

Principal Investigator

OHASHI Kazuhiko  Kyushu University, Faculty of Sciences, Associate Professor, 大学院数理学研究院, 助教授 (80213825)

Project Period (FY) 2005 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2005: ¥3,000,000 (Direct Cost: ¥3,000,000)
Keywordscluster / metal ion / laser spectroscopy / infrared Spectrum / density functional theory / solvation structure / coordination structure / hydrogen bonding / クラスター内反応
Research Abstract

Solvation structures of metal ions are explored by infrared (IR) photodissociation spectroscopy with the aid of density functional theory calculations. Selected examples of the results are as follows :
1. For Al / NH_3 system, the inserted [H-Al-NH_2]^+ structure is calculated to be higher in energy than the adduct [Al-NH_3]^+ structure. However, incremental solvation stabilizes the inserted structure more efficiently than the adduct structure, because of a larger effective charge on the Al atom in [H-Al-NH2]+. Actually, the IR spectra show that the [(H-Al-NH_2)(NH_3)_<n-1>]^+ ions are predominant over [Al-(NH_3)_n]^+ for n【greater than or equal】4.
2. The third H_2O attaches directly to Ag+ in a tri-coordinated form in Ag^+(H_2O)_3,while it occupies a hydrogen-bonding site in the second shell of the di-coordinated Cu+ in Cu^+(H_2O)_3. The preference of the tri-coordination is attributable to the inefficient 5s-4d hybridization in Ag+, in contrast to the extensive 4s-3d hybridization in Cu+ which retains the di-coordination. The fourth H_2O occupies the second shells of the tri-coordinated Ag+ and the di-coordinated Cu^+. Size dependent variations in the IR spectra of Cu+(H20)n, for n = 5-7 suggest that the di-coordinated structure acts as the core of further solvation processes.
3. In Cu^+(NH_3)_3, three NH_3 molecules are bonded directly to Cu+ in a tri-coordinated form. The IR spectra of Cu^+(NH_3)_n with n = 4 and 5 suggest the coexistence of multiple isomers, which have different coordination numbers (2, 3, and 4). With increasing n, however, the di-coordinated isomer is of growing importance until becoming predominant at n = 8. These results signify a strong tendency of Cu^+ to adopt the twofold linear coordination, as in the case of Cu^+(H_2O)_n.

Report

(3 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • Research Products

    (10 results)

All 2007 2006

All Journal Article (10 results)

  • [Journal Article] Coordination and solvation of noble metal ions : Infrared spectroscopy of Ag^+(H_2O)_n2007

    • Author(s)
      T.lino, K.Ohashi, et al.
    • Journal Title

      European Physical Journal D 43(in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Infrared spectroscopy of Cu^+(H_2O)_n and Ag^+(H_2O)_n : Coordination and solvation of noble-metal ions2007

    • Author(s)
      T.Iino, K.Ohashi, et al.
    • Journal Title

      Journal of Chemical Physics 126

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Coordination and solvation of noble metal ions : Infrared spectroscopy of Ag^+(H_2O)_n2007

    • Author(s)
      T.Iino, K.Ohashi, et al.
    • Journal Title

      European Physical Journal D 43(in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Infrared spectroscopy of Cu^+(H_2O)_n and Ag^+(H_2O)_n : Coordination and solvation of noble metal ions2007

    • Author(s)
      T.Iino, K.Ohashi, et al.
    • Journal Title

      Journal of Chemical Physics 126(in press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Infrared photodissociation spectroscopy of [Al(NH_3)_n]^+ (n = 1-5)2006

    • Author(s)
      Y.Mune, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 419

      Pages: 201-206

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Infrared photodissociation spectra and solvation structures of Cu^+(H_2O)_n (n = 1-4)2006

    • Author(s)
      T.lino, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 427

      Pages: 24-28

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Infrared photodissociation spectroscopy of [Al(NH_3)_n]^+ (n=1-5)2006

    • Author(s)
      Y.Mune, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 419

      Pages: 201-206

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Infrared photodissociation spectra and solvation structures of Cu^+(H_2O)_n (n=1-4)2006

    • Author(s)
      T.Iino, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 427

      Pages: 24-28

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Infrared photodissociation spectra and solvation structures of Cu^+(H_2O)_n(n=1-4)2006

    • Author(s)
      T.Iino, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 427

      Pages: 24-28

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Infrared photodissociation spectroscopy of [Al(NH_3)_n]^+(n=1-5)2006

    • Author(s)
      Y.Mune, K.Ohashi, et al.
    • Journal Title

      Chemical Physics Letters 419

      Pages: 201-206

    • Related Report
      2005 Annual Research Report

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Published: 2005-04-01   Modified: 2016-04-21  

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