Electronic and Vibrational Signatures of the Au(p-MBA) Cluster.

Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations...

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Publicado en:Journal of the American Chemical Society Vol. 133; no. 11; pp. 3752 - 3756
Autores principales: Hulkko, Eero, Lopez-Acevedo, Olga, Koivisto, Jaakko, Levi-Kalisman, Yael, Kornberg, Roger D., Pettersson, Mika, Häkkinen, Hannu
Formato: Artículo
Publicado: American Chemical Society 3/23/2011
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 3/23/2011
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      pub: American Chemical Society
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        10.1021/ja111077e
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        atl: Electronic and Vibrational Signatures of the Au(p-MBA) Cluster.
      aug:
        au:
          Hulkko, Eero
          Lopez-Acevedo, Olga
          Koivisto, Jaakko
          Levi-Kalisman, Yael
          Kornberg, Roger D.
          Pettersson, Mika
          Häkkinen, Hannu
        affil:
          Nanoscience Center, Department of Chemistry, P.O. Box 35, FI-40014 University of Jyväskylä, Finland
          Department of Structural Biology, Stanford University School of Medicine, Stanford, California 94305, United States
          Nanoscience Center, Department of Physics, P.O. Box 35, FI-40014 University of Jyväskylä, Finland
      su:
        Light absorption
        Vibrational circular dichroism
        Cluster analysis (Statistics)
        Density functionals
        Glutathione
      sug:
        subj:
          Light absorption
          Vibrational circular dichroism
          Cluster analysis (Statistics)
          Density functionals
          Glutathione
      ab: Optical absorption of a gold nanocluster of 102 Au atoms protected by 44 para-mercaptobenzoic acid (p-MBA) ligands is measured in the range of 0.05-6.2 eV (mid-IR to UV) by a combination of several techniques for purified samples in solid and solution phases. The results are compared to calculations for a model cluster Au(SMe) based on the time-dependent density functional theory in the linear-response regime and using the known structure of Au(p-MBA). The measured and calculated molar absorption coefficients in the NIR-vis region are comparable, within a factor of 2, in the absolute scale. Several characteristic features are observed in the absorption in the range of 1.5-3.5 eV. The onset of the electronic transitions in the mid-IR region is experimentally observed at 0.45 ± 0.05 eV which compares well with the lowest calculated transition at 0.55 eV. Vibrations in the ligand layer give rise to fingerprint IR features below the onset of low-energy metal-to-metal electronic transitions. Partial exchange of the p-MBA ligand to glutathione does not affect the onset of the electronic transitions, which indicates that the metal core of the cluster is not affected by the ligand exchange. The full spectroscopic characterization of the Au(p-MBA) reported here for the first time gives benchmarks for further studies of manipulation and functionalization of this nanocluster to various applications.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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