Probing the Electronic and Structural Properties of Chromium Oxide Clusters (CrO) and (CrO) (n = 1-5): Photoelectron Spectroscopy and Density Functional Calculations.

Photoelectron spectroscopy has been conducted for a series of (CrO) (n = 1-5) clusters and compared with density functional calculations. Well-resolved photoelectron spectra were obtained for (CrO) (n = 1-5) at 193 nm (6.424 eV) and 157 nm (7.866 eV) photon energies, allowing for accurate measuremen...

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Published in:Journal of the American Chemical Society Vol. 130; no. 15; pp. 5167 - 5178
Main Authors: Hua-Jin Zhai, Shenggang Li, Dixon, David A., Lai-Sheng Wang
Format: Article
Published: American Chemical Society 4/16/2008
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Online Access:View this record in EBSCOhost
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      dt: 4/16/2008
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        10.1021/ja077984d
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        atl: Probing the Electronic and Structural Properties of Chromium Oxide Clusters (CrO) and (CrO) (n = 1-5): Photoelectron Spectroscopy and Density Functional Calculations.
      aug:
        au:
          Hua-Jin Zhai
          Shenggang Li
          Dixon, David A.
          Lai-Sheng Wang
        affil:
          Department of Physics, Washington State University, 2710 University Drive, Rich/and, Washington 99354, Chemical & Materials Sciences Division, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352
          Chemistry Department, The University of Alabama, Shelby Hall, Box 870336, Tuscaloosa, Alabama 35487-0336
      su:
        Photoelectrons
        Binding energy
        Density functionals
        Functional analysis
        Molecular orbitals
        Electronic excitation
      sug:
        subj:
          Photoelectrons
          Binding energy
          Density functionals
          Functional analysis
          Molecular orbitals
          Electronic excitation
      ab: Photoelectron spectroscopy has been conducted for a series of (CrO) (n = 1-5) clusters and compared with density functional calculations. Well-resolved photoelectron spectra were obtained for (CrO) (n = 1-5) at 193 nm (6.424 eV) and 157 nm (7.866 eV) photon energies, allowing for accurate measurements of the electron binding energies, low-lying electronic excitations for n = 1 and 2, and the energy gaps. Density functional and molecular orbital theory (CCSD(T)) calculations were performed to locate the ground and low-lying excited states for the neutral clusters and to calculate the electron binding energies of the anionic species. The experimental and computational studies firmly establish the unique low-spin, nonplanar, cyclic ring structures for (CrO) and (CrO) for n ≥ 3. The structural parameters of (CrO) are shown to converge rapidly to those of the bulk CrO crystal. The extra electron in (CrO) (n ≥ 2) is shown to be largely delocalized over all Cr centers, in accord with the relatively sharp ground-state photoelectron bands. The measured energy gaps of (CrO) exhibit a sharp increase from n = 1 to n = 3 and approach to the bulk value of 2.25 eV at n = 4 and 5, consistent with the convergence of the structural parameters.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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