Intermediate neglect of differential overlap spectroscopic studies of lanthanide complexes: Diatomic lanthanide oxides PrO and TmO

https://doi.org/10.1016/0022-2852(91)90060-NGet rights and content

Abstract

The low-lying states of PrO and TmO arising from the atomic-like molecular ground states 4f26s and 4f126s, respectively, are calculated employing a spectroscopic intermediate neglect of differential overlap (INDO) molecular orbital procedure augmented by a double-group configuration interaction (CI) technique which includes spin-orbit interactions. The molecular states closely follow the coupling pattern of the atomic states, as is revealed in a display according to the approximate quantum number Ja characterizing the total angular momentum number of the lanthanide contribution to the leading determinant. Overall agreement with experiment and recent ligand field calculations is very good, especially for the manifold of the lowest-lying multiplet component of PrO (Jf=4). Both theoretical procedures reproduce the experimental ω value for the ground state, 3.5. However, the INDO approach predicts a different ω for the ground state of TmO than do ligand field calculations.

References (36)

  • M. Kotzian et al.

    Chem. Phys. Lett.

    (1989)
  • P. Carette et al.

    J. Mol. Spectrosc.

    (1988)
  • M. Dulick et al.

    J. Mol. Spectrosc.

    (1985)
  • E.A. Shenyavskaya et al.

    J. Mol. Spectrosc.

    (1973)
  • J.C. Beaufils et al.

    J. Mol. Spectrosc.

    (1979)
  • M. Dulick et al.

    J. Mol. Spectrosc.

    (1979)
  • M. Dulick et al.

    J. Mol. Spectrosc.

    (1981)
  • M. Dulick et al.

    J. Mol. Spectrosc.

    (1981)
  • J.P. Desclaux

    Comput. Phys. Commun.

    (1975)
  • J.C. Culberson et al.

    Theor. Chim. Acta

    (1987)
  • M. Kotzian, N. Rösch, and M. C. Zerner, Theor. Chim. Acta, to be...
  • M. Kotzian et al.

    Eur. J. Solid State Inorg. Chem.

    (1991)
  • M. Dulick et al.

    J. Chem. Phys.

    (1986)
  • J.M. Delaval et al.

    Can. J. Spectrosc.

    (1977)
  • R.W. Field

    Ber. Bunsenges. Phys. Chem.

    (1982)
  • J.A. Pople et al.

    J. Chem. Phys.

    (1967)
  • R. Pariser

    J. Chem. Phys.

    (1953)
  • J.E. Ridley et al.

    Theor. Chim. Acta

    (1973)
  • Cited by (21)

    • Elucidating cerium + H<inf>2</inf>O reactivity through electronic structure: A combined PES and DFT study

      2017, Journal of Molecular Spectroscopy
      Citation Excerpt :

      Shake-up transitions are common features in core X-ray photoelectron spectra and have also been observed in valence anion PE spectra of metal and metal oxide clusters [23,24,33,34]. Small lanthanide monoxides are predicted to have a 4fn 5d excited state approximately 1 eV above the ground state [21,22]. These higher energy features are therefore tentatively assigned to shake-up transitions involving photodetachment of an electron from the doubly-occupied 6s-based HOMO coupled to the promotion of the remaining electron from the HOMO to a Ce 5d-based molecular orbital.

    • Excited state calculations of Europium(III) complexes

      1997, Journal of Alloys and Compounds
    • Chapter 152 Electronic structure calculations for molecules containing lanthanide atoms

      1996, Handbook on the Physics and Chemistry of Rare Earths
    • Photoelectron spectrum of PrO<sup>-</sup>

      2015, Journal of Chemical Physics
    View all citing articles on Scopus
    View full text