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Theoretical Chemistry Accounts

, Volume 126, Issue 3–4, pp 243–255 | Cite as

Structural and optical properties of a neutral Nickel bisdithiolene complex: density functional versus ab initio methods

  • Fabienne Alary
  • Jean-Louis Heully
  • Anthony Scemama
  • Bénédicte Garreau-de Bonneval
  • Kathleen I. Chane-Ching
  • Michel Caffarel
Regular Article

Abstract

Density functional theory (DFT) and ab initio computations are applied to examine different properties of diamagnetic, square planar neutral nickel complexes that contain two bidentate ligands derived from bis ((ethylene)-1,2-dithiolato) ligands. Geometry, vibrational spectra (IR and Raman) are well reproduced in the density functional framework whereas TD-DFT methods are clearly insufficient to reproduce absorption properties. Multiconfigurational perturbation theory based on a complete active space self-consistent field wave function, i.e. MRPT2 and MRPT4 methods, reveal the pronounced multiconfigurational character of the ground state wave function. The singlet–triplet energy gap, the energy gained from symmetry breaking and the singlet diradical character are discussed in the DFT and ab initio frameworks. The complex of interest does not display a strong singlet diradical character. This molecule having a peculiar electronic structure; strong delocalization as shown by a new electron pair localization function analysis (EPLF); exemplifies the fragility of the TD-DFT method and thus, caution should be taken in the determination of the energetic properties of such compounds.

Keywords

Nickel bisdithiolene DFT Ab initio methods Biradical character EPLF 

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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Fabienne Alary
    • 1
  • Jean-Louis Heully
    • 1
  • Anthony Scemama
    • 1
  • Bénédicte Garreau-de Bonneval
    • 2
  • Kathleen I. Chane-Ching
    • 2
  • Michel Caffarel
    • 1
  1. 1.LCPQ-UMR 5626-IRSAMC-118Toulouse Cedex 07France
  2. 2.LCC-UPR 8241-205Toulouse Cedex 04France

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