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

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
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Fabienne Alary, Jean-Louis Heully, Anthony Scemama, Bénédicte Garreau-de Bonneval, Kathleen Moineau-Chane Ching, et al.. Structural and optical properties of a neutral Nickel bisdithiolene complex: density functional versus ab initio methods. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, Springer Verlag, 2010, 126 (3-4), pp.243-255. ⟨10.1007/s00214-009-0679-9⟩. ⟨hal-00834777⟩

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