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Association and insertion complexes of nickel with water and methanol studied using Kohn-Sham theory

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Summary

The complexes formed by simple association of the nickel atom with water and methanol, and those formed by insertion of nickel into O-H and O-C bonds, have been studied by the Linear Combination of Gaussian-type orbitalsdensity functional (LCGTO-DF) method. The binding energies calculated for theassociation complexes are 7 kcal/mol for both Ni(H2O) and Ni(CH3OH). These association complexes have equilibrium geometries characterized by a tetrahedral arrangement of bonds and lone pair around the oxygen atom. Theinsertion complexes HNiOH and HNiOCH3 are more stable than the association complexes by 14 and 18 kcal/mol, respectively. The H3CNiOH insertion complex is still more stable, by an additional 14 kcal/mol. In all five complexes, the lowest singlet and triplet states are nearly degenerate. Comparison of calculated frequencies with infrared spectra of matrix isolated species [MA Park (1988) PhD thesis, Rice University] indicates that only triplet states are seen in the experiment.

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  1. Steacie Institute for Molecular Sciences, National Research Council of Canada, K1A 0R6, Ottawa, Canada

    René Fournier

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  1. René Fournier
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Fournier, R. Association and insertion complexes of nickel with water and methanol studied using Kohn-Sham theory. Theoret. Chim. Acta 91, 129–146 (1995). https://doi.org/10.1007/BF01114981

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  • DOI: https://doi.org/10.1007/BF01114981

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