The electronic structure of Ni- And Ni2-ethylene cluster complexes

Harold Basch, M. D. Newton, J. W. Moskowitz

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The electronic structure of metal cluster-ethylene complexes has been investigated by carrying out ab initio bonding pair-correlated, self-consistent field, and configuration interaction (CI) calculations on the NiC 2H4 and Ni2C2H4 species. The π-NiC2H4 and π-Ni2C2H 4 cluster complexes are found to be bound, the former only with CI, while diσ-Ni2C2H4 has only a repulsive Ni2-C2H4 ground state potential curve. The bonding in the π-type cluster complexes can be described as follows: the metal atom configuration is 3d 94s1 with the 4s hybridized (by the metal 4p) away from the ethylene molecule, thereby allowing the σ orbital to form a dative σ bond with the metal atom. The bonding interaction is promoted by the presence of a second nickel atom behind the first one, leading to a 4s orbital electron deficiency of the bonded nickel atom and thus making this nickel atom a better electron acceptor. Back donation from the occupied metal 3d into the ethylene π* molecular orbital also takes place to some extent, and thus both features of the classical Dewar-Chatt-Duncanson model are observed. The π-Ni2C 2H4 species is analyzed in terms of the addition of a bare nickel atom to a π-NiC2H4 cluster complex, with concomitant stabilization of the orbitals of the bonded nickel atom. A study of the excited electronic states of π-NiC2H4 shows that low-lying 4s→π* and 3d→π*(M→L) charge transfer transitions are predicted. The former is not observed experimentally, probably due to the diffuse nature of the 4s orbital. The relationship between small cluster-ethylene complex systems and ethylene chemisorption on a nickel metal surface is discussed.

Original languageEnglish
Pages (from-to)584-597
Number of pages14
JournalJournal of Chemical Physics
Issue number2
StatePublished - 1978


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