Spin states and quenching of magnetism in naked and carbonylated nickel clusters
1987; Elsevier BV; Volume: 134; Issue: 5 Linguagem: Inglês
10.1016/0009-2614(87)87163-4
ISSN1873-4448
AutoresGianfranco Pacchioni, Piercarlo Fantucci,
Tópico(s)Advanced Chemical Physics Studies
ResumoThe electronic structures of bare and carbonylated Ni3 and Ni5 clusters have been theoretically investigated by means of MO INDO calculations. In naked Ni3 and Ni5 clusters high-spin states are found to be much more stable than diamagnetic states. The bonding in these systems originates from the interaction of Ni atoms in a 3d94s1-like configuration. The progressive carbonylation of the cluster reduces the paramagnetism and the residual spin is preferentially localized on the coordinatively unsaturated Ni atoms. In fully carbonylated complexes, like Ni5(CO)12, the quenching of the magnetism is complete. The interaction with the carbonyl ligands markedly reduces the occupancy of the 4s orbitals and is expected to modify to some extent the nature of the metal-metal interaction.
Referência(s)