Atomic bonding of neutral and cationic Mn clusters

Abstract

By using the spin-polarized DV-Xα-LCAO method, electronic states of neutral and cationic Mn _N clusters (N=2∼5) are calculated to study atomic bonding of Mn clusters. For the neutral Mn₂ cluster, the equilibrium interatomic distance is much larger than that of the bulk crystal. The 3d-derived states are nearly half-filled, and the 4s-derived states are almost fully occupied,i.e. the electronic configuration is close to that of the isolated atom. These indicate that the Mn₂ cluster is bound by the van der Waals force. The same situation is true for the larger neutral clusters while the equilibrium interatomic distance becomes smaller and thes-d mixing becomes larger. For the cationic clusters, the behaviors tend to become metallic. The equilibrium interatomic distances are smaller and thes-d mixings are larger than those of the corresponding neutral clusters. However, the Mn ⁺₂ and Mn ⁺₄ clusters still remain the van der Waals characters. Contrary to these clusters, the Mn ⁺₅ cluster, whose interatomic distance is smaller than that of the bulk crystal, shows strong metallic bonding. These results seem to correspond to the magic number observed on the mass spectroscopy of cationic Mn clusters.