Several general trends are recognized in determining the structure of Fe–Ni clusters. Larger clusters, containing both iron and nickel, are most stable with Fe atoms located in the inner parts of the cluster and Ni metals on outside. In other terms, when iron and nickel form body-centered cubic structures the preferred position of Ni atoms is at the surface, instead of at the center of the cluster, as it is energetically unfavorable for two nickel atoms to occupy nearest-neighbor positions.
Metal–metal bonds, being d-orbital interactions, happen at larger distances. More stable metal–metal bonds are expected to be longer than unstable bonds. This is shown by the fact that the Fe–Ni bond length is in between Ni–Ni and Fe–Fe bond lengths. For example, in Fe–Ni four-atom clusters (FeNi) which are most stable in a tetrahedral structure, the bond length of metal–metal Fe–Ni bond is 2.65Å and Fe–Fe bond is 2.85 Å. When bonding in these structures is examined, it follows that lowest energy cluster structures of iron and nickel are given by geometries with a maximum number of Fe–Fe bonds, and a small number of Ni–Ni bonds.
The simplest Fe–Ni clusters are of one iron atom and one nickel atom bonded together. More complex clusters can be added through the addition of another atom. Some pictures of sample geometries are shown in Fig. 2.
All Fe–Ni clusters exhibit some degree of distortion from usual geometry. This distortion generally becomes more pronounced as the number of Fe atoms increases.
Notice how in the above cluster diagrams, as calculated by Rollmann and colleagues, the symmetry of the cluster changes from a pure octahedron (D) to a square pyramid (C) as more iron atoms are added.