ABSTRACT
The geometries and electronic structures of small Ninz clusters (n = 8, 9, 10) (z = 0, ±1, 2) have been elucidated for a range of multiplicities for each cluster size and charge, using density functional theory methods. These clusters have been found to conform in part to the existing superatomic model, with each cluster having a filled superatomic S-orbital, filled or partially filled superatomic P-orbitals, and empty or partially filled superatomic D-orbitals. Despite local states of mixed symmetry being present in the immediate vicinity of the Fermi energy, the addition or removal of a single electron from these systems causes a significant shift in the relative energies of the superatomic orbitals. In addition, this study demonstrates the possibility for d-electrons to contribute into superatomic orbitals to a greater or lesser extent, depending on the local environment. In summary, these observations lead to the prospect of a predictive model for electronic shell closings in some transition metal cluster systems.
