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Structure and electronic properties of iron oxide clusters: A first-principles study

Abstract:

In this study we present results of electronic structure calculations for some iron oxide clusters of the form Fen Om on the basis of the GGA+U approximation. The cluster size ranged between 33 and 113 atoms corresponding to length scales between around 7 Å and 12 Å in diameter, respectively. Initial atomic configurations before relaxation were created by considering two different space groups corresponding to the cubic Fd 3̄ m and monoclinic P2/c symmetries. The charge and the magnetization per atom were computed. In particular, the charge distribution of the cluster relaxed from cubic symmetry and containing 113 atoms reveals a well-defined periodic pattern of Fe pairs consistent with a partial charge-ordering scenario. Results evidence that the ground-state cohesive energy is smaller in the clusters originated from the P2/c symmetry. This fact indicates that at least in the largest cluster, having more tendency to preserve the initial structure, the low-temperature monoclinic phase is energetically more stable. Clusters starting from monoclinic symmetry are characterized by an insulating state, whereas those optimized from cubic symmetry exhibit a very small electronic gap. Finally, radial and angular distribution functions reveal strong modifications of the starting crystalline structures after relaxation with a tendency of forming cagelike structures. © 2009 The American Physical Society.