First-principles study on MRh12 (M = Rh, Fe, Co, AND Ni) clusters

In this paper, a first-principles study on the stability, electronic and magnetic properties of MRh₁₂ (M = Rh, Fe, Co and Ni) clusters is performed. By optimizing the geometrical structure, we find that MRh₁₂ clusters change from a perfect icosahedron to a distorted structure and have an obvious bond length contraction as compared with the corresponding bulk phase; FeRh₁₂, CoRh₁₂, and NiRh₁₂ clusters are more energetically stable than the RhRh₁₂ cluster. The effect of the impurity M on the density of states, valence band width, HOMO and LUMO for MRh₁₂ clusters is not significant, but when the central Rh atom is substituted with M, the magnetic moment of MRh₁₂ reduces dramatically. The Mulliken population analysis indicates that there are more charge transfers from other orbitals to Rh4d and M3d orbitals, and the spd hybrid effect in d orbitals of MRh₁₂ clusters is stronger than that in the RhRh₁₂ cluster. this situation means that the unpaired d electrons have more chance to be paired, and the magnetic moments of MRh₁₂ clusters can be reduced reasonably.