A density-functional study of the structures, binding energies and total spins of Ni-Fe clusters using nonlocal...

We report ab initio calculations of the structures, binding energies, and total spins of the clusters Ni(13), Ni(19), Ni(23), Ni(26), Ni(12)Fe, Ni(11)Fe(2), Ni(18)Fe, Ni(17)Fe(2), Ni(22)Fe, Ni(20)Fe(3), and Ni(25)Fe using a density-functional method that employs linear combination of atomic orbitals as basis sets, nonlocal norm-conserving pseudopotentials, and the generalized gradient approximation for exchange and correlation. Our results show that the Fe-doped Ni clusters, which have icosahedral or polyicosahedral ground-state structures similar to those of the corresponding pure Ni clusters, are most stable with the Fe atoms occupying internal positions, as has also been inferred from experimental results on the adsorption of molecular nitrogen on the cluster surfaces. We also rule out the possibility that the experimentally observed difference between the (nonpolyicosahedral) configurations of N(2)-saturated Ni(26) and N(2)-saturated Ni(25)Fe be due to the influence of the Fe atom on the energy of the underlying metal cluster.