Assessment of density functional theory optimized basis sets for gradient corrected functionals to transition metal systems:: The case of small Nin (n≤5) clusters

Density functional calculations have been performed for small nickel clusters, Ni-n, Ni-n(+), and Ni-n(-) (n <= 5), using the linear combination of Gaussian-type orbital density functional theory approach. Newly developed nickel all-electron basis sets optimized for generalized gradient approximation (GGA) as well as an all-electron basis set optimized for the local density approximation were employed. For both neutral and charged systems, several isomers and different multiplicities were studied in order to determine the lowest energy structures. A vibrational analysis was performed in order to characterize these isomers. Structural parameters, harmonic frequencies, binding energies, ionization potentials, and electron affinities are reported. This work shows that the employed GGA basis sets for the nickel atom are important for the correct prediction of the ground state structures of small nickel clusters and that the structural assignment of these systems can be performed, with a good resolution, over the ionization potential. (C) 2007 American Institute of Physics.