Theoretical study of the geometric and electronic structure of neutral and anionic doped silver clusters, Ag 5X 0,− with X = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni

Abstract

Density functional theory (DFT) has been applied to investigate the low-lying electronic states of neutral and anionic transition metal doped silver clusters Ag 5X 0,− with X = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni using the B3LYP functional with the Stuttgart SDD basis sets. The structural features, frontier orbital energy gaps (HOMO and LUMO), vertical detachment energies, and vertical and adiabatic electronic affinities are evaluated. For all doped silver clusters, both in neutral and anionic states, two-dimensional and three-dimensional low-energy isomers are found to coexist. For neutral clusters, dopant Sc, Ti, V, and Mn atoms largely decrease the frontier orbital energy gaps, while they are markedly increased by Sc and Fe atoms in the anionic clusters. A completely quenched dopant magnetic moment is found in Ag 5Sc, while high spin magnetic moments are located on the other dopant atoms in Ag 5X 0,−.