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Small lanthanide clusters have interesting magnetic properties, but theirstructures are unknown. We have identified the structures of small terbiumcluster cations Tb (n = 5-9) in the gas phase, by analysis of their vibrationalspectra. The spectra have been measured via IR multiple photon dissociation oftheir complexes with Ar atoms in the 50-250 1/cm range with an infrared freeelectron laser. Density functional theory calculations using a 4f-in-coreeffective core potential (ECP) accurately reproduce the experimental far-IRspectra. The ECP corresponds to a 4f85d16s2 trivalent configuration of terbium.The assigned structures are similar to those observed in several othertransition metal systems. From this, we conclude that the bonding in Tbclusters is through the interactions between the 5d and 6s electrons, and thatthe 4f electrons have only an indirect effect on the cluster structures.

Structure of Magnetic Lanthanide Clusters from Far-IR Spectroscopy: Tb (n = 5-9)