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Communication: structure of magnetic lanthanide clusters from far-IR spectroscopy: Tb(n)+ (n = 5-9)
John Bowlan1, Dan J Harding, Jeroen Jalink
1Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany. jbowlan@fhi-berlin.mpg.de
Abstract:
Small lanthanide clusters have interesting magnetic properties, but their structures are unknown. We have identified the structures of small terbium cluster cations Tb(n)(+) (n = 5-9) in the gas phase by analysis of their vibrational spectra. The spectra have been measured via IR multiple photon dissociation of their complexes with Ar atoms in the 50-250 cm(-1) range with an infrared free electron laser. Density functional theory calculations using a 4f-in-core effective core potential (ECP) accurately reproduce the experimental far-IR spectra. The ECP corresponds to a 4f(8)5d(1)6s(2) trivalent configuration of terbium. The assigned structures are similar to those observed in several other transition metal systems. From this, we conclude that the bonding in Tb clusters is through the interactions between the 5d and 6s electrons, and that the 4f electrons have only an indirect effect on the cluster structures.
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