We investigate the electronic density of states (DOS) of isolated neutral cobalt clusters by probing the temperature-modulated population of electronic states through UV photoionization. The temperature is controlled via resonant excitation of lattice vibrations using the free-electron laser FELICE, after which the vibrational and electronic systems equilibrate through the electron-phonon coupling, redistributing the population of electronic states. The data are analyzed by surface photoemission theory, modified to incorporate the realistic DOS.

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.

Bi-metallic nanoalloys of mixed 3d-4d or 3d-5d elements are promising candidates for technological applications. The large magnetic moment of the 3d materials in combination with a high spin-orbit coupling of the 4d or 5d materials give rise to a material with a large magnetic moment and a strong magnetic anisotropy, making them ideally suitable in for example magnetic storage devices. Especially for clusters, which already have a higher magnetic moment compared to the bulk, these alloys can profit from the cooperative role of alloying and size reduction in order to obtain magnetically stable materials with a large magnetic moment. Here, the influence of doping of small cobalt clusters on the spin and orbital magnetic moment has been studied for the cations [Co(8-14)Au](+) and [Co(10-14)Rh](+). Compared to the undoped pure cobalt [Co(N)](+) clusters we find a significant increase in the spin moment for specific Co(N-1)Au(+) clusters and a very strong increase in the orbital moment for some Co(N-1)Rh(+) clusters, with more than doubling for Co12Rh(+). This result shows that substitutional doping of a 3d metal with even just one atom of a 4d or 5d metal can lead to dramatic changes in both spin and orbital moment, opening up the route to novel applications.

We recorded IR spectra for neutral cobalt clusters via two-color IR-UV ionization, using the Free Electron Laser for intracavity experiments (FELICE). Well-resolved IR spectra are presented for Co n (n = 4-10, 13) and analyzed with the help of Density Functional Theory calculations using two different correlation exchange functionals: the revisited Tao-Perdew-Staroverov-Scuseria (revTPSS) and the frequently used Perdew-Burke-Ernzerhof (PBE) approaches. Although we have not performed an extensive structure search, we tentatively assign the spectra for all cluster sizes except for n = 7, and n = 10. We find that neither of the two functionals chosen clearly outperforms the other in predicting IR spectra, and that relatively low scaling factors of 0.82 (PBE) and 0.8 (revTPSS) are required. In contrast to the magnetic moments, the calculated electric dipole moments fluctuate strongly as a function of cluster size and could therefore be used as an indirect probe to the cluster structure.