Cryogenic cluster beam experiments have provided crucial insights into the evolution of the metallic state from the atom to the bulk. Surprisingly, one of the most fundamental metallic properties, the ability of a metal to efficiently screen electric fields, is still poorly understood in small clusters. Theory has predicted that many small Na clusters are unable to screen charge inhomogeneities and thus have permanent dipole moments. High precision electric deflection experiments on cryogenically cooled NaN (N < 200) clusters show that the electric dipole moments are at least an order of magnitude smaller than predicted, and are consistent with zero, as expected for a metal. The polarizabilities of Na clusters also show metal sphere behavior, with fine size oscillations caused by the shell structure.
The magnetic moments and electric dipoles of Tb and Pr clusters are investigated using the SternGerlach deflection technique. The addition of a single oxygen atom induces an increase in the electric dipole of Tb N clusters, however the magnetic moment is largely not affected. In Pr neither the magnetic moment nor the electric dipole is affected. This raises questions as to the role of conduction electrons in the exchange interaction of rare earth clusters, and puts into doubt the validity of the Ruderman-Kittel-Kasuya-Yosida ͑RKKY͒ exchange mechanism in small systems.
Homonuclear cobalt and iron clusters Co(N) and Fe(N) measured in a cryogenic molecular beam exist in two states with distinct magnetic moments (μ), polarizabilities, and ionization potentials, indicating distinct valences. The μ is approximately quantized: μ(N)∼2Nμ(B) in the ground states and μ(N)(*)∼Nμ(B) in the excited states for Co; μ(N)∼3Nμ(B) and μ(N)(*)∼Nμ(B) for Fe. At a large size, the average μ of the two states converges to the bulk value with diminishing ionization potential differences. The experiments suggest localized ferromagnetism in the two states and that itinerant ferromagnetism emerges from their superposition.
A unique property of size-resolved metal nanocluster particles is their "superatom"-like electronic shell structure. The shell levels are highly degenerate, and it has been predicted that this can enable exceptionally strong superconducting-type electron pair correlations in certain clusters composed of just tens to hundreds of atoms. Here we report on the observation of a possible spectroscopic signature of such an effect. A bulge-like feature appears in the photoionization yield curve of a free cold aluminum cluster and shows a rapid rise as the temperature approaches ≈100 K. This is an unusual effect, not previously reported for clusters. Its characteristics are consistent with an increase in the effective density of states accompanying a pairing transition, which suggests a high-temperature superconducting state with Tc ≳ 100 K. Our results highlight the promise of metal nanoclusters as high-Tc building blocks for materials and networks.
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