TEM characterization of chemically synthesized copper–gold nanoparticles

Dodecanethiol-capped Cu–Au nanoparticles, synthesized via a successive two-phase (water/toluene) and galvanic-exchange procedure, were characterized using transmission electron microscopy (TEM). The size range of the particles is around 1–7 nm. Electron-induced morphological evolution was observed under high resolution (HR) TEM. Cuboctahedral morphology was found to be thermodynamically stable. Electron-induced aggregation of two particles was also observed. Chemical ordering of cuboctahedral particles was studied by atomic-resolution high angle annular dark field (HAADF) imaging in scanning TEM (STEM) mode and energy dispersive X-ray (EDX) element mapping using a silicon drift detector (SDD). The particles were found to be Cu–Au mixed, and to be stable in air. Surface plasmon resonance (SPR), which is dependent on local structure and morphology, was investigated by electron energy loss spectroscopy (EELS).     

NMR in metal cluster compounds compared to glasses

The field and temperature dependence of the³¹P nuclear spin lattice relaxation rate in the metal cluster compound Ru₅₅(P(t-Bu)₃)₁₂Cl₂₀ follows a power law: 1/T ₁ ∝T ⁿ B ^?m , withn=1.5±0.1 at 3.25 T andn=1.3±0.1 at 6.45 T;m ? 1.4. Such dependences have so far only been observed in inorganic glasses and been attributed to two level systems. The correspondence suggests that the relaxation rate is due to interaction of theP-nuclear moment with electronic spins of stochastically moving charge carriers, which are thought to be responsible for the electrical conductivity through hopping between neigboring cluster molecules.     

Dielectric relaxation losses in lead chloride and lead bromide: Localized dipoles

A further analysis of previous reported measurements of dielectric relaxation losses in lead chloride and lead bromide crystals shows that the dipoles may occupy several energetically different positions, giving rise to localization of the dipoles and anomalous behaviour of the susceptibility. This energy difference is determined. Inspection of the crystal structure shows that the anion vacancy, being the mobile part of the dipole (which is an associate like (Me_Pb·V_X)^x or (O_X·V_X)^x where X = Cl, Br), may jump indeed between halide ion sites with different coordination number.A comparison between the dipole concentration as calculated from the observed losses and the associate concentration as estimated from ionic conductivity experiments leads to the conclusion that local field corrections in the calculations are important.     

69,71Ga NMR studies of a superconducting Ga 84 cluster compound

We present ^69,71Ga-NMR experiments on microcrystalline samples of the recently discovered supramolecular compound Ga ₈₄ [ N ( SiMe ₃ ) ₂ ] ₂₀ Li ₆ Br ₂ ( thf ) ₂₀ ^. 2 toluene, which is composed of ligand-coordinated Ga₈₄ metal clusters, packed together in a fully ordered crystalline matrix. The compound is highly conducting and even shows superconductivity below T _c ~ 7.2 K. Our preliminary results between 10-300 K show a metallic-like behavior: the nuclear spin-lattice relaxation rate T ₁ ^-1 follows the Korringa law ⁶⁹ ( T ₁ T ) ^-1 = 0.36 s ^-1 K ^-1 , but with a relaxation rate approximately three times smaller than in bulk -Ga metal. No quantum-size effects are observed, the Korringa law being followed down to 10 K, whereas the quantum-gaps for individual clusters should amount to ~ 10 ³ K. These results therefore suggest a transport process based on intermolecular charge transfer, similar as in alkali-doped fullerenes and silicon-clathrates.