Insights into the geometries, electronic and magnetic properties of neutral and charged palladium clusters

We performed an unbiased structure search for low-lying energetic minima of neutral and charged palladium Pd(n)(Q) (n = 2–20, Q = 0, + 1 and –1) clusters using CALYPSO method in combination with density functional theory (DFT) calculations. The main candidates for the lowest energy neutral, cationic and anionic clusters are identified, and several new candidate structures for the cationic and anionic ground states are obtained. It is found that the ground state structures of small palladium clusters are more sensitive to the charge states. For the medium size Pd(n)(0/+/–) (n = 16–20) clusters, a fcc-like growth behavior is found. The structural transition from bilayer-like structures to cage-like structures is likely to occur at n = 14 for the neutral and cationic clusters. In contrast, for the anionic counterparts, the structural transition occurs at Pd(13)(–). The photoelectron spectra (PES) of palladium clusters are simulated based on the time-dependent density functional theory (TD-DFT) method and compared with the experimental data. The good agreement between the experimental PES and simulated spectra provides us unequivocal structural information to fully solve the global minimum structures, allowing for new molecular insights into the chemical interactions in the Pd cages

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag

Vibrational spectra of mass-selected Ag+(H2O)n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H2O molecules is found to be absent for cold Ag+(H2O)3, but detected for Ag+(H2O)4 through characteristic changes in the position and intensity of OH-stretching transitions. The third H2O coordinates directly to Ag+, but the fourth H2O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag+, in contrast to the efficient 4s–3d hybridization in Cu+. For Ag+(H2O)4, however, di-coordinated isomers are identified in addition to the tri-coordinated one

Photo-induced evolution of copper sheets from cluster molecules and its application to photolithographic copper patterning

UV photoexcitation of (t-butylethynyl copper)24 cluster films induces segregation of the crystals into metallic and organic phases and leads to evolve the metallic sheets sandwiched by organic polymers. The growth of the metallic crystals in the plane of the photo-electromagnetic field is attributed due to plasmon-plasmon interaction among nanoparticles embedded in dielectric polymer matrices. The surface enhanced photochemical reaction of residual cluster molecules on the photon incident direction is expected to take an important role for joining the metal particles to produce a metallic sheet. We can apply this phenomenon for photolithographic copper pattern generation on a flexible base plate

The polymerization of acetylene on supported metal clusters

The polymerization of acetylene was studied by thermal programmed reaction on model catalysts consisting of size-selected Ag, Rh, and Pd atoms and Pdn (1 ≤ n ≤ 30) clusters on well-characterized MgO(111) thin films. In a single-pass heating cycle experiment, benzene, butadiene, and butane were catalyzed with different selectivities as function of cluster size: palladium and rhodium atoms selectively produce benzene, and the highest selectivity for butadiene is observed for Pd₆, whereas Pd₂₀ reveals the highest selectivity for butane. Ag atoms are inert. These results provide an atom-by-atom observation of the selectivity of small cluster catalysts

Electronic and geometric properties of exohedral sodium- and gold-fullerenes

The electronic and geometric properties of gas-phase exohedral C60Na_N^-, C70Na_N^-, and C60Au_N^- cluster anions are investigated. Time-of-flight mass spectrometry and photoelectron spectroscopy (PES) reveal complex-specific arrangements of the sodium and the gold atoms on the fullerene cage. The electron affinity of C60AuN clearly shows even\ufffdodd alternation with the number of Au atoms, which suggests a "dry" structure where Au atoms aggregate as a cluster on the C60. In contrast, C60NaN and C70NaN show a "wet" structure having the Na atoms packed into stable trimers on the surface. For C60NaN (N = 0 to 4), PES experiments at a high photodetachment energy (5.81 eV) allow us to deduce the net charge transferred from the sodium atoms to the lowest unoccupied molecular orbital of the fullerene. For larger C60NaN, moreover, a metallic transition is shown to occur at N~13, and analysis of the adiabatic electron affinity variations allows the identification of the first magic sizes corresponding to electronic shell closure in the sodium layer.Peer reviewed: YesNRC publication: Ye

Very small “window of opportunity” for generating CO oxidation-active Au_n on TiO₂

Recent research in heterogeneous catalysis, especially on size-selected model systems under UHV conditions and also in realistic catalytic environments, has proved that it is necessary to think in terms of the exact number of atoms when it comes to catalyst design. This is of utmost importance if the amount of noble metal, gold in particular, is to be reduced for practical reactions like CO oxidation. Here it is shown that on TiO2 only Au6 and Au7 clusters are active for CO oxidation which holds for the single crystal, thin films, and titania clusters deposited on HOPG. Size-selected cluster deposition and TPD methods have been employed to investigate the CO oxidation activity of Aun/TiO2 systems which are compared to recent results reported by Lee et al. to form a consistent picture in which only two species can be regarded as “active”. The efficiency of investigated Aun/(TiO2)93/HOPG composite materials is attributed to carbon-assisted oxygen spillover from gold to support particles and across grain boundaries