Formation of Core-Shell Ethane-Silver Clusters in He Droplets.

Ethane core-silver shell clusters consisting of several thousand particles have been assembled in helium droplets upon capture of ethane molecules followed by Ag atoms. The composite clusters were studied via infrared laser spectroscopy in the range of the C-H stretching vibrations of ethane. The spectra reveal a splitting of the vibrational bands, which is ascribed to interaction with Ag. A rigorous analysis of band intensities for a varying number of trapped ethane molecules and Ag atoms indicates that the composite clusters consist of a core of ethane that is covered by relatively small Ag clusters. This metastable structure is stabilized due to fast dissipation in superfluid helium droplets of the cohesion energy of the clusters.

Formation of Large Ag Clusters with Shells of Methane, Ethylene, and Acetylene in He Droplets.

Helium droplets were used to assemble composite metal-molecular clusters. Produced clusters have several hundreds of silver atoms in the core, immersed in a shell consisting of methane, ethylene, or acetylene molecules. The structure of the clusters was studied via infrared spectra of the C-H stretches of the hydrocarbon molecules. The spectra of the clusters containing methane and acetylene show two distinct features due to molecules on the interface with silver core and those in the volume of the neat molecular part of the clusters. The relative intensities of the peaks are in good agreement with the estimates based on the number of the captured particles. Experiments also suggest that selection rules for infrared transitions for molecules adsorbed on metal surfaces are also valid for silver clusters as small as 300 atoms.

Formation of core-shell silver-ethane clusters in He droplets.

Here, we have studied the utility of large He droplets of 10(5)-10(7) atoms for the growth of composite clusters consisting of an Ag core and a shell of ethane molecules. The clusters have been assembled by doping He droplets with up to 10(3) Ag atoms and ethane molecules in two sequential pickup cells and studied via infrared spectroscopy in the C-H stretch region of the ethane molecules. We found that the ν7 band of ethane molecules at the interface with the Ag atoms has a low frequency shift of approximately 15 cm(-1) with respect to that of more distant ethane molecules away from the interface. The intensity ratio of the two bands was used for evaluation of the Ag core and ethane shell cluster structure. We found that the number of surface ethane molecules is in good agreement with a model that assumes a dense, core-shell structure for clusters containing less than about 100 atoms. However, large Ag clusters consisting of about 3000 atoms have a factor of about 5 larger surface area than that predicted by the model, indicating a ramified structure for such larger Ag clusters obtained in liquid He. Moreover, we demonstrate that He droplets behave as calorimeters for measurements of the number of captured atoms and molecules as well as the amount of absorbed laser energy.

Traces of vortices in superfluid helium droplets.

We report on the observation of vortices in superfluid 4He droplets produced in the expansion of liquid He. The vortices were traced by introducing Ag atoms, which clustered along the vortex lines, into the droplets. The Ag clusters were subsequently surface-deposited and imaged via electron microscopy. The prevalence of elongated track-shaped deposits shows that vortices are present in droplets larger than about 300 nm and that their lifetime exceeds a few milliseconds. We discuss the possible formation mechanisms and the stability of the vortices.

Sizes of large He droplets.

Helium droplets spanning a wide size range, N(He) = 10(3)-10(10), were formed in a continuous-nozzle beam expansion at different nozzle temperatures and a constant stagnation pressure of 20 bars. The average sizes of the droplets have been obtained by attenuation of the droplet beam through collisions with argon and helium gases at room temperature. The results obtained are in good agreement with previous measurements in the size range N(He) = 10(5)-10(7). Moreover, the measurements give the average sizes in the previously uncharacterized range of very large droplets of 10(7)-10(10) atoms. The droplet sizes and beam flux increase rapidly at nozzle temperatures below 6 K, which is ascribed to the formation of droplets within the nozzle interior. The mass spectra of the droplet beam upon electron impact ionization have also been obtained. The spectra show a large increase in the intensity of the He(4) (+) signal upon increase of the droplet size, an effect which can be used as a secondary size standard in the droplet size range N(He) = 10(4)-10(9) atoms.

Photoabsorption of Ag(n)(N∼6-6000) nanoclusters formed in helium droplets: transition from compact to multicenter aggregation.

Ag(N) clusters with up to thousands of atoms were grown in large He droplets and studied by optical spectroscopy. For N≲10(3) the spectra are dominated by a surface plasmon resonance near 3.8 eV and a broad feature in the UV, consistent with absorption by individual metallic particles. Larger clusters reveal unexpectedly strong broad absorption at low frequencies, extending down to ≈0.5 eV. This suggests a transition from single-center to multicenter formation, in agreement with estimates of cluster growth kinetics in He droplets. Moreover, the spectra of large clusters develop a characteristic dispersion profile at 3.5-4.5 eV, indicative of the coexistence of localized and delocalized electronic excitations in composite clusters, as predicted theoretically.

Surface deposition and imaging of large Ag clusters formed in He droplets.

The utility of a continuous beam of He droplets for the assembly and surface deposition of Ag(N) clusters, ~ 300-6000, is studied with transmission electron microscopy. Images of the clusters on amorphous carbon substrates obtained at short deposition times have provided for a measure of the size distribution of the metal clusters. The average sizes of the deposited clusters are in good agreement with an energy balance based estimate of Ag(N) cluster growth in He droplets. Measurements of the deposition rate indicate that upon impact with the surface the He-embedded cluster is attached with high probability. The stability of the deposited clusters on the substrate is discussed.