Nanoplasmonic electron acceleration in silver clusters studied by angular-resolved electron spectroscopy

The nanoplasmonic field enhancement effects in the energetic electron emission from few-nm-sized silver clusters exposed to intense femtosecond dual pulses are investigated by high-resolution double differential electron spectroscopy. For moderate laser intensities of 10 14Wcm -2, the delaydependent and angular-resolved electron spectra show laser-aligned emission of electrons up to keV kinetic energies, exceeding the ponderomotive potential by two orders of magnitude. The importance of the nanoplasmonic field enhancement due to resonant Mie-plasmon excitation observed for optimal pulse delays is investigated by a direct comparison with molecular dynamics results. The excellent agreement of the key signatures in the delay-dependent and angular-resolved spectra with simulation results allows for a quantitative analysis of the laser and plasmonic contributions to the acceleration process. The extracted field enhancement at resonance verifies the dominance of surfaceplasmon-assisted re-scattering

Unoccupied states of individual silver clusters and chains on Ag(111)

Size-selected silver clusters on Ag(111) were fabricated with the tip of a scanning tunneling microscope. Unoccupied electron resonances give rise to image contrast and spectral features which shift toward the Fermi level with increasing cluster size. Linear assemblies exhibit higher resonance energies than equally sized compact assemblies. Density functional theory calculations reproduce the observed energies and enable an assignment of the resonances to hybridized atomic 5s and 5p orbitals with silver substrate states.Comment: 9 pages, 8 figure

Ultrafast X-ray scattering of xenon nanoparticles: imaging transient states of matter

Sem informaçãoFemtosecond x-ray laser flashes with power densities of up to 10(14) W/cm(2) at 13.7 nm wavelength were scattered by single xenon clusters in the gas phase. Similar to light scattering from atmospheric microparticles, the x-ray diffraction patterns carry information about the optical constants of the objects. However, the high flux of the x-ray laser induces severe transient changes of the electronic configuration, resulting in a tenfold increase of absorption in the developing nanoplasma. The modification in opaqueness can be correlated to strong atomic charging of the particle leading to excitation of Xe4+. It is shown that single-shot single-particle scattering on femtosecond time scales yields insight into ultrafast processes in highly excited systems where conventional spectroscopy techniques are inherently blind.Femtosecond x-ray laser flashes with power densities of up to 10(14) W/cm(2) at 13.7 nm wavelength were scattered by single xenon clusters in the gas phase. Similar to light scattering from atmospheric microparticles, the x-ray diffraction patterns carry information about the optical constants of the objects. However, the high flux of the x-ray laser induces severe transient changes of the electronic configuration, resulting in a tenfold increase of absorption in the developing nanoplasma. The modification in opaqueness can be correlated to strong atomic charging of the particle leading to excitation of Xe4+. It is shown that single-shot single-particle scattering on femtosecond time scales yields insight into ultrafast processes in highly excited systems where conventional spectroscopy techniques are inherently blind.108915Sem informaçãoSem informaçãoBMBF [05KS4KT1, 05KS7KT2]HGF Virtuelles Institut [VH-VI-103, VH-VI-302]Sem informaçãoWe would like to thank all staff at FLASH for their outstanding support. Funding is acknowledged from BMBF 05KS4KT1 and 05KS7KT2, as well as HGF Virtuelles Institut VH-VI-103 and VH-VI-302

Recycling supercapacitors based on shredding and mild thermal treatment

Supercapacitors are widely used in electric and hybrid vehicles, wind farm and low-power equipment due to their high specific power density and huge number of charge–discharge cycles. Waste supercapacitors should be recycled according to EU directive 2002/96/EC on waste electric and electronic equipment. This paper describes a recycling approach for end-of-life supercapacitors based on shredding and mild thermal treatment. At first, supercapacitors are shredded using a Retsch cutting mill. The shredded mixture is then undergone thermal treatment at 200 °C to recycle the organic solvent contained in the activated carbon electrodes. After the thermal treatment, the mixture is roughly separated using a fluidized bed method to remove the aluminium foil particles and paper particles from the activated carbon particles, which is subsequently put into water for a wet shredding into fine particles that can be re-used. The recycled activated carbon has a BET surface area of up to 1200 m2/g and the recycled acetonitrile has a high purity

Aromaticity in a Surface Deposited Cluster: Pd4_4 on TiO2_2 (110)

We report the presence of \sigma-aromaticity in a surface deposited cluster, Pd$_4$ on TiO$_2$ (110). In the gas phase, Pd$_4$ adopts a tetrahedral structure. However, surface binding promotes a flat, \sigma-aromatic cluster. This is the first time aromaticity is found in surface deposited clusters. Systems of this type emerge as a promising class of catalyst, and so realization of aromaticity in them may help to rationalize their reactivity and catalytic properties, as a function of cluster size and composition.Comment: 4 pages, 3 figure

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 clusters, ~ 300 - 6 000, 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 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.Comment: 24 pages, 5 figure

Chemical Synthesis of Staphyloferrin B Affords Insight into the Molecular Structure, Iron Chelation, and Biological Activity of a Polycarboxylate Siderophore Deployed by the Human Pathogen

Staphyloferrin B (SB) is a citrate-based polycarboxylate siderophore produced and utilized by the human pathogen Staphylococcus aureus for acquiring iron when colonizing the vertebrate host. The first chemical synthesis of SB is reported, which enables further molecular and biological characterization and provides access to structural analogues of the siderophore. Under conditions of iron limitation, addition of synthetic SB to bacterial growth medium recovered the growth of the antibiotic resistant community isolate S. aureus USA300 JE2. Two structural analogues of SB, epiSB and SBimide, were also synthesized and employed to investigate how epimerization of the citric acid moiety or imide formation influence its function as a siderophore. Epimerization of the citric acid stereocenter perturbed the iron-binding properties and siderophore function of SB as evidenced by experimental and computational modeling studies. Although epiSB provided growth recovery to S. aureus USA300 JE2 cultured in iron-deficient medium, the effect was attenuated relative to that of SB. Moreover, SB more effectively sequestered the Fe(III) bound to human holo-transferrin, an iron source of S. aureus, than epiSB. SBimide is an imide analogous to the imide forms of other citric acid siderophores that are often observed when these molecules are isolated from natural sources. Here, SBimide is shown to be unstable, converting to native SB at physiological pH. SB is considered to be a virulence factor of S. aureus, a pathogen that poses a particular threat to public health because of the number of drug-resistant strains emerging in hospital and community settings. Iron acquisition by S. aureus is important for its ability to colonize the human host and cause disease, and new chemical insights into the structure and function of SB will inform the search for new therapeutic strategies for combating S. aureus infections.Alfred Benzon Foundation (Postdoctoral fellowship)Pacific Southwest Regional Center of ExcellenceAlfred P. Sloan Foundatio