Substrate-Selective Adhesion of Metal Nanoparticles to Graphene Devices.

Nanostructured electronic devices, such as those based on graphene, are typically grown on top of the insulator SiO2. Their exposure to a flux of small size-selected silver nanoparticles has revealed remarkably selective adhesion: the graphene channel can be made fully metallized, while the insulating substrate remains coverage-free. This conspicuous contrast derives from the low binding energy between the metal nanoparticles and a contaminant-free passivated silica surface. In addition to providing physical insight into nanoparticle adhesion, this effect may be of value in applications involving deposition of metallic layers on device working surfaces: it eliminates the need for masking the insulating region and the associated extensive and potentially deleterious pre- and postprocessing.

Probing the presence and absence of metal-fullerene electron transfer reactions in helium nanodroplets by deflection measurements.

Metal-fullerene compounds are characterized by significant electron transfer to the fullerene cage, giving rise to an electric dipole moment. We use the method of electrostatic beam deflection to verify whether such reactions take place within superfluid helium nanodroplets between an embedded C60 molecule and either alkali (heliophobic) or rare-earth (heliophilic) atoms. The two cases lead to distinctly different outcomes: C60Nan (n = 1-4) display no discernable dipole moment, while C60Yb is strongly polar. This suggests that the fullerene and small alkali clusters fail to form a charge-transfer bond in the helium matrix despite their strong van der Waals attraction. The C60Yb dipole moment, on the other hand, is in agreement with the value expected for an ionic complex.

Shells in CO2 clusters.

Abundance spectra of (CO2)N clusters up to N ≈ 500 acquired under a wide range of adiabatic expansion conditions are analyzed within the evaporative ensemble framework. The analysis reveals that the cluster stability functions display a strikingly universal pattern for all expansion conditions. These patterns reflect the inherent properties of individual clusters. From this analysis the size-dependent cluster binding energies are determined, shell and subshell closing sizes are identified, and cuboctahedral packing ordering for sizes above N ≈ 130 is confirmed. It is demonstrated that a few percent variation in the dissociation energies translates into significant abundance variations, especially for the larger clusters.

Kinetic energy deposited into a nanodroplet, cluster, or molecule in a sticking collision with background gas.

In processes when particles such as nanodroplets, clusters, or molecules move through a dilute background gas and undergo capture collisions, it is often important to know how much translational kinetic energy is deposited into the particles by these pick-up events. For sticking collisions with a Maxwell-Boltzmann gas, an exact expression is derived, which is valid for arbitrary relative magnitudes of the particle and thermal gas speeds.

Electric deflection of imidazole dimers and trimers in helium nanodroplets: Dipole moments, structure, and fragmentation.

Deuterated imidazole (IM) molecules, dimers, and trimers formed in liquid helium nanodroplets are studied by the electrostatic beam deflection method. Monitoring the deflection profile of (IM)D+ provides a direct way to establish that it is the primary product of the ionization-induced fragmentation both of (IM)2 and (IM)3. The magnitude of the deflection determines the electric dipole moments of the parent clusters: nearly 9 D for the dimer and 14.5 D for the trimer. These very large dipole values confirm theoretical predictions and derive from a polar chain bonding arrangement of the heterocyclic imidazole molecules.

Strong permanent magnet gradient deflector for Stern-Gerlach-type experiments on molecular beams.

We describe the design, assembly, and testing of a magnet intended to deflect beams of paramagnetic nanoclusters, molecules, and atoms. It is energized by high-grade permanent neodymium magnets. This offers a convenient option in terms of cost, portability, and scalability of the construction while providing field and gradient values (1.1 T, 330 T/m), which are fully comparable with those of commonly used electromagnet deflectors.

Oriented Polar Molecules Trapped in Cold Helium Nanodropets: Electrostatic Deflection, Size Separation, and Charge Migration.

Helium nanodroplets doped with polar molecules are studied by electrostatic deflection. This broadly applicable method allows even polyatomic molecules to attain subkelvin temperatures and nearly full orientation in the field. The resulting intense force from the field gradient strongly deflects even droplets with tens of thousands of atoms, the most massive neutral systems studied by beam "deflectometry." We use the deflections to extract droplet size distributions. Moreover, since each host droplet deflects according to its mass, spatial filtering of the deflected beam translates into size filtering of neutral fragile nanodroplets. As an example, we measure the dopant ionization probability as a function of droplet radius and determine the mean free path for charge hopping through the helium matrix. The technique will enable separation of doped and neat nanodroplets and size-dependent spectroscopic studies.

Direct detection of polar structure formation in helium nanodroplets by beam deflection measurements.

Long-range intermolecular forces are able to steer polar molecules submerged in superfluid helium nanodroplets into highly polar metastable configurations. We demonstrate that the presence of such special structures can be identified, in a direct and determinative way, by electrostatic deflection of the doped nanodroplet beam. The measurement also establishes the structures' electric dipole moments. In consequence, the introduced approach is complementary to spectroscopic studies of low-temperature molecular assembly reactions. It is enabled by the fact that within the cold superfluid matrix the molecular dipoles become nearly completely oriented by the applied electric field. As a result, the massive (tens of thousands of helium atoms) nanodroplets undergo significant deflections. The method is illustrated here by an application to dimers and trimers of dimethyl sulfoxide (DMSO) molecules. We interpret the experimental results with ab initio theory, mapping the potential energy surface of DMSO complexes and simulating their low temperature aggregation dynamics.

Controlled deposition of size-selected MnO nanoparticle thin films for water splitting applications: reduction of onset potential with particle size.

Emulating water oxidation catalyzed by the oxomanganese clusters in the photosynthetic apparatus of plants has been a long-standing scientific challenge. The use of manganese oxide films has been explored, but while they may be catalytically active on the surface, their poor conductivity hinders their overall performance. We have approached this problem by using manganese oxide nanoparticles with sizes of 4, 6 and 8 nm, produced in a sputter-gas-aggregation source and soft-landed onto conducting electrodes. The mass loading of these catalytic particles was kept constant and corresponded to 45%-80% of a monolayer coverage. Measurements of the water oxidation threshold revealed that the onset potential decreases significantly with decreasing particle size. The final stoichiometry of the catalytically active nanoparticles, after exposure to air, was identified as predominantly MnO. The ability of such a sub-monolayer film to lower the reaction threshold implies that the key role is played by intrinsic size effects, i.e., by changes in the electronic properties and surface fields of the nanoparticles with decreasing size. We anticipate that this work will serve to bridge the knowledge gap between bulk thick film electrocatalysts and natural photosynthetic molecular-cluster complexes.

Electrostatic Deflection of a Molecular Beam of Massive Neutral Particles: Fully Field-Oriented Polar Molecules within Superfluid Nanodroplets.

Electric deflection measurements on liquid helium nanodroplets doped with individual polar molecules demonstrate that the cold superfluid matrix enables full orientation of the molecular dipole along the external field. This translates into a deflection force that is increased enormously by comparison with typical deflection experiments, and it becomes possible to measurably deflect neutral doped droplets with masses of tens to hundreds of thousands of Daltons. By using continuous fluxes of fully oriented polar molecules and measuring the deflection of the doped nanodroplet beam, this approach makes it possible to directly determine the dipole moments of internally cryogenically cold molecules. The technique is broadly and generally applicable, including to complex and biological molecules.

Water cluster fragmentation probed by pickup experiments.

Electron ionization is a common tool for the mass spectrometry of atomic and molecular clusters. Any cluster can be ionized efficiently by sufficiently energetic electrons, but concomitant fragmentation can seriously obstruct the goal of size-resolved detection. We present a new general method to assess the original neutral population of the cluster beam. Clusters undergo a sticking collision with a molecule from a crossed beam, and the velocities of neat and doped cluster ion peaks are measured and compared. By making use of longitudinal momentum conservation, one can reconstruct the sizes of the neutral precursors. Here this method is applied to H2O and D2O clusters in the detected ion size range of 3-10. It is found that water clusters do fragment significantly upon electron impact: the deduced neutral precursor size is ∼3-5 times larger than the observed cluster ions. This conclusion agrees with beam size characterization by another experimental technique: photoionization after Na-doping. Abundant post-ionization fragmentation of water clusters must therefore be an important factor in the interpretation of experimental data; interestingly, there is at present no detailed microscopic understanding of the underlying fragmentation dynamics.

Energies and densities of electrons confined in elliptical and ellipsoidal quantum dots.

We consider a droplet of electrons confined within an external harmonic potential well of elliptical or ellipsoidal shape, a geometry commonly encountered in work with semiconductor quantum dots and other nanoscale or mesoscale structures. For droplet sizes exceeding the effective Bohr radius, the dominant contribution to average system parameters in the Thomas-Fermi approximation comes from the potential energy terms, which allows us to derive expressions describing the electron droplet's shape and dimensions, its density, total and capacitive energy, and chemical potential. The analytical results are in very good agreement with experimental data and numerical calculations, and make it possible to follow the dependence of the properties of the system on its parameters (the total number of electrons, the axial ratios and curvatures of the confinement potential, and the dielectric constant of the material). An interesting feature is that the eccentricity of the electron droplet is not the same as that of its confining potential well.

Note: Contamination-free loading of lithium metal into a nozzle source.

This note describes a system for transferring a load of high purity lithium metal into a molecular or cluster beam source. A hot loading vessel is thoroughly baked out while empty and overpressured with argon. A clean Li rod is then dropped in through a long narrow tube. The thoroughly degassed interior of the vessel and the rapid melting of the inserted rod facilitate contamination-free transfer of the highly reactive liquid metal into the source oven.

Nanocluster ionization energies and work function of aluminum, and their temperature dependence.

Ionization threshold energies of Al(n) (n = 32-95) nanoclusters are determined by laser ionization of free neutral metal clusters thermalized to several temperatures in the range from 65 K to 230 K. The photoion yield curves of cold clusters follow a quadratic energy dependence above threshold, in agreement with the Fowler law of surface photoemission. Accurate data collection and analysis procedures make it possible to resolve very small (few parts in a thousand) temperature-induced shifts in the ionization energies. Extrapolation of the data to the bulk limit enables a determination of the thermal shift of the polycrystalline metal work function, found to be in excellent agreement with theoretical prediction based on the influence of thermal expansion. Small clusters display somewhat larger thermal shifts, reflecting their greater susceptibility to thermal expansion. Ionization studies of free size-resolved nanoclusters facilitate understanding of the interplay of surface, electronic, and lattice properties under contamination-free conditions.

Proton transfer in histidine-tryptophan heterodimers embedded in helium droplets.

We used cold helium droplets as nano-scale reactors to form and ionize, by electron bombardment and charge transfer, aromatic amino acid heterodimers of histidine with tryptophan, methyl-tryptophan, and indole. The molecular interaction occurring through an N-H···N hydrogen bond leads to a proton transfer from the indole group of tryptophan to the imidazole group of histidine in a radical cationic environment.

Electric dipole moments of nanosolvated acid molecules in water clusters.

The electric dipole moments of (H2O)nDCl (n=3-9) clusters have been measured by the beam-deflection method. Reflecting the (dynamical) charge distribution within the system, the dipole moment contributes information about the microscopic structure of nanoscale solvation. The addition of a DCl molecule to a water cluster results in a strongly enhanced susceptibility. There is evidence for a noticeable rise in the dipole moment occurring at n≈5-6. This size is consistent with predictions for the onset of ionic dissociation. Additionally, a molecular-dynamics model suggests that even with a nominally bound impurity an enhanced dipole moment can arise due to the thermal and zero-point motion of the proton and the water molecules. The experimental measurements and the calculations draw attention to the importance of fluctuations in defining the polarity of water-based nanoclusters and generally to the essential role played by motional effects in determining the response of fluxional nanoscale systems under realistic conditions.

A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T ≳ 100 K.

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.

Double and triple ionization of silver clusters by electron impact.

The production of silver cluster cations Ag(n)(2+) (for several selected sizes in the range n = 39-119) and Ag(n)(3+) (for n = 58, 61, 67) by electron impact ionization of neutral precursors has been studied. The scaling of appearance energies with cluster radius follows the metallic droplet model but, curiously, with a slope which is estimated to be quite different from the literature values for single ionization, Ag(n)(+), as well as for the appearance of smaller Ag(n)(2+) ions. It is also found that as the electron energy increases, the yield of high-charge cations grows faster than that of singly-charged Ag(n)(+). This behavior is consistent with the power-law dependence of post-threshold ionization. The mechanisms involved in multiple ionization phenomena in clusters of noble metals are not yet fully understood and call for further experimental and theoretical examination.

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.

Slow electron attachment as a probe of cluster evaporation processes.

Neutral alkali clusters efficiently capture low-energy electrons with the aid of long-range polarization attraction. Upon attachment, the electron affinity and kinetic energy are dissipated into vibrations, heating the cluster and triggering evaporation of atoms and dimers. This process offers a novel means to explore nanocluster bonding and evaporation kinetics. The present work investigates the formation of Na(N)(-). A crossed-beam experiment reveals that relative anion abundances become strongly and nontrivially restructured with respect to the neutral precursor beam. This restructuring is explained in quantitative detail by an analysis of evaporative cascades initiated by the attachment. The analysis thus furnishes a complete description of the electron attachment process, from initial attraction to final rearrangement of the cluster population. In addition, the paper describes a systematic derivation of cluster evaporation kinetics and internal temperature distributions; a new relation between the dissociation energies of cationic, neutral, and anionic metal clusters; and a scenario for inferring the neutral cluster population in the supersonic beam from the cationic mass spectrum.