Range Of Cluster Sizes Research Articles

Upgrades at ClusterTrap and latest results

For the last decade the production of polyanionic metal clusters in the gas phase and the investigation of their size- and charge-state dependent properties was the main objective of the ClusterTrap experiment. An upgrading of the ion-trapping devices extends the range of anionic charge states: a recently installed Penning trap with a 12-T superconducting magnet provides an increased mass and thus cluster-size range, crucial to reach higher anionic charge states by means of the electron-bath method. Its cylindrical Penning trap is characterized and compared with respect to the previous asymptotically hyperbolical setup. In addition, polyanionic cluster production in a linear radio-frequency quadrupole (RFQ) trap has been initiated. Preliminary results for gold-cluster polyanion production in the new Penning trap, the RFQ trap, as well as the combined use of these traps are presented.

Critical Size Range of Sub-Nanometer Au Clusters for the Catalytic Activity in the Hydrogen Oxidation Reaction

Au clusters (25 atoms) are up to 180 times more active for the hydrogen oxidation reaction (HOR) than bulk Au. They were created from catalytically inactive Au clusters (2–5 atoms) by electrochemical activation in the presence of Au ions. The HOR activity depends on the cluster's size and it is related to the fact that the position of the LUMO is below the redox potential for the HOR, while HOMO is below the H 1s-Au d antibonding resonance.

A size resolved investigation of large water clusters

Size selected water clusters are generated by photoionizing sodium doped clusters close to the ionization threshold. This procedure is free of fragmentation. Upon infrared excitation, size- and isomer-specific OH-stretch spectra are obtained over a large range of cluster sizes. In one application of this method the infrared spectra of single water cluster sizes are investigated. A comparison with calculations, based on structures optimized by genetic algorithms, has been made to tentatively derive cluster structures which reproduce the experimental spectra. We identified a single all-surface structure for n = 25 and mixtures with one or two interior molecules for n = 24 and 32. In another application the sizes are determined at which the crystallization sets in. Surprisingly, this process strongly depends on the cluster temperature. The crystallization starts at sizes below n = 200 at higher temperatures and the onset is shifted to sizes above n = 400 at lower temperatures.

Fischer–Tropsch Synthesis: Oxidation of a Fraction of Cobalt Crystallites in Research Catalysts at the Onset of FT at Partial Pressures Mimicking 50 % CO Conversion

Freshly H2-reduced catalyst samples and FTS catalyst samples (i.e., freshly reduced and immediately exposed to the onset of FTS conditions corresponding to 50 % CO conversion) were prepared. Each sample was coated in situ using molten polywax and solidified so that an air-protected sample was obtained, which was stored in inert gas. XAS was utilized to investigate the oxidation state of cobalt. A fraction of cobalt crystallites in the freshly reduced research catalysts having lower-than-commercial loading and smaller crystallites undergoes a degree of oxidation to CoO at the onset of FTS conditions simulating 50 % CO conversion (i.e., the H2O partial pressure is high enough to induce some oxidation). Therefore, by decreasing Co content with the aim of improving the dispersion of cobalt and Co efficiency, very small Co crystallites are obtained. Their reoxidation at the onset of FTS is an unintended consequence. Thus, catalysts should be designed to have an optimum narrow cluster size range—small enough to increase Co surface site densities, but large enough to avoid reoxidation, and the stability problems that arise from having unreduced Co in the working catalyst (e.g., a complex coalescence and reduction mechanism).

Vibrational spectroscopy of water in hydrated lipid multi-bilayers. III. Water clustering and vibrational energy transfer

Water clustering and connectivity around lipid bilayers strongly influences the properties of membranes and is important for functions such as proton and ion transport. Vibrational anisotropic pump-probe spectroscopy is a powerful tool for understanding such clustering, as the measured anisotropy depends upon the time-scale and degree of intra- and intermolecular vibrational energy transfer. In this article, we use molecular dynamics simulations and theoretical vibrational spectroscopy to help interpret recent experimental measurements of the anisotropy of water in lipid multi-bilayers as a function of both lipid hydration level and isotopic substitution. Our calculations are in satisfactory agreement with the experiments of Piatkowski, Heij, and Bakker, and from our simulations we can directly probe water clustering and connectivity. We find that at low hydration levels, many water molecules are in fact isolated, although up to 70% of hydration water forms small water clusters or chains. At intermediate hydration levels, water forms a wide range of cluster sizes, while at higher hydration levels, the majority of water molecules are part of a large, percolating water cluster. Therefore, the size, number, and nature of water clusters are strongly dependent on lipid hydration level, and the measured anisotropy reflects this through its dependence on intermolecular energy transfer.

Conductance and bulk vertical detachment energy of hydrated sulphate and oxalate dianions: a theoretical study

Analytical expressions have been derived for the vertical detachment energy (VDE) for hydrated sulphate (SO2 −4) and oxalate (C2O2 −4) dianions that can be used to calculate the same over a wide range of cluster sizes including the bulk from the knowledge of VDE for a finite number of stable clusters. The calculated bulk detachment energies are found to be very good in agreement (within 5%) with the available experimental results for both the systems. It is observed that two or more water molecules will be essential for the stability of sulphate and oxalate dianions against spontaneous electron loss and this is consistent with the experiment. We have, for the first time, provided a scheme to calculate the radius of the solvent berg for sulphate and oxalate dianions. The calculated conductivity values for the sulphate and oxalate dianions using Stokes–Einstein relation and the radius of solvent berg are found to be very good in agreement (within 4%) with the available experimental results.

Displacement damage rate dependence of defect cluster formation in α-Fe during irradiation

Formation kinetics of defect clusters in pure iron during irradiation has been numerically investigated by reaction rate theory, with focusing on nucleation process of vacancy clusters (voids) and self-interstitial-atoms (SIA) clusters under a wide range of atomic displacement damage rate (dpa rate) and temperature conditions. In the rate theory model, the size dependence of thermal stability of a defect cluster is treated for a wide range of cluster size. The numerical analysis shows that the nucleation processes of voids and SIA-clusters are quite different from each other. As to the voids, the nucleation rate of voids depends much on temperature and dpa rate, and has the individual peak temperature for each dpa rate, during which the peak temperature increases with increasing dpa rate. This tendency for void nucleation is similar to that for void swelling observed in experiments. As to the SIA-clusters, the nucleation rate of SIA-clusters does not depend much on temperature and has no peak temperatures because of the relatively high thermal stability of an SIA-cluster, indicating that the conventional model (di-interstitial model) is applicable to describe the nucleation of SIA-clusters in a wide range of temperature.

Refractive Index Functions of TiO2 Nanoparticles

Wavelength-dependent refractive index functions (RIFs) of (TiO2)n nanoparticles (n = 2, 8, 18, 28, or 38) have been calculated by using the data from our previous density functional theory and time-dependent density functional theory photoabsorption calculations. The results show significant blueshifts and increased anisotropy in the RIFs of the nanoparticles, when compared to experimental bulk values. On the basis of the results, we conclude that, in the case of these ultrasmall particles, the RIFs may depend notably on the shape and structure of the cluster and on the other hand the fundamental absorption characteristics do not depend much on the rather limited cluster size range. The results also support the proposition that, in light-scattering measurements, one should not use the bulk RIF to model nanosize particles, at least in the case of TiO2 particles. Our results shed some light into this computationally and experimentally very challenging area of nanoparticle properties.

Inverse H/D Isotope Effects in Benzene Activation by Cationic and Anionic Cobalt Clusters

Reactions under single collision conditions with benzene C(6)H(6) and with benzene-d(6) C(6)D(6) of size selected cationic cobalt clusters Co(n)(+) and of anionic cobalt clusters Co(n)(-) in the cluster size range n = 3-28 revealed that dehydrogenation by cationic clusters is sparse, whereas it is ubiquitous in reactions by anionic clusters. Kinetic isotope effects (KIE) in total reaction rates are inverse and, in part, large. Dehydrogenation isotope effects (DIE) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate unravels a possible origin of the inverse KIE: Single step C-H bond activation is swift (no KIE in forward direction) and largely reversible (normal KIE backward) whereas H/D tunneling is likely to contribute (backward). DFT calculations of the structures and energetics along the reaction path in [Co(13)C(6)H(6)](+) lend support to the proposed multistep model. The observed effects on rates and KIEs of cluster charges and of cluster sizes are noted to elucidate further.

The cluster‐size dependence of self‐diffusion behavior: A single Re adatom on a hexahedral surface

AbstractThe self‐diffusion of a single Re adatom on the Re clusters with 967–8263 atoms is studied. The minimum‐energy diffusion paths and the corresponding energy barriers for adatom diffusion on the Re hexahedral structure clusters surfaces are determined through a combination of the quenched molecular dynamics (MD) and nudged elastic bands (NEB) methods. Within the studied cluster size range, the ES barriers for an adatom across the step from a (0001) facet to a neighboring ($1{\bar {1}}01$) facet are the same. This means that the ES barriers are independent of the size of the clusters, while, the ES barriers for an adatom across the step between two ($1{\bar {1}}01$) facet have some dependence on the number of the shell (k). The ES barriers of the clusters with k = even number is lower than that of the clusters with k = odd number. For the former, the ES barriers decrease with increasing cluster size.

Characterization of oil shale, isolated kerogen, and postpyrolysis residues using advanced 13C solid-state nuclear magnetic resonance spectroscopy

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360C, which contained more total aromatic carbon with a wide range of cluster sizes.

Quantitative Super-Resolution Imaging Reveals Protein Stoichiometry and Nanoscale Morphology of Assembling HIV-Gag Virions

The HIV structural protein Gag assembles to form spherical particles of radius ∼70 nm. During the assembly process, the number of Gag proteins increases over several orders of magnitude from a few at nucleation to thousands at completion. The challenge in studying protein assembly lies in the fact that current methods such as standard fluorescence or electron microscopy techniques cannot access all stages of the assembly process in a cellular context. Here, we demonstrate an approach using super-resolution fluorescence imaging that permits quantitative morphological and molecular counting analysis over a wide range of protein cluster sizes. We applied this technique to the analysis of hundreds of HIV-Gag clusters at the cellular plasma membrane, thus elucidating how different fluorescent labels can change the assembly of virions.

Molecular Dynamics Simulations of Competitive Freezing in Gold Nanoclusters

Molecular dynamics simulations are used to study the competitive freezing of icosahedral, decahedral, polydecahedral, and face-centered cubic structures in gold nanoclusters for a range of cluster sizes and temperatures. Measuring the probability of observing each cluster type in an ensemble of freezing events, along with the overall rate at which liquid drops freeze to any structure, allows us to calculate the rate of formation for each structure. An analysis of the freezing trajectories of the clusters reveals that both the icosahedron and the decahedron structures nucleate through the initial formation of a 5-fold symmetric cap. The icosahedron then continues to grow through the sequential growth of neighboring tetrahedral subunits, while the decahedral cluster grows out from the cap along the central 5-fold axis of symmetry.

Nonstandard cages in the formation process of methane clathrate: Stability, structure, and spectroscopic implications from first-principles

Endohedral CH(4)@(H(2)O)(n) (n = 16, 18, 20, 22, 24) clusters with standard and nonstandard cage configurations containing four-, five-, six-, seven-membered rings were generated by spiral algorithm and were systematically explored using DFT-D methods. The geometries of all isomers were optimized in vacuum and aqueous solution. In vacuum, encapsulation of methane molecules can stabilize the hollow (H(2)O)(n) cage by 2.31~5.44 kcal/mol; but the endohedral CH(4)@(H(2)O)(n) cages are still less stable than the pure (H(2)O)(n) clusters. Aqueous environment could promote the stabilities of the hollow (H(2)O)(n) cages as well as the CH(4)@(H(2)O)(n) clusters, and the CH(4)@(H(2)O)(n) clusters possess larger stabilization energies with regard to the pure (H(2)O)(n) clusters except for n = 24. The lowest energy structures of the CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cages are identical to the building units in the crystalline sI clathrate hydrate. All of the low-energy cages (including both regular and irregular ones) have large structural similarity and can be connected by "dimer-insertion" operation and Stone-Wales transformation. Our calculation also showed that in the range of cluster size n = 16-24, the relative energies of cage isomers tend to decrease with increasing number of the adjacent pentagons in the oxygen skeleton structures. In addition to the regular endohedral CH(4)@(H(2)O)(20) and CH(4)@(H(2)O)(24) cage structures, some nonstandard CH(4)@(H(2)O)(n) (n = 18, 20, 22, 24) cages have lower energies and might appear during nucleation process of methane hydrate. For the methane molecules in these low-energy cage isomers, we found that the C-H symmetric stretching frequencies show a red-shift trend and the (13)C NMR chemical shifts generally move toward negative values as the cavity size increases. These theoretical results are comparable to the available experimental data and might help experimental identification of the endohedral water cages during nucleation.

Scale-Invariant Correlations in Dynamic Bacterial Clusters

In Bacillus subtilis colonies, motile bacteria move collectively, spontaneously forming dynamic clusters. These bacterial clusters share similarities with other systems exhibiting polarized collective motion, such as bird flocks or fish schools. Here we study experimentally how velocity and orientation fluctuations within clusters are spatially correlated. For a range of cell density and cluster size, the correlation length is shown to be 30% of the spatial size of clusters, and the correlation functions collapse onto a master curve after rescaling the separation with correlation length. Our results demonstrate that correlations of velocity and orientation fluctuations are scale invariant in dynamic bacterial clusters.

Hydration of cellobiose: Structure and dynamics of cellobiose –(H2O)n, n = 5–25

Solvation of β-cellobiose isomers, cis and trans, in increasingly larger water clusters, is examined here by means of ab initio dynamics. A previously suggested hydration motif, based on a cluster with 2 waters, provides a stable nucleation center for growth of the larger cluster. Key results: (a) the cis form is energetically favored throughout the cluster size range; (b) cis conformer exhibits surfactant properties while (c) trans is better enveloped by water. Water organization at the sugar surface, is significantly different in the two isomers. Rotamer transitions, observed in the isolated sugar at 300K, are inhibited by the incomplete hydration shell.

Effect of internal mixture on black carbon radiative forcing

The effects of coating on black carbon (BC) optical properties and global climate forcing are revisited with more realistic approaches. We use the Generalized Multiparticle Mie method along with a realistic size range of monomers and clusters to compute the optical properties of uncoated BC clusters. Mie scattering is used to compute the optical properties of BC coated by scattering material. When integrated over the size distribution, we find the coating to increase BC absorption by up to a factor of 1.9 (1.8–2.1). We also find the coating can significantly increase or decrease BC backscattering depending on shell size and how shell material would be distributed if BC is uncoated. The effect of coating on BC forcing is computed by the Monte-Carlo Aerosol Cloud Radiation model with observed clouds and realistic BC spatial distributions. If we assume all the BC particles to be coated, the coating increases global BC forcing by a factor of 1.4 from the 1.9× absorption increase alone. Conversely, the coating can decrease the forcing by up to 60% or increase it by up to 40% by only the BC backscattering changes. Thus, the combined effects generally, but not necessarily, amplify BC forcing.

Theoretical study on microhydration of [formula omitted]: On the number of water molecules necessary to stabilize the dianion

Microhydration of SeO42-·nH2O (n=1–5) clusters are reported at B3LYP/Aug-cc-pvtz level of theory. Lower size hydrated clusters are stabilized by only double-hydrogen-bonding arrangements and the most stable conformer for higher size cluster (n>3) contains a cyclic water ring. It is observed that at least one water molecule is necessary to stabilize the dianion in the gas phase against spontaneous electron loss. The microscopic theory based expression provides a route to predict the instability of bare SeO42- and to obtain the VDE for a wide range of cluster sizes including the bulk from the knowledge of the same for a few stable hydrated clusters.

Self-energy and Fermi surface of the two-dimensional Hubbard model

We present an exact diagonalization study of the self-energy of the two-dimensional Hubbard model. To increase the range of available cluster sizes we use a corrected t-J model to compute approximate Greens functions for the Hubbard model. This allows to obtain spectra for clusters with 18 and 20 sites. The self-energy has several `bands' of poles with strong dispersion and extended incoherent continua with k-dependent intensity. We fit the self-energy by a minimal model and use this to extrapolate the cluster results to the infinite lattice. The resulting Fermi surface shows a transition from hole pockets in the underdoped regime to a large Fermi surface in the overdoped regime. We demonstrate that hole pockets can be completely consistent with the Luttinger theorem. Introduction of next-nearest neighbor hopping changes the self-energy stronlgy and the spectral function with nonvanishing next-nearest-neighbor hopping in the underdoped region is in good agreement with angle resolved photoelectron spectroscopy.

Conformationally averaged vertical detachment energy of finite size NO3−·nH2O clusters: a route connecting few to many

We report conformationally averaged VDEs (VDE(w)(n)) for different sizes of NO(3)(-)·nH(2)O clusters calculated by using uncorrelated HF, correlated hybrid density functional (B3LYP, BHHLYP) and correlated ab intio (MP2 and CCSD(T)) theory. It is observed that the VDE(w)(n) at the B3LYP/6-311++G(d,p), B3LYP/Aug-cc-Pvtz and CCSD(T)/6-311++G(d,p) levels is very close to the experimentally measured VDE. It is shown that the use of calculated results of the conformationally averaged VDE for small-sized solvated negatively-charged clusters and a microscopic theory-based general expression for the same provides a route to obtain the VDE for a wide range of cluster sizes, including bulk.