Showing papers on "Cluster (physics) published in 2015"

Role of Anions Associated with the Formation and Properties of Silver Clusters

Abstract: Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

Catalysis Applications of Size-Selected Cluster Deposition

Abstract: In this Perspective, we review recent studies of size-selected cluster deposition for catalysis applications performed at the U.S. DOE National Laboratories, with emphasis on work at Argonne National Laboratory (ANL) and Brookhaven National Laboratory (BNL). The focus is on the preparation of model supported catalysts in which the number of atoms in the deposited clusters is precisely controlled using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques. This approach is particularly effective for investigations of small nanoclusters, 0.5–2 nm (<200 atoms), where the rapid evolution of the atomic and electronic structure makes it essential to have precise control over cluster size. Cluster deposition allows for independent control of cluster size, coverage, and stoichiometry (e.g., the metal-to-oxygen ratio in an oxide cluster) and can be used to deposit on any substrate without constraints of nucleation and growth. Examples are presented for metal, metal oxide, a...

Prescribed nanoparticle cluster architectures and low-dimensional arrays built using octahedral DNA origami frames

Abstract: Three-dimensional mesoscale clusters that are formed from nanoparticles spatially arranged in pre-determined positions can be thought of as mesoscale analogues of molecules. These nanoparticle architectures could offer tailored properties due to collective effects, but developing a general platform for fabricating such clusters is a significant challenge. Here, we report a strategy for assembling three-dimensional nanoparticle clusters that uses a molecular frame designed with encoded vertices for particle placement. The frame is a DNA origami octahedron and can be used to fabricate clusters with various symmetries and particle compositions. Cryo-electron microscopy is used to uncover the structure of the DNA frame and to reveal that the nanoparticles are spatially coordinated in the prescribed manner. We show that the DNA frame and one set of nanoparticles can be used to create nanoclusters with different chiroptical activities. We also show that the octahedra can serve as programmable interparticle linkers, allowing one- and two-dimensional arrays to be assembled with designed particle arrangements.

Structure Determination of [Au18(SR)14]

Abstract: Unravelling the atomic structures of small gold clusters is the key to understanding the origin of metallic bonds and the nucleation of clusters from organometallic precursors. Herein we report the X-ray crystal structure of a charge-neutral [Au18(SC6H11)14] cluster. This structure exhibits an unprecedented bi-octahedral (or hexagonal close packing) Au9 kernel protected by staple-like motifs including one tetramer, one dimer, and three monomers. Until the present, the [Au18(SC6H11)14] cluster is the smallest crystallographically characterized gold cluster protected by thiolates and provides important insight into the structural evolution with size. Theoretical calculations indicate charge transfer from surface to kernel for the HOMO-LUMO transition.

Binding of dinitrogen to an iron–sulfur–carbon site

Abstract: Nitrogenases are the enzymes by which certain microorganisms convert atmospheric dinitrogen (N2) to ammonia, thereby providing essential nitrogen atoms for higher organisms. The most common nitrogenases reduce atmospheric N2 at the FeMo cofactor, a sulfur-rich iron-molybdenum cluster (FeMoco). The central iron sites that are coordinated to sulfur and carbon atoms in FeMoco have been proposed to be the substrate binding sites, on the basis of kinetic and spectroscopic studies. In the resting state, the central iron sites each have bonds to three sulfur atoms and one carbon atom. Addition of electrons to the resting state causes the FeMoco to react with N2, but the geometry and bonding environment of N2-bound species remain unknown. Here we describe a synthetic complex with a sulfur-rich coordination sphere that, upon reduction, breaks an Fe-S bond and binds N2. The product is the first synthetic Fe-N2 complex in which iron has bonds to sulfur and carbon atoms, providing a model for N2 coordination in the FeMoco. Our results demonstrate that breaking an Fe-S bond is a chemically reasonable route to N2 binding in the FeMoco, and show structural and spectroscopic details for weakened N2 on a sulfur-rich iron site.

Gold tetrahedra coil up: Kekulé-like and double helical superstructures.

Abstract: Magic-sized clusters, as the intermediate state between molecules and nanoparticles, exhibit critical transitions of structures and material properties. We report two unique structures of gold clusters solved by x-ray crystallography, including Au40 and Au52 protected by thiolates. The Au40 and Au52 clusters exhibit a high level of complexity, with the gold atoms in the cluster first segregated into four-atom tetrahedral units—which then coil up into a Kekule-like ring in the Au40 cluster and a DNA-like double helix in Au52. The solved structures imply a new “supermolecule” origin for revealing the stability of certain magic-sized gold clusters. The formation of supermolecular structures originates in the surface ligand bonding–induced stress and its propagation through the face-centered cubic (FCC) lattice. Moreover, the two structures reveal anisotropic growth of the FCC lattice in the cluster regime, which provides implications for the important roles of ligands at the atomic level. The rich structural information encoded in the Au40 and Au52 clusters provides atomic-scale insight into some important issues in cluster, nanoscale, and surface sciences.

Cobalt-centred boron molecular drums with the highest coordination number in the CoB16− cluster

Abstract: The electron deficiency and strong bonding capacity of boron have led to a vast variety of molecular structures in chemistry and materials science. Here we report the observation of highly symmetric cobalt-centered boron drum-like structures of CoB16(-), characterized by photoelectron spectroscopy and ab initio calculations. The photoelectron spectra display a relatively simple spectral pattern, suggesting a high symmetry structure. Two nearly degenerate isomers with D8d (I) and C4v (II) symmetries are found computationally to compete for the global minimum. These drum-like structures consist of two B8 rings sandwiching a cobalt atom, which has the highest coordination number known heretofore in chemistry. We show that doping of boron clusters with a transition metal atom induces an earlier two-dimensional to three-dimensional structural transition. The CoB16(-) cluster is tested as a building block in a triple-decker sandwich, suggesting a promising route for its realization in the solid state.

Cool Core Clusters from Cosmological Simulations

Abstract: We present results obtained from a set of cosmological hydrodynamic simulations of galaxy clusters, aimed at comparing predictions with observational data on the diversity between cool-core (CC) and non-cool-core (NCC) clusters. Our simulations include the effects of stellar and AGN feedback and are based on an improved version of the smoothed particle hydrodynamics code GADGET-3, which ameliorates gas mixing and better captures gas-dynamical instabilities by including a suitable artificial thermal diffusion. In this Letter, we focus our analysis on the entropy profiles, the primary diagnostic we used to classify the degree of cool-coreness of clusters, and on the iron profiles. In keeping with observations, our simulated clusters display a variety of behaviors in entropy profiles: they range from steadily decreasing profiles at small radii, characteristic of cool-core systems, to nearly flat core isentropic profiles, characteristic of non-cool-core systems. Using observational criteria to distinguish between the two classes of objects, we find that they occur in similar proportions in both simulations and in observations. Furthermore, we also find that simulated cool-core clusters have profiles of iron abundance that are steeper than those of NCC clusters, which is also in agreement with observational results. We show that the capability of our simulations to generate a realistic cool-core structure in the cluster population is due to AGN feedback and artificial thermal diffusion: their combined action allows us to naturally distribute the energy extracted from super-massive black holes and to compensate for the radiative losses of low-entropy gas with short cooling time residing in the cluster core.

Approximately A Thousand Ultra Diffuse Galaxies in the Coma cluster

Abstract: We report the discovery of 854 ultra diffuse galaxies (UDGs) in the Coma cluster using deep R band images, with partial B, i, and Halpha band coverage, obtained with the Subaru telescope. Many of them (332) are Milky Way-sized with very large effective radii of r_e>1.5kpc. This study was motivated by the recent discovery of 47 UDGs by van-Dokkum et al. (2015); our discovery suggests >1,000 UDGs after accounting for the smaller Subaru field. The new UDGs show a distribution concentrated around the cluster center, strongly suggesting that the great majority are (likely longtime) cluster members. They are a passively evolving population, lying along the red sequence in the CM diagram with no Halpha signature. Star formation was, therefore, quenched in the past. They have exponential light profiles, effective radii re ~ 800 pc- 5 kpc, effective surface brightnesses mu_e(R)=25-28 mag arcsec-2, and stellar masses ~1x10^7 - 5x10^8Msun. There is also a population of nucleated UDGs. Some MW-sized UDGs appear closer to the cluster center than previously reported; their survival in the strong tidal field, despite their large sizes, possibly indicates a large dark matter fraction protecting the diffuse stellar component. The indicated baryon fraction ~<1% is less than the cosmic average, and thus the gas must have been removed from the possibly massive dark halo. The UDG population appears to be elevated in the Coma cluster compared to the field, indicating that the gas removal mechanism is related primarily to the cluster environment.

Electric-field–induced assembly and propulsion of chiral colloidal clusters

Abstract: Chiral molecules with opposite handedness exhibit distinct physical, chemical, or biological properties. They pose challenges as well as opportunities in understanding the phase behavior of soft matter, designing enantioselective catalysts, and manufacturing single-handed pharmaceuticals. Microscopic particles, arranged in a chiral configuration, could also exhibit unusual optical, electric, or magnetic responses. Here we report a simple method to assemble achiral building blocks, i.e., the asymmetric colloidal dimers, into a family of chiral clusters. Under alternating current electric fields, two to four lying dimers associate closely with a central standing dimer and form both right- and left-handed clusters on a conducting substrate. The cluster configuration is primarily determined by the induced dipolar interactions between constituent dimers. Our theoretical model reveals that in-plane dipolar repulsion between petals in the cluster favors the achiral configuration, whereas out-of-plane attraction between the central dimer and surrounding petals favors a chiral arrangement. It is the competition between these two interactions that dictates the final configuration. The theoretical chirality phase diagram is found to be in excellent agreement with experimental observations. We further demonstrate that the broken symmetry in chiral clusters induces an unbalanced electrohydrodynamic flow surrounding them. As a result, they rotate in opposite directions according to their handedness. Both the assembly and propulsion mechanisms revealed here can be potentially applied to other types of asymmetric particles. Such kinds of chiral colloids will be useful for fabricating metamaterials, making model systems for both chiral molecules and active matter, or building propellers for microscale transport.

An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

Abstract: An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C– or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C– ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface ca...

Hubble Space Telescope Proper Motion (HSTPROMO) Catalogs of Galactic Globular Cluster. II. Kinematic Profiles and Maps

Abstract: We present kinematical analyses of 22 Galactic globular clusters using the Hubble Space Telescope proper motion catalogs recently presented in Bellini et al. For most clusters, this is the first proper-motion study ever performed, and, for many, this is the most detailed kinematic study of any kind. We use cleaned samples of bright stars to determine binned velocity-dispersion and velocity-anisotropy radial profiles and two-dimensional velocity-dispersion spatial maps. Using these profiles, we search for correlations between cluster kinematics and structural properties. We find the following: (1) more centrally concentrated clusters have steeper radial velocity-dispersion profiles; (2) on average, at 1σ confidence in two dimensions, the photometric and kinematic centers of globular clusters agree to within ∼1″, with a cluster-to-cluster rms of 4″(including observational uncertainties); (3) on average, the cores of globular clusters have isotropic velocity distributions to within 1% (), with a cluster-to-cluster rms of 2% (including observational uncertainties); (4) clusters generally have mildly radially anisotropic velocity distributions (–1.0) near the half-mass–radius, with bigger deviations from isotropy for clusters with longer relaxation times; and (5) there is a relation between and ellipticity, such that the more flattened clusters in the sample tend to be more anisotropic, with –1.0. Aside from these general results and correlations, the profiles and maps presented here can provide a basis for detailed dynamical modeling of individual globular clusters. Given the quality of the data, this is likely to provide new insights into a range of topics concerning globular cluster mass profiles, structure, and dynamics.

Doping Effects in Cluster‐Mediated Bond Activation

Abstract: Gas-phase investigations of judiciously doped oxide clusters permit to address fundamental challenges related to, for example, the low-temperature oxidation of CO or the selective conversion of hydrocarbons. Modifying the size and composition of a free cluster in a controlled way enables the modification of local charge effects and of spin states, and spectroscopic studies in combination with computational work help to identify the active site of a catalyst and to unravel mechanistic details. Also, the interplay of the support material with the reactive part of a composite catalyst cluster can be addressed. Examples will be presented demonstrating how and why the gas-phase reactivities of heteronuclear clusters, in comparison with their homonuclear counterparts, toward small, generally rather inert molecules can be increased, decreased, or not significantly affected.

Stellar Radial Velocities in the Old Open Cluster M67 (NGC 2682). I. Memberships, Binaries, and Kinematics

Abstract: (Abridged) We present results from 13776 radial-velocity (RV) measurements of 1278 candidate members of the old (4 Gyr) open cluster M67 (NGC 2682). The measurements are the results of a long-term survey that includes data from seven telescopes with observations for some stars spanning over 40 years. For narrow-lined stars, RVs are measured with precisions ranging from about 0.1 to 0.8 km/s. The combined stellar sample reaches from the brightest giants in the cluster down to about 4 magnitudes below the main-sequence turnoff (V = 16.5), covering a mass range of about 1.34 MSun to 0.76 MSun. Spatially, the sample extends to a radius of 30 arcmin (7.4 pc in projection at a distant of 850 pc or 6-7 core radii). We find M67 to have a mean RV of +33.64 km/s (with an internal precision of +/- 0.03 km/s). For stars with >=3 measurements, we derive RV membership probabilities and identify RV variables, finding 562 cluster members, 142 of which show significant RV variability. We use these cluster members to construct a color-magnitude diagram and identify a rich sample of stars that lie far from the standard single star isochrone, including the well-known blue stragglers, sub-subgiants and yellow giants. These exotic stars have a binary frequency of (at least) 80%, more than three times that detected for stars in the remainder of the sample. We confirm that the cluster is mass segregated, finding the binaries to be more centrally concentrated than the single stars in our sample at the 99.8% confidence level. The blue stragglers are centrally concentrated as compared to the solar-type main-sequence single stars in the cluster at the 99.7% confidence level. Accounting for both measurement precision and undetected binaries, we derive a RV dispersion in M67 of 0.59 +0.07 -0.06 km/s, which yields a virial mass for the cluster of 2100 +610 -550 MSun. WIYN Open Cluster Study. LXVII.

Can Single-Reference Coupled Cluster Theory Describe Static Correlation?

Abstract: While restricted single-reference coupled cluster theory truncated to singles and doubles (CCSD) provides very accurate results for weakly correlated systems, it usually fails in the presence of static or strong correlation. This failure is generally attributed to the qualitative breakdown of the reference, and can accordingly be corrected by using a multideterminant reference, including higher-body cluster operators in the ansatz, or allowing symmetry breaking in the reference. None of these solutions are ideal; multireference coupled cluster is not black box, including higher-body cluster operators is computationally demanding, and allowing symmetry breaking leads to the loss of good quantum numbers. It has long been recognized that quasidegeneracies can instead be treated by modifying the coupled cluster ansatz. The recently introduced pair coupled cluster doubles (pCCD) approach is one such example which avoids catastrophic failures and accurately models strong correlations in a symmetry-adapted frame...

A cluster in the making: alma reveals the initial conditions for high-mass cluster formation

Abstract: G0.253+0.016 is a molecular clump that appears to be on the verge of forming a high-mass cluster: its extremely low dust temperature, high mass, and high density, combined with its lack of prevalent star formation, make it an excellent candidate for an Arches-like cluster in a very early stage of formation. Here we present new Atacama Large Millimeter/Sub-millimeter Array observations of its small-scale (∼0.07 pc) 3 mm dust continuum and molecular line emission from 17 different species that probe a range of distinct physical and chemical conditions. The data reveal a complex network of emission features with a complicated velocity structure: there is emission on all spatial scales, the morphology of which ranges from small, compact regions to extended, filamentary structures that are seen in both emission and absorption. The dust column density is well traced by molecules with higher excitation energies and critical densities, consistent with a clump that has a denser interior. A statistical analysis supports the idea that turbulence shapes the observed gas structure within G0.253+0.016. We find a clear break in the turbulent power spectrum derived from the optically thin dust continuum emission at a spatial scale of ∼0.1 pc, which may correspond to the spatial scale at which gravity has overcome the thermal pressure. We suggest that G0.253+0.016 is on the verge of forming a cluster from hierarchical, filamentary structures that arise from a highly turbulent medium. Although the stellar distribution within high-mass Arches-like clusters is compact, centrally condensed, and smooth, the observed gas distribution within G0.253+0.016 is extended, with no high-mass central concentration, and has a complex, hierarchical structure. If this clump gives rise to a high-mass cluster and its stars are formed from this initially hierarchical gas structure, then the resulting cluster must evolve into a centrally condensed structure via a dynamical process.

Studying the YMC population of M83: how long clusters remain embedded, their interaction with the ISM and implications for GC formation theories

Abstract: The study of young massive clusters can provide key information for the formation of globular clusters, as they are often considered analogues. A currently unanswered question in this field is how long these massive clusters remain embedded in their natal gas, with important implications for the formation of multiple populations that have been used to explain phenomena observed in globular clusters. We present an analysis of ages and masses of the young massive cluster population of M83. Through visual inspection of the clusters, and comparison of their spectral energy distributions (SEDs) and position in colour–colour space, the clusters are all exposed (no longer embedded) by <4 Myr, most likely less, indicating that current proposed age spreads within older clusters are unlikely. We also present several methods of constraining the ages of very young massive clusters. This can often be difficult using SED fitting due to a lack of information to disentangle age–extinction degeneracies and possible inaccurate assumptions in the models used for the fitting. The individual morphology of the Hα around each cluster has a significant effect on the measured fluxes, which contributes to inaccuracies in the age estimates for clusters younger than 10 Myr using SED fitting. This is due to model uncertainties and aperture effects. Our methods to help constrain ages of young clusters include using the near-infrared and spectral features, such as Wolf–Rayet stars.

Geometry flexibility of copper iodide clusters: variability in luminescence thermochromism.

Abstract: An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of “eared cubane” cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.

Finding the Most Catalytically Active Platinum Clusters With Low Atomicity

Abstract: On a subnanometer scale, an only one-atom difference in a metal cluster may cause significant transitions in the catalytic activity due to the electronic and geometric configurations. We now report the atomicity-specific catalytic activity of platinum clusters with significantly small atomicity, especially below 20. The atomic coordination structure is completely different from that of the larger face-centered cubic (fcc) nanocrystals. Here, an electrochemical study on such small clusters, in which the atomicity ranged between 12 and 20, revealed Pt19 as the most catalytically active species. In combination with a theoretical study, a common structure that leads to a high catalytic performance is proposed.

Direct observation of particle interactions and clustering in charged granular streams

Abstract: By eliminating the effects of gravity with a free-falling camera, high-resolution imaging of charged grains reveals Keplerian orbits and electrostatically stable clusters—with implications for astrophysical and industrial cluster formation.

Cosmology and astrophysics from relaxed galaxy clusters – I. Sample selection

Abstract: This is the first in a series of papers studying the astrophysics and cosmology of massive, dynamically relaxed galaxy clusters. Here we present a new, automated method for identifying relaxed clusters based on their morphologies in X-ray imaging data. While broadly similar to others in the literature, the morphological quantities that we measure are specifically designed to provide a fair basis for comparison across a range of data quality and cluster redshifts, to be robust against missing data due to point-source masks and gaps between detectors, and to avoid strong assumptions about the cosmological background and cluster masses. Based on three morphological indicators - Symmetry, Peakiness and Alignment - we develop the SPA criterion for relaxation. This analysis was applied to a large sample of cluster observations from the Chandra and ROSAT archives. Of the 361 clusters which received the SPA treatment, 57 (16 per cent) were subsequently found to be relaxed according to our criterion. We compare our measurements to similar estimators in the literature, as well as projected ellipticity and other image measures, and comment on trends in the relaxed cluster fraction with redshift, temperature, and survey selection method. Code implementing our morphological analysis will be made available on the web.

A cluster in the making: ALMA reveals the initial conditions for high-mass cluster formation

Abstract: G0.253+0.016 is a molecular clump that appears to be on the verge of forming a high mass, Arches-like cluster. Here we present new ALMA observations of its small-scale (~0.07 pc) 3mm dust continuum and molecular line emission. The data reveal a complex network of emission features, the morphology of which ranges from small, compact regions to extended, filamentary structures that are seen in both emission and absorption. The dust column density is well traced by molecules with higher excitation energies and critical densities, consistent with a clump that has a denser interior. A statistical analysis supports the idea that turbulence shapes the observed gas structure within G0.253+0.016. We find a clear break in the turbulent power spectrum derived from the optically thin dust continuum emission at a spatial scale of ~0.1 pc, which may correspond to the spatial scale at which gravity has overcome the thermal pressure. We suggest that G0.253+0.016 is on the verge of forming a cluster from hierarchical, filamentary structures that arise from a highly turbulent medium. Although the stellar distribution within Arches-like clusters is compact, centrally condensed and smooth, the observed gas distribution within G0.253+0.016 is extended, with no high-mass central concentration, and has a complex, hierarchical structure. If this clump gives rise to a high-mass cluster and its stars are formed from this initially hierarchical gas structure, then the resulting cluster must evolve into a centrally condensed structure via a dynamical process.

Efficient Cluster Algorithm for Spin Glasses in Any Space Dimension

Abstract: Spin systems with frustration and disorder are notoriously difficult to study, both analytically and numerically. While the simulation of ferromagnetic statistical mechanical models benefits greatly from cluster algorithms, these accelerated dynamics methods remain elusive for generic spin-glass-like systems. Here, we present a cluster algorithm for Ising spin glasses that works in any space dimension and speeds up thermalization by at least one order of magnitude at temperatures where thermalization is typically difficult. Our isoenergetic cluster moves are based on the Houdayer cluster algorithm for two-dimensional spin glasses and lead to a speedup over conventional state-of-the-art methods that increases with the system size. We illustrate the benefits of the isoenergetic cluster moves in two and three space dimensions, as well as the nonplanar chimera topology found in the D-Wave Inc. quantum annealing machine.

DNA-Protected Silver Clusters for Nanophotonics

Abstract: DNA-protected silver clusters (AgN-DNA) possess unique fluorescence properties that depend on the specific DNA template that stabilizes the cluster. They exhibit peak emission wavelengths that range across the visible and near-IR spectrum. This wide color palette, combined with low toxicity, high fluorescence quantum yields of some clusters, low synthesis costs, small cluster sizes and compatibility with DNA are enabling many applications that employ AgN-DNA. Here we review what is known about the underlying composition and structure of AgN-DNA, and how these relate to the optical properties of these fascinating, hybrid biomolecule-metal cluster nanomaterials. We place AgN-DNA in the general context of ligand-stabilized metal clusters and compare their properties to those of other noble metal clusters stabilized by small molecule ligands. The methods used to isolate pure AgN-DNA for analysis of composition and for studies of solution and single-emitter optical properties are discussed. We give a brief overview of structurally sensitive chiroptical studies, both theoretical and experimental, and review experiments on bringing silver clusters of distinct size and color into nanoscale DNA assemblies. Progress towards using DNA scaffolds to assemble multi-cluster arrays is also reviewed.

Mesoscopic turbulence and local order in Janus particles self-propelling under an ac electric field

Abstract: To elucidate mechanisms of mesoscopic turbulence exhibited by active particles, we experimentally study turbulent states of nonliving self-propelled particles. We realize an experimental system with dense suspensions of asymmetrical colloidal particles (Janus particles) self-propelling on a two-dimensional surface under an ac electric field. Velocity fields of the Janus particles in the crowded situation can be regarded as a sort of turbulence because it contains many vortices and their velocities change abruptly. Correlation functions of their velocity field reveal the coexistence of polar alignment and antiparallel alignment interactions, which is considered to trigger mesoscopic turbulence. Probability distributions of local order parameters for polar and nematic orders indicate the formation of local clusters with particles moving in the same direction. A broad peak in the energy spectrum of the velocity field appears at the spatial scales where the polar alignment and the cluster formation are observed. Energy is injected at the particle scale and conserved quantities such as energy could be cascading toward the larger clusters.

Alkynyl-protected Au23 nanocluster: a 12-electron system.

Abstract: A 23-gold-atom nanocluster was prepared by NaBH4-mediated reduction of a solution of PhCCAu and Ph3PAuSbF6 in CH2Cl2. The cluster composition was determined to be [Au23(PhCC)9(Ph3P)6]2+ and single-crystal X-ray diffraction revealed that the cluster has an unprecedented Au17 kernel protected by three PhC2-Au-C2(Ph)-Au-C2Ph motifs and six Ph3P groups. The Au17 core can be viewed as the fusion of two Au10 units sharing a Au3 triangle. Electronic structure analysis from DFT calculations suggests that the stability of this unusual 12-electron cluster is a result of the splitting of the superatomic 1D orbitals under D3h symmetry of the Au17 kernel. The discovery and determination of the structure of the Au23 cluster demonstrates the versatility of the alkynyl ligand in leading to the formation of new cluster compounds.

Reversible Size Control of Silver Nanoclusters via Ligand-Exchange

Abstract: The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another, a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid–liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG = glutathionate] and Ag44(4-FTP)30 [4-FTP = 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (<5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a rece...

Inorganic Molybdenum Octahedral Nanosized Cluster Units, Versatile Functional Building Block for Nanoarchitectonics

Abstract: Recently, Nanoarchitectonics has been introducedas a new concept that refers to a technology systemfor arranging nanoscale structural units in a requiredarchitecture. Multifunctional properties are achieved by acombination of several materials in a well-defined architecture.In the frame of this concept, composite nanoarchitecturesrepresent a new class of nanostructured entitiesthat integrate various dissimilar nanoscale building blocksincluding clusters, particles, wires and films. The heterogeneouscomposite nanostructured materials are composedby definition of multi-(nano)components, each tailored toaddress different requirements. As one of the nanocomponents,nanometer sized metal clusters (<2 nm), whichconsist of less than a few dozens of metal atoms, could bedefined as a link between atom and nanoparticle. In thispaper, we will focus on our results on new nano-compositesinvolving Mo6 atom nanosized cluster units for optical,nanobiotechnology, energy and environmental applications.

Advances in the Engineering of Near Infrared Emitting Liquid Crystals and Copolymers, Extended Porous Frameworks, Theranostic Tools and Molecular Junctions Using Tailored Re6 Cluster Building Blocks

Abstract: At the occasion of the fiftieth birthday of the introduction of the term 'metal atom cluster' by F. A. Cotton in inorganic chemistry, it is the good time to make a review on the advances in the engineering of molecular assemblies and nanomaterials based on octahedral Re6 metal atom clusters. The latter exhibit unique intrinsic structural and physicochemical properties (orthogonal disposition of metallic sites that can be selectively functionalized, photoluminescence, redox, generation of singlet oxygen) that make them relevant building blocks for the structuration at the nanometric scale and functionalization of hybrid organic-inorganic materials and supramolecular frameworks. After synthesis by solid state chemistry techniques at high temperature, inorganic precursors built up on face-capped [(Re6Yi8)Ya6] cluster units (Y = chalcogen and/or halogen) can be functionalized via solution chemistry techniques or organic melts to form [(Re6Yi8)La6] (L = CN, OH, various organic ligands...). This work reports advances in the synthesis of [(Re6Yi8)Ya6] and [(Re6Yi8)La6] cluster units as well as on their use in the elaboration of supramolecular frameworks, nanoparticles, hybrid nanomaterials (co-polymers and liquid crystals) and active molecular junctions.

The Seven Sisters DANCe - I. Empirical isochrones, luminosity, and mass functions of the Pleiades cluster

Abstract: Context. The DANCe survey provides photometric and astrometric (position and proper motion) measurements for approximately 2 million unique sources in a region encompassing ~80 deg2 centered on the Pleiades cluster.Aims. We aim at deriving a complete census of the Pleiades and measure the mass and luminosity functions of the cluster.Methods. Using the probabilistic selection method previously described, we identified high probability members in the DANCe (i ≥ 14 mag) and Tycho-2 (V ≲ 12 mag) catalogues and studied the properties of the cluster over the corresponding luminosity range.Results. We find a total of 2109 high-probability members, of which 812 are new, making it the most extensive and complete census of the cluster to date. The luminosity and mass functions of the cluster are computed from the most massive members down to ~0.025 M ⊙ . The size, sensitivity, and quality of the sample result in the most precise luminosity and mass functions observed to date for a cluster. Conclusions. Our census supersedes previous studies of the Pleiades cluster populations, in terms of both sensitivity and accuracy.