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Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals
Strong metal–support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H 2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO 2 and Nb 2 O 5 . In this report we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H 2 in a Pt structure dependent manner. Reductive treatment in H 2 at 300 °C induces the formation of an AlO x SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso) exposed available for catalysis. The remaining exposed Pt iso species possess a more uniform local coordination environment than has been observed on other forms of Al 2 O 3 , suggesting that the AlO x native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H 2 -induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.
HIDING IN PLAIN SIGHT: RECORD-BREAKING COMPACT STELLAR SYSTEMS IN THE SLOAN DIGITAL SKY SURVEY
Motivated by the recent, serendipitous discovery of the densest known galaxy, M60-UCD1, we present two initial findings from a follow-up search, using the Sloan Digital Sky Survey, Subaru/Suprime-Cam, and Hubble Space Telescope imaging, and SOuthern Astrophysical Research (SOAR)/Goodman spectroscopy. The first object discovered, M59-UCD3, has a similar size to M60-UCD1 (half-light radius of r{sub h} ∼ 20 pc) but is 40% more luminous (M{sub V} ∼ −14.6), making it the new densest-known galaxy. The second, M85-HCC1, has a size like a typical globular cluster (GC; r{sub h} ∼ 1.8 pc) but is much more luminous (M{sub V} ∼ −12.5). This hypercompact cluster is by far the densest confirmed free-floating stellar system, and is equivalent to the densest known nuclear star clusters. From spectroscopy, we find that both objects are relatively young (∼9 and ∼3 Gyr, respectively), with metal-abundances that resemble those of galaxy centers. Their host galaxies show clear signs of large-scale disturbances, and we conclude that these dense objects are the remnant nuclei of recently accreted galaxies. M59-UCD3 is an ideal target for follow-up with high-resolution imaging and spectroscopy to search for an overweight central supermassive black hole as was discovered in M60-UCD1. These findings also emphasize the potential value of ultra-compact dwarfs and massive GCs as tracers of the assembly histories of galaxies.
LIGHT-ELEMENT ABUNDANCES OF GIANT STARS IN THE GLOBULAR CLUSTER M71 (NGC 6838)
Aluminum is the heaviest light element displaying large star-to-star variations in Galactic globular clusters (GCs). This element may provide additional insight into the origin of the multiple populations, now known to be common place in GCs, and also the nature of the first-generation stars responsible for a cluster's chemical inhomogeneities. In a previous analysis, we found that unlike more metal-poor GCs, 47 Tuc did not exhibit a strong Na-Al correlation, which motivates a careful study of the similar metallicity but less massive GC M71. We present chemical abundances of O, Na, Al, and Fe for 33 giants in M71 using spectra obtained with the WIYN-Hydra spectrograph. Our spectroscopic analysis finds that similar to 47 Tuc and in contrast with more metal-poor GCs, M71 stars do not exhibit a strong Na-Al correlation and span a relatively narrow range in [Al/Fe], which are characteristics that GC formation models must reproduce.
Physical nature of longevity of light actinides in dynamic failure phenomenon
It is shown in this work that the physical nature of the longevity of light actinides under extreme conditions in a range of nonequilibrium states of t ∼ 10{sup –6}–10{sup –10} s is determined by the time needed for the formation of a critical concentration of a cascade of failure centers, which changes connectivity of the body. These centers form a percolation cluster. The longevity is composed of waiting time t{sub w} for the appearance of failure centers and clusterization time t{sub c} of cascade of failure centers, when connectivity in the system of failure centers and the percolation cluster arise. A unique mechanism of the dynamic failure process, a unique order parameter, and an equal dimensionality of the space in which the process occurs determine the physical nature of the longevity of metals, including fissionable materials.
On the Use of Field RR Lyrae As Galactic Probes: IV. New Insights Into and Around the Oosterhoff Dichotomy
We discuss the largest and most homogeneous spectroscopic data set of field RR Lyrae variables (RRLs) available to date. We estimated abundances using both high-resolution and low-resolution ($Δ$S method) spectra for fundamental (RRab) and first overtone (RRc) RRLs. The iron abundances for 7941 RRLs were supplemented with similar estimates that are available in the literature, ending up with 9015 RRLs (6150 RRab, 2865 RRc). The metallicity distribution shows a mean value of $\langle$[Fe/H]$\rangle$ = -1.51 ± 0.01, and $σ$(standard deviation) = 0.41 dex with a long metal-poor tail approaching [Fe/H] ≃ - 3 and a sharp metal-rich tail approaching solar iron abundance. The RRab variables are more metal-rich ( $\langle$[Fe/H]$\rangle$ ab = -1.48 ± 0.01, $σ$ = 0.41 dex) than RRc variables ($\langle$[Fe/H]$\rangle$ c = -1.58 ± 0.01, $σ$ = 0.40 dex). The relative fraction of RRab variables in the Bailey diagram (visual amplitude versus period) located along the short-period (more metal-rich) and the long-period (more metalpoor) sequences are 80% and 20%, while RRc variables display an opposite trend, namely 30% and 70%, respectively. We found that the pulsation period of both RRab and RRc variables steadily decreases when moving from the metal-poor to the metal-rich regime. Furthermore, the visual amplitude shows the same trend, but RRc amplitudes are almost two times more sensitive than RRab amplitudes to metallicity. We also investigated the dependence of the population ratio (N $c$ /N tot ) of field RRLs on the metallicity and we found that the distribution is more complex than in globular clusters. The population ratio steadily increases from ~0.25 to ~0.36 in the metal-poor regime, it decreases from ~0.36 to ~0.18 for -1.8 ≤ [Fe/H] ≤ -0.9 and it increases to a value of ~0.3 approaching solar iron abundance.
Bonding and Acidity of the Formal Hydride in the Prototypical Au 9 (PPh 3 ) 8 H 2+ Nanocluster
Abstract The role of hydrogen atoms as surface ligands on metal nanoclusters is of profound importance but remains difficult to directly study. While hydrogen atoms often appear to be incorporated formally as hydrides, evidence suggests that they donate electrons to the cluster's delocalized superatomic orbitals and may consequently behave as acidic protons that play key roles in synthetic or catalytic mechanisms. Here we directly test this assertion for the prototypical Au 9 (PPh 3 ) 8 H 2+ nanocluster, formed by addition of a hydride to the well‐characterized Au 9 (PPh 3 ) 8 3+ . Using gas‐phase infrared spectroscopy, we were able to unambiguously isolate Au 9 (PPh 3 ) 8 H 2+ and Au 9 (PPh 3 ) 8 D 2+ , revealing an Au−H stretching mode at 1528 cm −1 that shifts to 1038 cm −1 upon deuteration. This shift is greater than the maximum expected for a typical harmonic potential, suggesting a potential governing cluster‐H bonding that has some square‐well character consistent with the hydrogen nucleus behaving as a metal atom in the cluster core. Complexing this cluster with very weak bases reveals a redshift of 37 cm −1 in the Au−H vibration, consistent with those typically seen for moderately acidic groups in gas phase molecules and providing an estimate of the acidity of Au 9 (PPh 3 ) 8 H 2+ , at least with regard to its surface reactivity.
Soar adaptive optics observations of the globular cluster NGC 6496
We present high-quality BVRI photometric data in the field of globular cluster NGC 6496 obtained with the SOAR Telescope Adaptive Module (SAM). Our observations were collected as part of the ongoing SAM commissioning. The distance modulus and cluster color excess as found from the red clump are (m – M) {sub V} = 15.71 ± 0.02 mag and E(V – I) = 0.28 ± 0.02 mag. An age of 10.5 ± 0.5 Gyr is determined from the difference in magnitude between the red clump and the subgiant branch. These parameters are in excellent agreement with the values derived from isochrone fitting. From the color-magnitude diagram we find a metallicity of [Fe/H] = –0.65 dex and hence support a disk classification for NGC 6496. The complete BVRI data set for NGC 6469 is made available in the electronic edition of the Journal.
Spatially resolved distribution function and the medium-range order in metallic liquid and glass
The structural description of disordered systems has been a longstanding challenge in physical science. We propose an atomic cluster alignment method to reveal the development of three-dimensional topological ordering in a metallic liquid as it undercools to form a glass. By analyzing molecular dynamic (MD) simulation trajectories of a Cu 64.5 Zr 35.5 alloy, we show that medium-range order (MRO) develops in the liquid as it approaches the glass transition. Specifically, around Cu sites, we observe 'Bergman triacontahedron' packing (icosahedron, dodecahedron and icosahedron) that extends out to the fourth shell, forming an interpenetrating backbone network in the glass. The discovery of Bergman-type MRO from our order-mining technique provides unique insights into the topological ordering near the glass transition and the relationship between metallic glasses and quasicrystals.
Metallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer
We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc 3-x N@C 80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S 1 –T 1 gap decrease in this row. For Sc 3 N@C 80 , we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14 N, 45 Sc, and 89 Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y 3 N to Sc 3 N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.
Understanding the unique optical and vibrational signatures of sequential infiltration synthesis derived indium oxyhydroxide clusters for CO 2 absorption
Sequential infiltration synthesis (SIS) is a vapor phase synthesis technique with potential to exert precise control over metal oxyhydroxide incorporation into polymer scaffolds. Here, we observe strong size-dependent properties of InO x (OH) y few-atom clusters deposited with variable SIS cycle numbers within a polymethylmethacrylate (PMMA) matrix. Infrared spectroscopy and ultraviolet-visible absorption spectroscopy reveal that the metal atom coordination and optical properties of the clusters depend on the number of SIS cycles performed as well as the choice of processing parameters. The incorporation of indium oxyhydroxide in PMMA via SIS presents an opportunity to improve the CO 2 absorption capacity and gas selectivity of inexpensive polymers.
Spectroscopic confirmation of a mature galaxy cluster at a redshift of 2
Galaxy clusters are the most massive virialized structures in the Universe and are formed through the gravitational accretion of matter over cosmic time. The discovery of an evolved galaxy cluster at redshift z = 2, corresponding to a look-back time of 10.4 billion years, provides an opportunity to study its properties. The galaxy cluster XLSSC 122 was originally detected as a faint, extended X-ray source in the XMM Large Scale Structure survey and was revealed to be coincident with a compact over-density of galaxies with photometric redshifts of 1.9 ± 0.2. Subsequent observations at millimetre wavelengths detected a Sunyaev–Zel’dovich decrement along the line of sight to XLSSC 122, thus confirming the existence of hot intracluster gas, while deep imaging spectroscopy from the European Space Agency’s X-ray Multi-Mirror Mission (XMM-Newton) revealed an extended, X-ray-bright gaseous atmosphere with a virial temperature of 60 million Kelvin, enriched with metals to the same extent as are local clusters. Here we report optical spectroscopic observations of XLSSC 122 and identify 37 member galaxies at a mean redshift of 1.98, corresponding to a look-back time of 10.4 billion years. We use photometry to determine a mean, dust-free stellar age of 2.98 billion years, indicating that star formation commenced in these galaxies at a mean redshift of 12, when the Universe was only 370 million years old. The full range of inferred formation redshifts, including the effects of dust, covers the interval from 7 to 13. These observations confirm that XLSSC 122 is a remarkably mature galaxy cluster with both evolved stellar populations in the member galaxies and a hot, metal-rich gas composing the intracluster medium.
First Principles Modeling of Cluster-Based Solid Electrolytes (Final Technical Report)
Given the trend of global warming and the urgent need to transition from fossil fuels to green energy, lithium-ion batteries continue to be an integral part of our lives. Design, development, and understanding of novel solid-state electrolyte materials play the key role for achieving next-generation all-solid-state batteries with high energy and great safety. The current modeling schemes to develop advanced solid electrolytes are focusing on materials in which the building blocks are individual atoms. Our theoretical approach is a paradigm shift in solid-state electrolyte design. Instead of atoms, we focus on clusters as the building blocks and model these solid electrolytes and their interfaces with electrodes, especially Li-metal anode, for their successful implementation in solid-state batteries. The advantage of using the cluster ions to replace elemental ions is that the size, composition, and shape of the former can be tailored to achieve higher ionic conductivity at room temperature, electrochemical stability, and charge transfer across solid-solid interfaces than conventional materials. Specifically, the project includes: (1) Developing cluster-based solid electrolytes, where the halogen components are replaced by cluster ions that mimic the chemistry of halogens but are characterized by additional degrees of freedom, including the size, shape, composition, and motional dynamics under excitation. (2) Providing a fundamental understanding of the ion conduction mechanism in the developed cluster-based solid electrolytes; (3) Modeling the interfacial properties (i.e., structural, chemical, and transport properties) between the cluster-based solid electrolytes and electrodes at the atomic level. For the cluster-based solid electrolytes incompatible with the Li-metal anode or cathode materials, potential candidates for interfacial coatings are identified and studied. (4) Providing a theoretical framework towards optimizing critical parameters of the solid-state electrolytes that guides experimentalists to attain desired cathode-electrode interface for cluster-based solid-state electrolytes.
Applications of Polarizable Continuum Models To Determine Accurate Solution-Phase Thermochemical Values Across a Broad Range of Cation Charge – The Case of U(III–VI)
Contributing factors to the solution-phase correction to the free energy of the molecular clusters U(H 2 O) n 3+/4+ and UO 2 (H 2 O) m 1+/2+ ( n = 8, 9, 30, 41, 77; m = 4, 5, 30, 41, 77) have been examined as a function of cavity type in the integrated-equation-formalism-protocol (IEF) and SMD polarizable continuum models (PCMs). It is observed that the free energy correction, G corr , does not smoothly converge to zero as the number of explicitly solvating water molecules approaches the bulk limit, and the convergence behavior varies significantly with cavity and model. The rates of convergence of the gas-phase hydration energy, Δ G hyd , wherein the bare metal ion is inserted into a molecular water cluster and Δ G corr for the reaction exhibit wide variations as a function of ion charge, cavity, and model. This is the likely source of previously reported discrepancies in predicted free energies of solvation for metal ions when using different PCM cavities and/or models. The cancellation of errors in Δ G hyd and Δ G corr is optimal for clusters consisting of only a second solvation shell of explicit water molecules ( n = m = 30). Finally, the UFF cavity within IEF, in particular, exhibits the most consistent cancellation of errors when using a molecular cluster consisting of a second shell of solvating water for all oxidation states of uranium, leading to accurate free energies of solvation Δ G solv for these species.
Pd n Ag (4-n) and Pd n Pt (4-n) clusters on MgO (100): a density functional surface genetic algorithm investigation
We employed the novel surface mode of the Birmingham Cluster Genetic Algorithm (S-BCGA) for the global optimisation of noble metal tetramers upon an MgO(100) substrate at the GGA-DFT level of theory. The effect of element identity and alloying in surface-bound neutral subnanometre clusters is determined by energetic comparison between all compositions of Pd n Ag (4-n) and Pd n Pt (4-n) . And while the binding strengths to the surface increase in the order Pt > Pd > Ag, the excess energy profiles suggest a preference for mixed clusters for both cases. The binding of CO is also modelled, showing that the adsorption site can be predicted solely by electrophilicity. Comparison to CO binding on a single metal atom shows a reversal of the 5s-d activation process for clusters, weakening the cluster surface interaction on CO adsorption. Charge localisation determines homotop, CO binding and surface site preferences. Furthermore, the electronic behaviour, which is intermediate between molecular and metallic particles allows for tunable features in the subnanometre size range.
AGE AND MASS SEGREGATION OF MULTIPLE STELLAR POPULATIONS IN GALACTIC NUCLEI AND THEIR OBSERVATIONAL SIGNATURES
Nuclear stellar clusters (NSCs) are known to exist around massive black holes in galactic nuclei. They are thought to have formed through in situ star formation following gas inflow to the nucleus of the galaxy and/or through the infall of multiple stellar clusters. Here we study the latter, and explore the composite structure of the NSC and its relation to the various stellar populations originating from its progenitor infalling clusters. We use N-body simulations of cluster infalls and show that this scenario may produce observational signatures in the form of age segregation: the distribution of the stellar properties (e.g., stellar age and/or metallicity) in the NSCs reflects the infall history of the different clusters. The stellar populations of clusters, infalling at different times (dynamical ages), are differentially segregated in the NSC and are not fully mixed even after a few gigayears of evolution. Moreover, the radial properties of stellar populations in the progenitor cluster are mapped to their radial distribution in the final NSC, potentially leading to efficient mass segregation in NSCs, even those where relaxation times are longer than a Hubble time. Finally, the overall structures of the stellar populations present non-spherical configurations and show significant cluster to cluster population differences.
Formation of active sites on transition metals through reaction-driven migration of surface atoms
Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. Here we used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH 3 ) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought.
Asteroseismic study on cluster distance moduli for red giant branch stars in NGC 6791 and NGC 6819
Stellar distance is an important basic parameter in stellar astrophysics. Stars in a cluster are thought to be formed coevally from the same interstellar cloud of gas and dust; therefore, they are expected to have common properties. These common properties strengthen our ability to constrain theoretical models and/or to determine fundamental parameters, such as stellar mass, metal fraction, and distance, when tested against an ensemble of cluster stars. Here we derive a new relation based on solar-like oscillations, photometric observations, and the theory of stellar structure and evolution of red giant branch stars to determine cluster distance moduli through the global oscillation parameters Δν and ν{sub max} and photometric data V. The values of Δν and ν{sub max} are derived from Kepler observations. At the same time, it is used to interpret the trends between V and Δν. From the analyses of this newly derived relation and observational data of NGC 6791 and NGC 6819, we devise a method in which all stars in a cluster are regarded as one entity to determine the cluster distance modulus. This approach fully reflects the characteristic of member stars in a cluster as a natural sample. From this method we derive true distance moduli of 13.09 ± 0.10 mag for NGC 6791 and 11.88 ± 0.14 mag for NGC 6819. Additionally, we find that the distance modulus only slightly depends on the metallicity [Fe/H] in the new relation. A change of 0.1 dex in [Fe/H] will lead to a change of 0.06 mag in the distance modulus.