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NASA NTRS2012

Constraints on Cosmic Rays, Magnetic Fields, and Dark Matter from Gamma-ray Observations of the Coma Cluster of Galaxies with VERITAS and FERMI

Observations of radio halos and relics in galaxy clusters indicate efficient electron acceleration. Protons should likewise be accelerated and, on account of weak energy losses, can accumulate, suggesting that clusters may also be sources of very high energy (VHE; E greater than100 GeV) gamma-ray emission. We report here on VHE gamma-ray observations of the Coma galaxy cluster with the VERITAS array of imaging Cerenkov telescopes, with complementing Fermi Large Area Telescope observations at GeV energies. No significant gamma-ray emission from the Coma Cluster was detected. Integral flux upper limits at the 99 confidence level were measured to be on the order of (2-5) x 10(sup -8) photons m(sup -2) s(sup -1) (VERITAS,greater than 220 GeV) and approximately 2 x 10(sup -6) photons m(sup -2) s(sup -1) (Fermi, 1-3 GeV), respectively. We use the gamma-ray upper limits to constrain cosmic rays (CRs) and magnetic fields in Coma. Using an analytical approach, the CR-to-thermal pressure ratio is constrained to be less than 16% from VERITAS data and less than 1.7% from Fermi data (averaged within the virial radius). These upper limits are starting to constrain the CR physics in self-consistent cosmological cluster simulations and cap the maximum CR acceleration efficiency at structure formation shocks to be 50. Alternatively, this may argue for non-negligible CR transport processes such as CR streaming and diffusion into the outer cluster regions. Assuming that the radio-emitting electrons of the Coma halo result from hadronic CR interactions, the observations imply a lower limit on the central magnetic field in Coma of approximately (2-5.5)microG, depending on the radial magnetic field profile and on the gamma-ray spectral index. Since these values are below those inferred by Faraday rotation measurements in Coma (for most of the parameter space), this renders the hadronic model a very plausible explanation of the Coma radio halo. Finally, since galaxy clusters are dark matter (DM) dominated, the VERITAS upper limits have been used to place constraints on the thermally averaged product of the total self-annihilation cross section and the relative velocity of the DM particles, (sigma upsilon)

cosmic↗
DOE OSTI2025

FLAMINGO: combining kinetic SZ effect and galaxy–galaxy lensing measurements to gauge the impact of feedback on large-scale structure

Energetic feedback processes associated with accreting supermassive black holes can expel gas from massive haloes and significantly alter various measures of clustering on $\sim$Mpc scales, potentially biasing the values of cosmological parameters inferred from analyses of large-scale structure (LSS) if not modelled accurately. Here, we use the state-of-the-art FLAMINGO suite of cosmological hydrodynamical simulations to gauge the impact of feedback on large-scale structure by comparing to Planck + ACT stacking measurements of the kinetic Sunyaev–Zel’dovich (kSZ) effect of SDSS BOSS galaxies. We make careful like-with-like comparisons to the observations, aided by high precision KiDS and DES galaxy–galaxy lensing measurements of the BOSS galaxies to inform the selection of the simulated galaxies. In qualitative agreement with several recent studies using dark matter only simulations corrected for baryonic effects, we find that the kSZ effect measurements prefer stronger feedback than predicted by simulations which have been calibrated to reproduce the gas fractions of low redshift X-ray-selected groups and clusters. We find that the increased feedback can help to reduce the so-called $S_8$ tension between the observed and CMB-predicted clustering on small scales as probed by cosmic shear (although at the expense of agreement with the X-ray group measurements). However, the increased feedback is only marginally effective at reducing the reported offsets between the predicted and observed clustering as probed by the thermal SZ (tSZ) effect power spectrum and tSZ effect – weak lensing cross-spectrum, both of which are sensitive to higher halo masses than cosmic shear.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Existence of tidal tails for the globular cluster NGC 5824

Context: Several dynamically cold streams have been associated with certain globular clusters (GCs) based on orbital energies and angular momenta. Some of these streams are surprisingly far apart from their progenitors and one such pair is Triangulum and NGC 5824. Triangulum can be considered as a piece of the leading tail of NGC 5824 since the cluster’s future orbit matches well with the stream’s track. The existence of the leading tail of NGC 5824 is the motivation behind the search for its trailing tail. Aims: Our goal is to confirm the connection between Triangulum and NGC 5824. We also search for the trailing tail of the cluster. Methods: The selection of member stars of Triangulum is made through various cuts in metallicity, proper motions (PMs), radial velocity and a color–magnitude diagram (CMD). The selected members are compared in phase space to a mock stream that models the disruption of NGC 5824. We then try to detect the trailing tail of the cluster based on a modified matched-filter technique. Stars are assigned weights using their color differences from the cluster’s locus in the CMD. These weights are further scaled, based on the stars’ departures from expected PMs of the model stream. Results: A total of 26 member stars for Triangulum are obtained, 16 of which are newly identified. These members are consistent with the mock stream in the phase space, and their metalicity and position on the CMD are in good agreement with NGC 5824. By applying the matched filter, a tenuous trailing tail of the cluster is detected, spanning ~50° long on sky. The signature matches well with the mock stream’s trajectory. Conclusions: Our results support that the Triangulum stream acts as a part of the leading tail for NGC 5824. On the trailing side, we detected a 50° tail extending from the cluster. The existence of both leading and trailing tails for the GC NGC 5824 is verified.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Passivating Nucleobases Bring Charge Transfer Character to Optically Active Transitions in Small Silver Nanoclusters

DNA-wrapped silver nanoclusters (DNA–AgNCs) are known for their efficient luminescence. However, their emission is highly sensitive to the DNA sequence, the cluster size, and its charge state. To get better insights into photophysics of these hybrid systems, simulations based on density functional theory (DFT) are performed. Our calculations elucidate the effect of the structural conformations, charges, solvent polarity, and passivating bases on optical spectra of DNA–AgNCs containing five and six Ag atoms. It is found that inclusion of water in calculations as a polar solvent media results in stabilization of nonplanar conformations of base-passivated clusters, while their planar conformations are more stable in vacuum, similar to the bare Ag5 and Ag6 clusters. Cytosines and guanines interact with the cluster twice stronger than thymines, due to their larger dipole moments. In addition to the base–cluster interactions, hydrogen bonds between bases notably contribute to the structure stabilization. While the relative intensity, line width, and the energy of absorption peaks are slightly changing depending on the cluster charge, conformations, and base types, the overall spectral shape with five well-resolved bands at 2.5–5.5 eV is consistent for all structures. Independent of the passivating bases and the cluster size and charge, the low energy optical transitions at 2.5–3.5 eV exhibit a metal to ligand charge transfer (MLCT) character with the main contribution emerging from Ag-core to the bases. Cytosines facilitate the MLCT character to a larger degree comparing to the other bases. However, the doublet transitions in clusters with the open shell electronic structure (Ag5 and Ag6 + ) result in appearance of additional red-shifted (<2.5 eV) and optically weak band with negligible MLCT character. The passivated clusters with the closed shell electronic structure (Ag5 + and Ag6) exhibit higher optical intensity of their lowest transitions with much higher MLCT contribution, thus having better potential for emission, than their open shell counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Archetypal TRMM Radar Profiles Identified Through Cluster Analysis

It is widely held that identifiable 'convective regimes' exist in nature, although precise definitions of these are elusive. Examples include land / Ocean distinctions, break / monsoon beahvior, seasonal differences in the Amazon (SON vs DJF), etc. These regimes are often described by differences in the realized local convective spectra, and measured by various metrics of convective intensity, depth, areal coverage and rainfall amount. Objective regime identification may be valuable in several ways: regimes may serve as natural 'branch points' in satellite retrieval algorithms or data assimilation efforts; one example might be objective identification of regions that 'should' share a similar 2-R relationship. Similarly, objectively defined regimes may provide guidance on optimal siting of ground validation efforts. Objectively defined regimes could also serve as natural (rather than arbitrary geographic) domain 'controls' in studies of convective response to environmental forcing. Quantification of convective vertical structure has traditionally involved parametric study of prescribed quantities thought to be important to convective dynamics: maximum radar reflectivity, cloud top height, 30-35 dBZ echo top height, rain rate, etc. Individually, these parameters are somewhat deficient as their interpretation is often nonunique (the same metric value may signify different physics in different storm realizations). Individual metrics also fail to capture the coherence and interrelationships between vertical levels available in full 3-D radar datasets. An alternative approach is discovery of natural partitions of vertical structure in a globally representative dataset, or 'archetypal' reflectivity profiles. In this study, this is accomplished through cluster analysis of a very large sample (0[107) of TRMM-PR reflectivity columns. Once achieved, the rainconditional and unconditional 'mix' of archetypal profile types in a given location and/or season provides a description of the local convective spectrum which retains vertical structure information. A further cluster analysis of these 'mixes' can identify recurrent convective spectra. These are a first step towards objective identification of convective regimes, and towards answering the question: 'What are the most convectively similar locations in the world?'

Boccippio, Dennis J.↗
NASA NTRS2016

The XXL Survey I. Scientific Motivations - Xmm-Newton Observing Plan - Follow-up Observations and Simulation Programme

The quest for the cosmological parameters that describe our universe continues to motivate the scientific community to undertake very large survey initiatives across the electromagnetic spectrum. Over the past two decades, the Chandra and XMM-Newton observatories have supported numerous studies of X-ray-selected clusters of galaxies, active galactic nuclei (AGNs), and the X-ray background. The present paper is the first in a series reporting results of the XXL-XMM survey; it comes at a time when the Planck mission results are being finalized. Aims. We present the XXL Survey, the largest XMM programme totaling some 6.9 Ms to date and involving an international consortium of roughly 100 members. The XXL Survey covers two extragalactic areas of 25 deg2 each at a point-source sensitivity of approx. 5 x 10(exp 15) erg/s/sq cm in the [0.5-2] keV band (completeness limit). The surveys main goals are to provide constraints on the dark energy equation of state from the space-time-distribution of clusters of galaxies and to serve as a pathfinder for future, wide-area X-ray missions. We review science objectives, including cluster studies, AGN evolution, and large-scale structure, that are being conducted with the support of approximately 30 follow-up programs. Methods. We describe the 542 XMM observations along with the associated multi- and numerical simulation programmes. We give a detailed account of the X-ray processing steps and describe innovative tools being developed for the cosmological analysis. Results. The paper provides a thorough evaluation of the X-ray data, including quality controls, photon statistics, exposure and background maps, and sky coverage. Source catalogue construction and multi-associations are briefly described. This material will be the basis for the calculation of the cluster and AGN selection functions, critical elements of the cosmological and science analyses. Conclusions. The XXL multi- data set will have a unique lasting legacy value for cosmological and extragalactic studies and will serve asa calibration resource for future dark energy studies with clusters and other X-ray selected sources. With the present article, we release the XMM XXL photon and smoothed images along with the corresponding exposure maps.

X-rays: general – large-scale structure of Unive↗
DOE OSTI2022

Stable CsPbBr 3 Nanoclusters Feature a Disk-like Shape and a Distorted Orthorhombic Structure

CsPbBr 3 nanoclusters have been synthesized by several groups and mostly employed as single-source precursors for the synthesis of anisotropic perovskite nanostructures or perovskite-based heterostructures. Yet, a detailed characterization of such clusters is still lacking due to their high instability. In this work, we were able to stabilize CsPbBr 3 nanoclusters by carefully selecting ad hoc ligands (benzoic acid together with oleylamine) to passivate their surface. The clusters have a narrow absorption peak at 400 nm, a band-edge emission peaked at 410 nm at room temperature, and their composition is identified as CsPbBr 2.3 . Synchrotron X-ray pair distribution function measurements indicate that the clusters exhibit a disk-like shape with a thickness smaller than 2 nm and a diameter of 13 nm, and their crystal structure is a highly distorted orthorhombic CsPbBr 3 . Based on small- and wide-angle X-ray scattering analyses, the clusters tend to form a two-dimensional (2D) hexagonal packing with a short-range order and a lamellar packing with a long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

A Cepheid Distance to NGC 4603 in the Centaurus Cluster

In an attempt to use Cepheid variables to determine the distance to the Centaurus cluster, we have obtained images of NGC 4603 with the Hubble Space Telescope for 9 epochs (totalling 24 orbits) over 14 months in the F555W filter and 2 epochs (totalling 6 orbits) in the F814W filter.

Cepheids distance redshifs large scale structure o↗
DOE OSTI2023

Heterologous expression of a fully active Azotobacter vinelandii nitrogenase Fe protein in Escherichia coli

ABSTRACT The functional versatility of the Fe protein, the reductase component of nitrogenase, makes it an appealing target for heterologous expression, which could facilitate future biotechnological adaptations of nitrogenase-based production of valuable chemical commodities. Yet, the heterologous synthesis of a fully active Fe protein of Azotobacter vinelandii ( Av NifH) in Escherichia coli has proven to be a challenging task. Here, we report the successful synthesis of a fully active Av NifH protein upon co-expression of this protein with Av IscS/U and Av NifM in E. coli . Our metal, activity, electron paramagnetic resonance, and X-ray absorption spectroscopy/extended X-ray absorption fine structure (EXAFS) data demonstrate that the heterologously expressed Av NifH protein has a high [Fe 4 S 4 ] cluster content and is fully functional in nitrogenase catalysis and assembly. Moreover, our phylogenetic analyses and structural predictions suggest that Av NifM could serve as a chaperone and assist the maturation of a cluster-replete Av NifH protein. Given the crucial importance of the Fe protein for the functionality of nitrogenase, this work establishes an effective framework for developing a heterologous expression system of the complete, two-component nitrogenase system; additionally, it provides a useful tool for further exploring the intricate biosynthetic mechanism of this structurally unique and functionally important metalloenzyme. IMPORTANCE The heterologous expression of a fully active Azotobacter vinelandii Fe protein (AvNifH) has never been accomplished. Given the functional importance of this protein in nitrogenase catalysis and assembly, the successful expression of AvNifH in Escherichia coli as reported herein supplies a key element for the further development of heterologous expression systems that explore the catalytic versatility of the Fe protein, either on its own or as a key component of nitrogenase, for nitrogenase-based biotechnological applications in the future. Moreover, the “clean” genetic background of the heterologous expression host allows for an unambiguous assessment of the effect of certain nif-encoded protein factors, such as AvNifM described in this work, in the maturation of AvNifH, highlighting the utility of this heterologous expression system in further advancing our understanding of the complex biosynthetic mechanism of nitrogenase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

TAMM: Tensor algebra for many-body methods

Tensor algebra operations such as contractions in computational chemistry consume a significant fraction of the computing time on large-scale computing platforms. The widespread use of tensor contractions between large multi-dimensional tensors in describing electronic structure theory has motivated the development of multiple tensor algebra frameworks targeting heterogeneous computing platforms. In this paper, we present Tensor Algebra for Many-body Methods (TAMM), a framework for productive and performance-portable development of scalable computational chemistry methods. TAMM decouples the specification of the computation from the execution of these operations on available high-performance computing systems. With this design choice, the scientific application developers (domain scientists) can focus on the algorithmic requirements using the tensor algebra interface provided by TAMM, whereas high-performance computing developers can direct their attention to various optimizations on the underlying constructs, such as efficient data distribution, optimized scheduling algorithms, and efficient use of intra-node resources (e.g., graphics processing units). The modular structure of TAMM allows it to support different hardware architectures and incorporate new algorithmic advances. We describe the TAMM framework and our approach to the sustainable development of scalable ground- and excited-state electronic structure methods. We present case studies highlighting the ease of use, including the performance and productivity gains compared to other frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

O 16 O 16 collisions at energies available at the BNL Relativistic Heavy Ion Collider and at the CERN Large Hadron Collider comparing α clustering versus substructure

Collisions of . light and heavy nuclei in relativistic heavy-ion collisions have been shown to be sensitive to nuclear structure. With a proposed 16 O 16 O run at the CERN Large Hadron Collider (LHC) and at the BNL Relativistic Heavy Ion Collider (RHIC) we study the potential for finding α clustering in 16 O. Here we use the state-of-the-art iEBE-VISHNU package with 16 O nucleonic configurations from ab initio nuclear lattice simulations. This setup was tuned using a Bayesian analysis on p Pb and PbPb systems. We find that the 16 O 16 O system always begins far from equilibrium and that at LHC and RHIC it approaches the regime of hydrodynamic applicability only at very late times. Finally, by taking ratios of flow harmonics we are able to find measurable differences between α-clustering, nucleonic, and subnucleonic degrees of freedom in the initial state.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Structure and Function of the Zinc Binding Protein ZrgA from Vibrio cholerae

ATP binding cassette (ABC) transporters are the primary means by which bacteria acquire trace elements from the environment. They rely on solute binding proteins (SBPs) to bind the relevant substrate and deliver it to the integral membrane permease for ATP-powered import into the cytoplasm. SBPs of cluster A-I are known to facilitate the transport of essential metals zinc, manganese, and iron, and many have been characterized to date. A group of ABC transporter operons dubbed zinc-regulated genes (zrg) have recently been shown to transport zinc with putative SBPs (zrgA) bearing no homology to the classical cluster A-I family, and a recent crystal structure of a representative protein from Pseudomonas aeruginosa shows no structural similarity to classical SBPs. Thus, the ZrgA proteins appear to represent a newly discovered family of zinc SBPs widespread among Gram-negative bacteria, including human pathogens. Here, we have determined the crystal structure of ZrgA from Vibrio cholerae and characterized its zinc binding in vitro and function in vivo. We also assessed the role of a histidine-rich sequence that appears to be a hallmark of ZrgA proteins that is particularly long in V. cholerae ZrgA. The results show that the zrgA gene is critical to the function of the operon, consistent with a function as an SBP in this system. Further, the His-rich region is not essential to the function of ZrgA, but it does provide additional zinc binding sites in vitro. The structure and zinc binding data for ZrgA reveal interesting differences between it and its homologue from P. aeruginosa, illustrating diversity within this little-studied protein family.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Superclustering with the Atacama Cosmology Telescope and Dark Energy Survey. I. Evidence for Thermal Energy Anisotropy Using Oriented Stacking

The cosmic web contains filamentary structure on a wide range of scales. On the largest scales, superclustering aligns multiple galaxy clusters along intercluster bridges, visible through their thermal Sunyaev–Zel'dovich signal in the cosmic microwave background. We demonstrate a new, flexible method to analyze the hot gas signal from multiscale extended structures. We use a Compton y-map from the Atacama Cosmology Telescope (ACT) stacked on redMaPPer cluster positions from the optical Dark Energy Survey (DES). Cutout images from the y-map are oriented with large-scale structure information from DES galaxy data such that the superclustering signal is aligned before being overlaid. We find evidence of an extended quadrupole moment of the stacked y signal at the 3.5σ level, demonstrating that the large-scale thermal energy surrounding galaxy clusters is anisotropically distributed. We compare our ACT × DES results with the Buzzard simulations, finding broad agreement. Using simulations, we highlight the promise of this novel technique for constraining the evolution of anisotropic, non-Gaussian structure using future combinations of microwave and optical surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1995

Cosmological implications of ROSAT observations of groups and clusters of galaxies

We have combined ROSAT Position Sensitive Proportional Counter (PSPC) and optical observations of a sample of groups and clusters of galaxies to determine the fundamental parameters of these systems (e.g., the dark matter distribution, gas mass fraction, baryon mass fraction, mass-to-light ratio, and the ratio of total-to-luminous mass). Imaging X-ray spectroscopy of groups and clusters show that the gas is essentially isothermal beyond the central region, indicating that the total mass density (mostly dark matter) scales as rho(sub dark) varies as 1/r squared. The density profile of the hot X-ray emitting gas is fairly flat in groups with rho(sub gas) varies as 1/r and becomes progressively steeper in hotter richer systems, with rho(sub gas) varies as 1/r squared in the richest clusters. These results show, that in general, the hot X-ray-emitting gas is the most extended mass component in groups and clusters, the galaxies are the most centrally concentrated component, and the dark matter is intermediate between the two. The flatter density rofile of the hot gas compared to the dark matter produces a gas mass fraction that increases with radius within each object. There is also a clear trend of increasing gas mass fraction (from 2% to 30%) between elliptical galaxies and rich clusters due to the greater detectable extent of the X-ray emission in richer systems. For the few systems in which the X-ray emission can be traced to the virial radius (where the overdensity delta is approximately equal 200), the gas mass fraction (essentially the baryon mass fraction) approaches a roughly constant value of 30%, suggesting that this is the true primordial value. Based on standard big bang nucleosynthesis, the large baryon mass fraction implies that Omega = 0.1 - 0.2. The antibiased gas distribution suggests that feedback from galaxy formation and hydrodynamics play important roles in the formation of structure on the scale of galaxies to rich clusters. All the groups and clusters in our sample have mass-to-light ratios of M/L(sub V) approximately 100 - 150 solar mass/solar luminosity, which strongly contrasts with the traditional view that the mass-to-light ratio of rich clusters is significantly greater than individual galaxies or groups with M/L(sub V) approximately 250 - 300 solar mass/solar luminosity. We also show that M/L(sub V is essentially constant within the virial radius of clusters (where delta is greater than or approximately 200), which is consistent with the peaks formalism of biased galaxy formation. While the mass-to-light ratios of groups and clusters are comparable (indicating a constant mass fraction of optically luminous material), the ratio of the total mass-to-luminous mass (gas plus stars) monotonically decreases between galaxies and clusters. The decrease in M(sub total)/M(sub lum) arises from two factors: (1) the composition of baryonic matter varies from a predominance of optically luminous material (stars) on the scale of galaxies (approximately 10 kpc) to a predominance of X-ray luminous material (hot gas) on the scale of rich clusters (approximately 1 Mpc), and (2) the hot gas has a more extended spatial distribution than the gravitating matter. The observed decrease M(sub total)/M(sub lum) between galaxies and clusters indicates that the universe actually becomes `brighter' on mass scales between 10(exp 12) and 10(exp 15) solar mass, in the sense that a greater fraction of the gravitating mass is observable.

David, Laurence P.↗
NASA NTRS1972

Structural aspects of Imbrium sculpture, part G

Apollo 16 metric photographs taken at low to high sun angles provided the first stereographic coverage of the distinctive landforms collectively referred to as Imbrium sculpture. The sculpture consists of a series of nearly linear ridges and troughs extending radially outward for more than 1000 km from the rim of the Imbrium Basin. The origin of the ridges and troughs, whether by deposition and impact scoring by fluidized clouds of ejecta from the Imbrium Basin or by faulting and volcanism during and subsequent to basin formation, is controversial. Evidence indicative of the mode of origin of Imbrium sculpture is summarized as follows. Evidence of volcano-tectonic mode of origin is favored by: (1) wide variation in relative age of parts of the sculpture; (2) furrows without rims; (3) absence of ballistic shielding; (4) asymmetry of sculpture; (5) absence of randomly oriented clusters; and (6) association with other features of structural origin. An origin by ejecta scoring and deposition is favored by the gradational ejecta with a Fra Mauro-type texture. Features that are ambiguous as to mode or origin are furrows made of coalesced crater chains and prominent rims on furrows.

Scott, D. H.↗
DOE OSTI2024

High-Entropy Metal-Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO 2 Utilization

High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO 2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, in this study, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO 2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Oxygen Defect Configurations in Single-Phase UO 2.15

Hyperstoichiometric UO 2.15 was characterized by neutron total scattering at high temperature in the single-phase UO 2+x region of the U/O phase diagram. The diffraction data confirmed a single-phase fluorite structure at high temperature. Analysis of the short-range data showed that the same structural model does not fit the pair distribution functions well. Instead, structural models containing specific configurations of oxygen defect clusters best represent the local atomic arrangement. In conclusion, prevalent defect clusters previously proposed were fit to the experimental data, and moderately distorted oxygen cuboctahedra hypothesized by recent molecular dynamics simulations fit the data most accurately.

neutron pair-distribution function analysis↗