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  1. Free, publicly-accessible full text available December 27, 2024
  2. Free, publicly-accessible full text available November 12, 2024

    We employ a sample of 135 873 RR Lyrae stars (RRLs) with precise photometric-metallicity and distance estimates from the newly calibrated P–ϕ31–R21–[Fe/H] and Gaia G band P–R21–[Fe/H] absolute magnitude–metallicity relations of Li et al., combined with available proper motions from Gaia EDR3, and 6955 systemic radial velocities from Gaia DR3 and other sources, in order to explore the chemistry and kinematics of the halo of the Milky Way (MW). This sample is ideally suited for characterization of the inner- and outer-halo populations of the stellar halo, free from the bias associated with spectroscopically selected probes, and for estimation of their relative contributions as a function of Galactocentric distance. The results of a Gaussian mixture model analysis of these contributions are broadly consistent with other observational studies of the halo, and with expectations from recent MW simulation studies. We apply the hdbscan clustering method to the specific energies and cylindrical actions (E, Jr, Jϕ, Jz), identifying 97 dynamically tagged groups (DTGs) of RRLs, and explore their associations with recognized substructures of the MW. The precise photometric-distance determinations (relative distance errors on the order of 5 per cent or better), and the resulting high-quality determination of dynamical parameters, yield highly statistically significant (low) dispersions of [Fe/H] for the stellar members of the DTGs compared to random draws from the full sample, indicating that they share common star-formation and chemical histories, influenced by their birth environments.

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    We use 3653 (2661 RRab, 992 RRc) RR Lyrae stars (RRLs) with 7D (3D position, 3D velocity, and metallicity) information selected from Sloan Digital Sky Survey, Large Sky Area Multi-Object Fiber Spectroscopic Telescope, and Gaia EDR3, and divide the sample into two Oosterhoff groups (Oo I and Oo II) according to their amplitude–period behaviour in the Bailey diagram. We present a comparative study of these two groups based on chemistry, kinematics, and dynamics. We find that Oo I RRLs are relatively more metal-rich, with predominately radially dominated orbits and large eccentricities, while Oo II RRLs are relatively more metal-poor, and have mildly radially dominated orbits. The Oosterhoff dichotomy of the Milky Way’s halo is more apparent for the inner-halo region than for the outer-halo region. Additionally, we also search for this phenomenon in the haloes of the two largest satellite galaxies, the Large and Small Magellanic clouds, and compare over different bins in metallicity. We find that the Oosterhoff dichotomy is not immutable, and varies based on position in the Galaxy and from galaxy to galaxy. We conclude that the Oosterhoff dichotomy is the result of a combination of stellar and galactic evolution, and that it is much more complex than the dichotomy originally identified in Galactic globular clusters.

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  5. Abstract

    Stereoselective ring-opening polymerization catalysts are used to produce degradable stereoregular poly(lactic acids) with thermal and mechanical properties that are superior to those of atactic polymers. However, the process of discovering highly stereoselective catalysts is still largely empirical. We aim to develop an integrated computational and experimental framework for efficient, predictive catalyst selection and optimization. As a proof of principle, we have developed a Bayesian optimization workflow on a subset of literature results for stereoselective lactide ring-opening polymerization, and using the algorithm, we identify multiple new Al complexes that catalyze either isoselective or heteroselective polymerization. In addition, feature attribution analysis uncovers mechanistically meaningful ligand descriptors, such as percent buried volume (%Vbur) and the highest occupied molecular orbital energy (EHOMO), that can access quantitative and predictive models for catalyst development.

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  6. Abstract

    We present results from high-resolution (R∼ 40,000) spectroscopic observations of over 200 metal-poor stars, mostly selected from the RAVE survey, using the Southern African Large Telescope. We were able to derive stellar parameters for a total of 108 stars; an additional sample of 50 stars from this same effort was previously reported on by Rasmussen et al. Among our newly reported observations, we identify 84 very metal-poor (VMP; [Fe/H] < −2.0, 53 newly identified) stars and three extremely metal-poor (EMP; [Fe/H] < −3.0, one newly identified) stars. The elemental abundances were measured for carbon, as well as several otherα-elements (Mg, Ca, Sc, and Ti), iron-peak elements (Mn, Co, Ni, and Zn), and neutron-capture elements (Sr, Ba, and Eu). Based on these measurements, the stars are classified by their carbon and neutron-capture abundances into carbon-enhanced metal-poor (CEMP; [C/Fe] > +0.70), CEMP subclasses, and by the level of theirr-process abundances. A total of 17 are classified as CEMP stars. There are 11 CEMP-rstars (eight newly identified), one CEMP-sstar (newly identified), two possible CEMP-istars (one newly identified), and three CEMP-no stars (all newly identified) in this work. We found 11 stars (eight newly identified) that are strongly enhanced inr-process elements (r-II; [Eu/Fe] > +0.70), 38 stars (31 newly identified) that are moderately enhanced inr-process elements (r-I; +0.30 < [Eu/Fe] ≤ + 0.70), and one newly identified limited-rstar.

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  7. Abstract

    The electrochemical nitrate reduction reaction (NO3RR) to ammonia is an essential step toward restoring the globally disrupted nitrogen cycle. In search of highly efficient electrocatalysts, tailoring catalytic sites with ligand and strain effects in random alloys is a common approach but remains limited due to the ubiquitous energy-scaling relations. With interpretable machine learning, we unravel a mechanism of breaking adsorption-energy scaling relations through the site-specific Pauli repulsion interactions of the metald-states with adsorbate frontier orbitals. The non-scaling behavior can be realized on (100)-type sites of ordered B2 intermetallics, in which the orbital overlap between the hollow *N and subsurface metal atoms is significant while the bridge-bidentate *NO3is not directly affected. Among those intermetallics predicted, we synthesize monodisperse ordered B2 CuPd nanocubes that demonstrate high performance for NO3RR to ammonia with a Faradaic efficiency of 92.5% at −0.5 VRHEand a yield rate of 6.25 mol h−1g−1at −0.6 VRHE. This study provides machine-learned design rules besides thed-band center metrics, paving the path toward data-driven discovery of catalytic materials beyond linear scaling limitations.

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  8. Abstract

    Orbital characteristics based on Gaia Early Data Release 3 astrometric parameters are analyzed for ∼4000 metal-poor stars ([Fe/H] ≤ −0.8) compiled from the Best and Brightest survey. Selected as metal-poor candidates based on broadband near- and far-IR photometry, 43% of these stars had medium-resolution (1200 ≲R≲ 2000) validation spectra obtained over a 7 yr campaign from 2014 to 2020 with a variety of telescopes. The remaining stars were chosen based on photometric metallicity determinations from the Huang et al. recalibration of the Sky Mapper Southern Survey. Dynamical clusters of these stars are obtained from the orbital energy and cylindrical actions using theHDBSCANunsupervised learning algorithm. We identify 52 dynamically tagged groups (DTGs) with between five and 21 members; 18 DTGs have at least 10 member stars. Milky Way (MW) substructures such as Gaia-Sausage-Enceladus, the Metal-Weak Thick-Disk, Thamnos, the Splashed Disk, and the Helmi Stream are identified. Associations with MW globular clusters are determined for eight DTGs; no recognized MW dwarf galaxies were associated with any of our DTGs. Previously identified dynamical groups are also associated with our DTGs, with emphasis placed on their structural determination and possible new identifications. Chemically peculiar stars are identified as members of several DTGs, with six DTGs that are associated withr-process-enhanced stars. We demonstrate that the mean carbon andα-element abundances of our DTGs are correlated with their mean metallicity in an understandable manner. Similarly, we find that the mean metallicity, carbon, andα-element abundances are separable into different regions of the mean rotational-velocity space.

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