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A few $4d$ and $5d$ transition metal compounds with various electron fillings were recently found to exhibit magnetic susceptibilities $\chi$ and magnetic moments that deviate from the well-established Kotani model. This model has been considered for decades to be the canonical expression to describe the temperature dependence of magnetism in systems with non-negligible spin-orbit coupling effects. In this work, we uncover the origin of such discrepancies and determine the applicability and limitations of the Kotani model by calculating the temperature dependence of the magnetic moments of a series of $4d$ (Ru-based) and $5d$ (W-based) systems at different electron fillings. For this purpose, we perform exact diagonalization of $ab~initio$-derived relativistic multiorbital Hubbard models on finite clusters and compute their magnetic susceptibilities. Comparison with experimentally measured magnetic properties indicates that contributions such as a temperature independent $\chi_0$ background, crystal field effects, Coulomb and Hund's couplings, and intersite interactions - not included in the Kotani model - are specially crucial to correctly describe the temperature dependence of $\chi$ and magnetic moments at various electron fillings in these systems. Based on our results, we propose a generalized approach to describe their magnetism., Comment: explained clearly the significance of deviations from Kotani model; added three-site cluster studies and calculations including the eg orbital

The development of high-performance sodium (Na) ion batteries requires improved electrode materials. The energy and power densities of Na superionic conductor (NaSICON) electrode materials are promising for large-scale energy storage applications. However, several practical issues limit the full utilization of the theoretical energy densities of NaSICON electrodes. A pressing challenge lies in the limited sodium extraction in low Na content NaSICONs, e.g., $\rm Na_1V^{IV}V^{IV}(PO_4)_3 \leftrightarrow V^{V}V^{IV}(PO_4)_3 + 1e^- + 1Na^+$. Hence, it is important to quantify the Na-ion mobility in a broad range of NaSICON electrodes. Using a kinetic Monte Carlo approach bearing the accuracy of first-principles calculations, we elucidate the variability of Na-ion transport vs. Na content in three important NaSICON electrodes, Na$_{\rm x}$Ti$_{2}$(PO$_{4}$)$_{3}$, Na$_{\rm x}$V$_{2}$(PO$_{4}$)$_{3}$, and Na$_{\rm x}$Cr$_{2}$(PO$_{4}$)$_{3}$. Our study suggests that Na$^+$ transport in NaSICON electrodes is almost entirely determined by the local electrostatic and chemical environment set by the transition metal and the polyanionic scaffold. The competition with the ordering-disordering phenomena of Na-vacancies also plays a role in influencing Na-transport. We link the variations in the Na$^+$ kinetic properties by analyzing the competition of ligand field stabilization transition metal ions and their ionic radii. We interpret the limited Na-extraction at $x = 1$ observed experimentally by gaining insights into the local Na-vacancy interplay. We propose that targeted chemical substitutions of transition metals disrupting local charge arrangements will be critical to reducing the occurrence of strong Na$^+$-vacancy orderings at low Na concentrations, thus, expanding the accessible capacities of these electrode materials.

Functional materials impact every area of our lives ranging from electronic and computing devices to transportation and health. In this Perspective, we examine the relationship between synthetic discoveries and the scientific breakthroughs that they have enabled. By tracing the development of some important examples, we explore how and why the materials were initially synthesized and how their utility was subsequently recognised. Three common pathways to materials breakthroughs are identified. In a small number of cases, such as the aluminosilicate zeolite catalyst ZSM-5, an important advance is made by using design principles based upon earlier work. There are also rare cases of breakthroughs that are serendipitous, such as the buckyball and Teflon(R). Most commonly, however, the breakthrough repurposes a compound that is already known and was often made out of curiosity or for a different application. Typically, the synthetic discovery precedes the discovery of functionality by many decades; key examples include conducting polymers, topological insulators and electrodes for lithium-ion batteries., Comment: 15 pages, two figures

Sparse aperture masking interferometry (SAM) is a high resolution observing technique that allows for imaging at and beyond a telescope's diffraction limit. The technique is ideal for searching for stellar companions at small separations from their host star; however, previous analysis of SAM observations of young stars surrounded by dusty disks have had difficulties disentangling planet and extended disk emission. We analyse VLT/SPHERE-IRDIS SAM observations of the transition disk LkCa\,15, model the extended disk emission, probe for planets at small separations, and improve contrast limits for planets. We fit geometrical models directly to the interferometric observables and recover previously observed extended disk emission. We use dynamic nested sampling to estimate uncertainties on our model parameters and to calculate evidences to perform model comparison. We compare our extended disk emission models against point source models to robustly conclude that the system is dominated by extended emission within 50 au. We report detections of two previously observed asymmetric rings at $\sim$17 au and $\sim$45 au. The peak brightness location of each model ring is consistent with the previous observations. We also, for the first time with imaging, robustly recover an elliptical Gaussian inner disk, previously inferred via SED fitting. This inner disk has a FWHM of ~5 au and a similar inclination and orientation as the outer rings. Finally, we recover no clear evidence for candidate planets. By modelling the extended disk emission, we are able to place a lower limit on the near infrared companion contrast of at least 1000., Comment: Accepted for publication in ApJ

In the pursuit of urgently-needed, energy dense solid-state batteries for electric vehicle and portable electronics applications, halide solid electrolytes offer a promising path forward with exceptional compatibility against high-voltage oxide electrodes, tunable ionic conductivities, and facile processing. For this family of compounds, synthesis protocols strongly affect cation site disorder and modulate Li+ mobility. In this work, we reveal the presence of a high concentration of stacking faults in the superionic conductor Li3YCl6 and demonstrate a method of controlling its Li+ conductivity by tuning the defect concentration with synthesis and heat treatments at select temperatures. Leveraging complementary insights from variable temperature synchrotron X-ray diffraction, neutron diffraction, cryogenic transmission electron microscopy, solid-state nuclear magnetic resonance, density functional theory, and electrochemical impedance spectroscopy, we identify the nature of planar defects and the role of nonstoichiometry in lowering Li+ migration barriers and increasing Li site connectivity in mechanochemically-synthesized Li3YCl6. We harness paramagnetic relaxation enhancement to enable 89Y solid-state NMR, and directly contrast the Y cation site disorder resulting from different preparation methods, demonstrating a potent tool for other researchers studying Y-containing compositions. With heat treatments at temperatures as low as 333 K (60{\deg}C), we decrease the concentration of planar defects, demonstrating a simple method for tuning the Li+ conductivity. Findings from this work are expected to be generalizable to other halide solid electrolyte candidates and provide an improved understanding of defect-enabled Li+ conduction in this class of Li-ion conductors.

We elucidate the thermodynamics of sodium (Na) intercalation into the sodium super-ionic conductor (NaSICON)-type electrode, Na$_x$V$_2$(PO$_4$)$_3$, for promising Na-ion batteries with high-power density. This is the first report of a computational temperature-composition phase diagram of the NaSICON-type electrode Na$_x$V$_2$(PO$_4$)$_3$. We identify two thermodynamically stable phases at the compositions Na$_2$V$_2$(PO$_4$)$_3$ and Na$_{3.5}$V$_2$(PO$_4$)$_3$, and their structural features are described for the first time based on our computational analysis. We unveil the crystal-structure and the electronic-structure origins of the ground-state compositions associated with specific Na/vacancy arrangements, which are driven by charge orderings on the vanadium sites. These results are significant for the optimization of high-energy and power densities electrodes for sustainable Na-ion batteries, Comment: 5 figures

Context. Direct imaging of debris discs gives important information about their nature, their global morphology, and allows us to identify specific structures possibly in connection with the presence of gravitational perturbers. It is the most straightforward technique to observe planetary systems as a whole. Aims. We present the first resolved images of the debris disc around the young F-type star HD 160305, detected in scattered light using the VLT/SPHERE instrument in the near infrared. Methods. We used a post-processing method based on angular differential imaging and synthetic images of debris discs produced with a disc modelling code (GRaTer) to constrain the main characteristics of the disc around HD 160305. All of the point sources in the field of the IRDIS camera were analysed with an astrometric tool to determine whether they are bound objects or background stars. Results. We detect a very inclined (~ 82{\deg}) ring-like debris disc located at a stellocentric distance of about 86au (deprojected width ~27 au). The disc displays a brightness asymmetry between the two sides of the major axis, as can be expected from scattering properties of dust grains. We derive an anisotropic scattering factor g>0.5. A second right-left asymmetry is also observed with respect to the minor axis. We measure a surface brightness ratio of 0.73 $\pm$ 0.18 between the bright and the faint sides. Because of the low signal-to-noise ratio (S/N) of the images we cannot easily discriminate between several possible explanations for this left-right asymmetry, such as perturbations by an unseen planet, the aftermath of the breakup of a massive planetesimal, or the pericenter glow effect due to an eccentric ring. Two epochs of observations allow us to reject the companionship hypothesis for the 15 point sources present in the field., Comment: 13 pages

Using the Atacama Large Millimeter/submillimeter Array (ALMA), we observed the young Herbig star HD 100546, host to a prominent disk with a deep, wide gap in the dust. The high-resolution 1.3 mm continuum observation reveals fine radial and azimuthal substructures in the form of a complex maze of ridges and trenches sculpting a dust ring. The $^{12}$CO(2-1) channel maps are modulated by wiggles or kinks that deviate from Keplerian kinematics particularly over the continuum ring, where deviations span 90$^\circ$ in azimuth, covering 5 km s$^{-1}$. The most pronounced wiggle resembles the imprint of an embedded massive planet of at least 5 M$_{\rm Jup}$ predicted from previous hydrodynamical simulations (Perez, Casassus, & Benitez-Llambay 2018). Such planet is expected to open a deep gap in both gas and dust density fields within a few orbital timescales, yet the kinematic wiggles lie near ridges in the continuum. The lesser strength of the wiggles in the $^{13}$CO and C$^{18}$O isotopologues show that the kinematic signature weakens at lower disk heights, and suggests qualitatively that it is due to vertical flows in the disk surface. Within the gap, the velocity field transitions from Keplerian to strongly non-Keplerian via a twist in position angle, suggesting the presence of another perturber and/or an inner warp. We also present VLT/SPHERE sparse aperture masking data which recovers scattered light emission from the gap's edges but shows no evidence for signal within the gap, discarding a stellar binary origin for its opening., Comment: 10 pages, 6 figures. Accepted for publication in ApJ Letters

Context. The interaction between low-mass companions and the debris discs they reside in is still not fully understood. A debris disc can evolve due to self-stirring, a process in which planetesimals can excite their neighbours to the point of destructive collisions. In addition, the presence of a companion could further stir the disc (companion-stirring). Additional information is necessary to understand this fundamental step in the formation and evolution of a planetary system, and at the moment of writing only a handful of systems are known where a companion and a debris disc have both been detected and studied at the same time. Aims. Our primary goal is to augment the sample of these systems and to understand the relative importance between self-stirring and companion-stirring. Methods. In the course of the VLT/NaCo Imaging Survey for Planets around Young stars (ISPY), we observed HD 193571, an A0 debris disc hosting star at a distance of 68 pc with an age between 60 and 170 Myr. We obtained two sets of observations in L' band and a third epoch in H band using the GPI instrument at Gemini-South. Results. A companion was detected in all three epochs at a projected separation of 11 au (0.17 arcsec), and co-motion was confirmed through proper motion analysis. Given the inferred disc size of 120 au, the companion appears to reside within the gap between the host star and the disc. Comparison between the L' and H band magnitude and evolutionary tracks suggests a mass of 0.31 - 0.39 solar masses . Conclusions. We discovered a previously unknown M-dwarf companion around HD 193571, making it the third low-mass stellar object discovered within a debris disc. A comparison to self- and companion-stirring models suggests that the companion is likely responsible for the stirring of the disc., Comment: 10 pages, 8 figures, accepted for publication in Astronomy&Astrophysics

Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology, and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of those already known. In particular --- while such nanoporous materials were traditionally seen as rigid crystalline structures --- there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder, are not the exception, but rather the norm, in metal-organic frameworks. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding, and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

The Gemini Planet Imager (GPI) contains a 10-hole non-redundant mask (NRM), enabling interferometric resolution in complement to its coronagraphic capabilities. The NRM operates both in spectroscopic (integral field spectrograph, henceforth IFS) and polarimetric configurations. NRM observations were taken between 2013 and 2016 to characterize its performance. Most observations were taken in spectroscopic mode with the goal of obtaining precise astrometry and spectroscopy of faint companions to bright stars. We find a clear correlation between residual wavefront error measured by the AO system and the contrast sensitivity by comparing phase errors in observations of the same source, taken on different dates. We find a typical 5-$\sigma$ contrast sensitivity of $2-3~\times~10^{-3}$ at $\sim\lambda/D$. We explore the accuracy of spectral extraction of secondary components of binary systems by recovering the signal from a simulated source injected into several datasets. We outline data reduction procedures unique to GPI's IFS and describe a newly public data pipeline used for the presented analyses. We demonstrate recovery of astrometry and spectroscopy of two known companions to HR 2690 and HD 142527. NRM+polarimetry observations achieve differential visibility precision of $\sigma\sim0.4\%$ in the best case. We discuss its limitations on Gemini-S/GPI for resolving inner regions of protoplanetary disks and prospects for future upgrades. We summarize lessons learned in observing with NRM in spectroscopic and polarimetric modes., Comment: Accepted to AJ, 22 pages, 14 figures

The diversity of halide materials related to important solar energy systems such as CsPbX3 (X = Cl, Br, I) is explored by introducing the transition metal element Fe. In particular a new compound, Cs3Fe2Br9 (space group P6_3/mmc with a = 7.5427(8) and c = 18.5849(13) {\AA}), has been synthesized and found to contain 0D face-sharing Fe2Br9 octahedral dimers. Unlike its isomorph, Cs3Bi2I9, it is black in color, has a low optical bandgap of 1.65 eV and exhibits antiferromagnetic behavior below TN = 13 K. Density functional theory calculations shed further light on these properties and also predict that the material should have anisotropic transport characteristics.