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Fast Atomic-Scale Elemental Mapping of Crystalline Materials by STEM Energy-Dispersive X-Ray Spectroscopy Achieved with Thin Specimens [Fast Atomic-Scale Chemical Imaging of Crystalline Materials by STEM Energy-Dispersive X-ray Spectroscopy Achieved with Thin Specimens].

Abstract Elemental mapping at the atomic-scale by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) provides a powerful real-space approach to chemical characterization of crystal structures. However, applications of this powerful technique have been limited by inefficient X-ray emission and collection, which require long acquisition times. Recently, using a lattice-vector translation method, we have shown that rapid atomic-scale elemental mapping using STEM-EDS can be achieved. This method provides atomic-scale elemental maps averaged over crystal areas of ~few 10 nm 2 with the acquisition time of ~2 s or less. Here we report the details of this method, and, in particular, investigate the experimental conditions necessary for achieving it. It shows, that in addition to usual conditions required for atomic-scale imaging, a thin specimen is essential for the technique to be successful. Phenomenological modeling shows that the localization of X-ray signals to atomic columns is a key reason. The effect of specimen thickness on the signal delocalization is studied by multislice image simulations. The results show that the X-ray localization can be achieved by choosing a thin specimen, and the thickness of less than about 22 nm is preferred for SrTiO 3 in [001] projection for 200 keV electrons.

47 OTHER INSTRUMENTATION↗

Source Attribution of Cyanides using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics

Chemical attribution signatures (CAS) for chemical threat agents (CTAs) are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. In a previous study, anionic impurity profiles developed using high performance ion chromatography (HPIC) were demonstrated as CAS for matching samples from eight potassium cyanide (KCN) stocks to their reported countries of origin. Herein, a larger number of solid KCN stocks (n = 13) and, for the first time, solid sodium cyanide (NaCN) stocks (n = 15) were examined to determine what additional sourcing information can be obtained through anion, carbon stable isotope, and elemental analyses of cyanide stocks by HPIC, isotope ratio mass spectrometry (IRMS), and inductively coupled plasma optical emission spectroscopy (ICP-OES), respectively. The HPIC anion data was evaluated using the variable selection methods of Fisher-ratio (F-ratio), interval partial least squares (iPLS), and genetic algorithm-based partial least squares (GAPLS) and the classification methods of partial least squares discriminate analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminate analysis (SVMDA). In summary, hierarchical cluster analysis (HCA) of anion impurity profiles from multiple cyanide stocks from six reported country of origins resulted in cyanide samples clustering into three groups: Czech Republic, Germany, and United States, independent of the associated alkali metal (K or Na). The three country groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries with known solid cyanide factories. Both the anion and elemental CAS are believed to originate from the aqueous alkali hydroxides used in cyanide manufacture. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). The carbon isotope CAS is believed to originate from the carbon source and process used to make the HCN utilized in cyanide synthesis. Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability (so far) of using anion impurities for matching a cyanide sample to its country of manufacture (i.e., factory). Variable selection reduced errors for those classification methods having errors greater than zero with iPLS-forward selection, and F-ratio typically providing the lowest errors. Finally, using anion profiles to match cyanides to a specific stock or stock group resulted in cross-validation errors ranging from zero to 5.3%.

chemical forensics↗

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlations of the Elemental Compositions of Primary Coal Tar and Char

We report that simulations of large-scale coal combustors rely on accurate submodels to describe the chemical and physical changes in coal during reaction. Typically, researchers use simplified empirical submodels tuned to experimental data to reduce the computational complexity. When data are not readily available, researchers use simplifying assumptions, which can create inaccuracies and biases in a large simulation. One such simplifying assumption in coal research is how to describe the elemental composition of primary pyrolysis products. This paper explores several different empirical model forms to predict the dry, ash-free fractions of C, H, O, N, and S in both the char and the tar, using variables such as parent coal composition, reaction conditions (temperatures and particle residence times), and key coal structural parameters derived from NMR measurements. These model forms were correlated to existing data using a wide range of experimental data using a cross-validation procedure. Since coal structural values can be expensive to measure, several correlations from the literature were used to estimate these values based on information from the proximate and ultimate analyses of the parent coal, including a new correlation for the coal aromaticity. These model forms were tested against a set of measured elemental compositions of tar and char to find the best fit to use in the cross-validation process. Lastly, the best empirical models are presented that predict elemental composition of the coal char and tar after devolatilization.

01 COAL, LIGNITE, AND PEAT↗

Multispecies Biofilms Transform Selenium Oxyanions into Elemental Selenium Particles: Studies Using Combined Synchrotron X-ray Fluorescence Imaging and Scanning Transmission X-ray Microscopy

Selenium (Se) is an element of growing environmental concern, because low aqueous concentrations can lead to biomagnification through the aquatic food web. Biofilms, naturally occurring microbial consortia, play numerous important roles in the environment, especially in biogeochemical cycling of toxic elements in aquatic systems. The complexity of naturally forming multispecies biofilms presents challenges for characterization because conventional microscopic techniques require chemical and physical modifications of the sample. Here, multispecies biofilms biotransforming selenium oxyanions were characterized using X-ray fluorescence imaging (XFI) and scanning transmission X-ray microscopy (STXM). These complementary synchrotron techniques required minimal sample preparation and were applied correlatively to the same biofilm areas. Sub-micrometer XFI showed distributions of Se and endogenous metals, while Se K-edge X-ray absorption spectroscopy indicated the presence of elemental Se (Se0). Nanoscale carbon K-edge STXM revealed the distributions of microbial cells, extracellular polymeric substances (EPS), and lipids using the protein, saccharide, and lipid signatures, respectively, together with highly localized Se0 using the Se LIII edge. Transmission electron microscopy showed the electron-dense particle diameter to be 50–700 nm, suggesting Se0 nanoparticles. The intimate association of Se0 particles with protein and polysaccharide biofilm components has implications for the bioavailability of selenium in the environment.

Yang, Soo In↗

One Structure, Two Elements—LuGe 2 Superconductor vs Ordinary Metallic Conductor LuSn 2 . A Case Study on How Site-Selective Germanium for Tin Atom Substitution Leads to Modulating of the Charge Distribution

The substitution of chemically similar elements in a given crystal structure is an effective way to enhance physical properties, but the understanding on such improvements is usually impeded because the substitutions are random, and the roles of the different atoms cannot be distinguished by crystallographic symmetry. Herein, we provide a detailed crystallographic analysis and property measurements for the continuous solid solutions LuGe x Sn 2–x (0 < x < 2). The results show that there is no apparent change of the global symmetry, with the end-members LuGe 2 and LuSn 2 , as well as the intermediate LuGe x Sn 2–x compositions adopting the ZrSi 2 type structure (space group Cmcm, Pearson index oC12). Yet, the refinements of the crystal structures from single-crystal X-ray diffraction data show that Ge–Sn atom substitutions are not random, but occur preferentially at the zig-zag chain. The patterned distribution of two group 14 elements leads to a significant variation in chemical bonding and charge ordering within the other structural fragment, the 2D square nets, thereby resulting in tuned electron transport. The enhancement is greater than the typical Bloch-Gruneisen model, and more akin to the parallel-resistor model. Magnetization measurements on single crystals show bulk superconductivity in all LuGe x Sn 2–x samples with shielding fractions as high as 90%. Specific heat data confirm the effect to originate from residual metallic tin in the material, indicating that Sn atom substitutions in the 2D square nets cause disruptions of the hypervalent bonding and local anisotropy, which ultimately leads to vanishing of the superconducting state in the end-member LuGe 2 . This work sheds light on how the complexity in chemical interactions by two different carbon congeners leads to changes in the physical properties and how they can be correlated with the induced charge distribution. Furthermore, these studies also provide a general approach to modulation of charge density, and thus, of emerging physical properties in other classes of intermetallic systems based on the main-group elements of groups 13 to 15.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heavy element effects in the diagonal Born–Oppenheimer correction within a relativistic spin-free Hamiltonian

Methodologies beyond the Born–Oppenheimer (BO) approximation are nowadays important to explain high precision spectroscopic measurements. Most previous evaluations of the BO correction are, however, focused on light-element molecules and based on a nonrelativistic Hamiltonian, so no information about the BO approximation (BOA) breakdown in heavy-element molecules is available. The present work is the first to investigate the BOA breakdown for the entire periodic table, by considering scalar relativistic effects in the Diagonal BO correction (DBOC). In closed shell atoms, the relativistic EDBOC scales as Z 1.25 and the nonrelativistic EDBOC scales as Z 1.17 , where Z is the atomic number. Hence, we found that EDBOC becomes larger in heavy element atoms and molecules, and the relativistic EDBOC increases faster than nonrelativistic EDBOC. We have further investigated the DBOC effects on properties such as potential energy curves, spectroscopic parameters, and various energetic properties. The DBOC effects for these properties are mostly affected by the lightest atom in the molecule. Furthermore, in X 2 or XAt molecule (X = H, Li, Na, K, Rb, and Cs) the effect of DBOC systematically decreases when X becomes heavier but in HX molecules, the effect of DBOC seems relatively similar among all the molecules.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sustainable Urban Mining of Critical Elements from Magnet and Electronic Wastes

Here, we created a straightforward and environment-friendly process for acid-free leaching of rare-earth elements and cobalt, which are vital materials, from waste magnet materials. The process also allows for selective leaching of rare-earth elements from magnet-containing electronic wastes, such as end-of-life hard disk drives and electric motors. The use of copper salts eliminates the use of volatile toxic acids in the dissolution and separation processes, which provides for a more eco-friendly approach to recovering critical elements and a safer work environment. Recovered critical materials were shown to be suitable for reinsertion into the materials supply chain.

36 MATERIALS SCIENCE↗

High-Energy Density Li-Ion Battery Cathode Using Only Industrial Elements

Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li 2 FeS 2 , composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al 3+ for Fe 2+ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g –1 ) and energy density (≳1000 Wh·kg –1 ). We show that Al 3+ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.

25 ENERGY STORAGE↗

Modeling of Stick-Slip Behavior in Sheared Granular Fault Gouge Using the Combined Finite-Discrete Element Method

Sheared granular layers undergoing stick-slip behavior are broadly employed to study the physics and dynamics of earthquakes. In this paper, a two-dimensional implementation of the combined finite-discrete element method (FDEM), which merges the finite element method (FEM) and the discrete element method (DEM), is used to explicitly simulate a sheared granular fault system including both gouge and plate, and to investigate the influence of different normal loads on seismic moment, macroscopic friction coefficient, kinetic energy, gouge layer thickness, and recurrence time between slips. In the FDEM model, the deformation of plates and particles is simulated using the FEM formulation while particle-particle and particle-plate interactions are modeled using DEM-derived techniques. The simulated seismic moment distributions are generally consistent with those obtained from the laboratory experiments. In addition, the simulation results demonstrate that with increasing normal load, (i) the kinetic energy of the granular fault system increases; (ii) the gouge layer thickness shows a decreasing trend; and (iii) the macroscopic friction coefficient does not experience much change. Analyses of the slip events reveal that, as the normal load increases, more slip events with large kinetic energy release and longer recurrence time occur, and the magnitude of gouge layer thickness decrease also tends to be larger; while the macroscopic friction coefficient drop decreases. Finally, the simulations not only reveal the influence of normal loads on the dynamics of sheared granular fault gouge, but also demonstrate the capabilities of FDEM for studying stick-slip dynamic behavior of granular fault systems.

58 GEOSCIENCES↗

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt 3 Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt 3 Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. Furthermore, this work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance.

36 MATERIALS SCIENCE↗

Enhanced sensitivity for electron affinity measurements of rare elements

The electron affinity (EA), the energy released when a neutral atom binds an additional electron, is a fundamental property of atoms that is governed by electron-electron correlations and is strongly related to an element’s chemical reactivity. However, conventional techniques for EA determination lack the experimental sensitivity to probe very scarce samples. As a result, the EA for the heaviest elements of the periodic table is entirely uncharted. Here, we present a novel technique to determine EAs through Laser Photodetachment Threshold Spectroscopy, performed in an electrostatic ion beam trap to increase the samples’ exposure to laser photons and, thus, improve the experimental signal sensitivity by three orders of magnitude. Moreover, the additional exposure time allows the use of lower-power continuous-wave narrow-band lasers that reduce uncertainties associated with broadening effects induced by the laser bandwidth. By applying this technique, we measure the EA of 35 Cl to be 3.612720(44) eV, achieving state-of-the-art precision while employing five orders of magnitude fewer anions. The demonstrated sensitivity paves the way for systematic EA measurements across isotopic chains - including isotope shifts and hyperfine splittings - and ultimately for the first direct determination of electron affinities in superheavy elements.

Maier, F. M. [Univ. of Greifswald (Germany); Europ↗

PRISMS-PF: A general framework for phase-field modeling with a matrix-free finite element method

Abstract A new phase-field modeling framework with an emphasis on performance, flexibility, and ease of use is presented. Foremost among the strategies employed to fulfill these objectives are the use of a matrix-free finite element method and a modular, application-centric code structure. This approach is implemented in the new open-source PRISMS-PF framework. Its performance is enabled by the combination of a matrix-free variant of the finite element method with adaptive mesh refinement, explicit time integration, and multilevel parallelism. Benchmark testing with a particle growth problem shows PRISMS-PF with adaptive mesh refinement and higher-order elements to be up to 12 times faster than a finite difference code employing a second-order-accurate spatial discretization and first-order-accurate explicit time integration. Furthermore, for a two-dimensional solidification benchmark problem, the performance of PRISMS-PF meets or exceeds that of phase-field frameworks that focus on implicit/semi-implicit time stepping, even though the benchmark problem’s small computational size reduces the scalability advantage of explicit time-integration schemes. PRISMS-PF supports an arbitrary number of coupled governing equations. The code structure simplifies the modification of these governing equations by separating their definition from the implementation of the numerical methods used to solve them. As part of its modular design, the framework includes functionality for nucleation and polycrystalline systems available in any application to further broaden the phenomena that can be used to study. The versatility of this approach is demonstrated with examples from several common types of phase-field simulations, including coarsening subsequent to spinodal decomposition, solidification, precipitation, grain growth, and corrosion.

36 MATERIALS SCIENCE↗

Computational discovery of ultra-strong, stable, and lightweight refractory multi-principal element alloys. Part I: design principles and rapid down-selection

Abstract Refractory metal-based multi-principal element alloys (MPEAs) are compelling materials for high-temperature (1000–2000 K) structural applications. However, only a minuscule fraction of their vast and heterogeneous compositional design space has been explored, leaving many potentially interesting alloys undiscovered. In this two-part work, a large region of the 11-element Al-Cr-Fe-Hf-Mo-Nb-Ta-Ti-V-W-Zr design space is computationally explored to identify refractory MPEAs with simultaneously high yield strength or specific yield strength and body-centered cubic (BCC) solid solution stability. In Part I , two case studies illuminate key factors and considerations in the yield strength versus phase stability tradeoff, provide guidelines for narrowing the expansive design space, and identify many candidates predicted to be stronger than refractory MPEAs reported to date, with BCC phase stability. Our findings indicate that medium entropy ternary alloys can outperform alloys with more elements and highlight the importance of exploring regions away from the equiatomic center of composition space.

36 MATERIALS SCIENCE↗

Complete miscibility of immiscible elements at the nanometre scale

Understanding the mixing behaviour of elements in a multielement material is important to control its structure and property. When the size of a multielement material is decreased to the nanoscale, the miscibility of elements in the nanomaterial often changes from its bulk counterpart. However, there is a lack of comprehensive and quantitative experimental insight into this process. Here, in this study, we explored how the miscibility of Au and Rh evolves in nanoparticles of sizes varying from 4 to 1 nm and composition changing from 15% Au to 85% Au. We found that the two immiscible elements exhibit a phase-separation-to-alloy transition in nanoparticles with decreased size and become completely miscible in sub-2 nm particles across the entire compositional range. Quantitative electron microscopy analysis and theoretical calculations were used to show that the observed immiscibility-to-miscibility transition is dictated by particle size, composition and possible surface adsorbates present under the synthesis conditions.

36 MATERIALS SCIENCE↗

Synthesis and chemistry of elemental 2D materials

2D materials have attracted considerable attention in the past decade for their superlative physical properties. These materials consist of atomically thin sheets exhibiting covalent in-plane bonding and weak interlayer and layer-substrate bonding. Following the example of graphene, most emerging 2D materials are derived from structures that can be isolated from bulk phases of layered materials, which form a limited library for new materials discovery. Entirely synthetic 2D materials provide access to a greater range of properties through the choice of constituent elements and substrates. Of particular interest are elemental 2D materials, because they provide the most chemically tractable case for synthetic exploration. In this Review, we explore the progress made in the synthesis and chemistry of synthetic elemental 2D materials, and offer perspectives and challenges for the future of this emerging field.

Mannix, Andrew J.↗

Expanded encyclopaedias of DNA elements in the human and mouse genomes

The human and mouse genomes contain instructions that specify RNAs and proteins and govern the timing, magnitude, and cellular context of their production. To better delineate these elements, phase III of the Encyclopedia of DNA Elements (ENCODE) Project has expanded analysis of the cell and tissue repertoires of RNA transcription, chromatin structure and modification, DNA methylation, chromatin looping, and occupancy by transcription factors and RNA-binding proteins. Here we summarize these efforts, which have produced 5,992 new experimental datasets, including systematic determinations across mouse fetal development. All data are available through the ENCODE data portal (https://www.encodeproject.org), including phase II ENCODE1 and Roadmap Epigenomics2 data. We have developed a registry of 926,535 human and 339,815 mouse candidate cis-regulatory elements, covering 7.9 and 3.4% of their respective genomes, by integrating selected datatypes associated with gene regulation, and constructed a web-based server (SCREEN; http://screen.encodeproject.org) to provide flexible, user-defined access to this resource. Collectively, the ENCODE data and registry provide an expansive resource for the scientific community to build a better understanding of the organization and function of the human and mouse genomes.

59 BASIC BIOLOGICAL SCIENCES↗

Heavy-element production in a compact object merger observed by JWST

The mergers of binary compact objects such as neutron stars and black holes are of central interest to several areas of astrophysics, including as the progenitors of gamma-ray bursts (GRBs), sources of high-frequency gravitational waves (GWs) and likely production sites for heavy-element nucleosynthesis by means of rapid neutron capture (the r -process). Here we present observations of the exceptionally bright GRB 230307A. We show that GRB 230307A belongs to the class of long-duration GRBs associated with compact object mergers and contains a kilonova similar to AT2017gfo, associated with the GW merger GW170817. We obtained James Webb Space Telescope (JWST) mid-infrared imaging and spectroscopy 29 and 61 days after the burst. The spectroscopy shows an emission line at 2.15 microns, which we interpret as tellurium (atomic mass A = 130) and a very red source, emitting most of its light in the mid-infrared owing to the production of lanthanides. These observations demonstrate that nucleosynthesis in GRBs can create r -process elements across a broad atomic mass range and play a central role in heavy-element nucleosynthesis across the Universe.

79 ASTRONOMY AND ASTROPHYSICS↗