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At least 235 records · Page 13

The Euler characteristic as a basis for teaching topology concepts to crystallographers

The simple Euler polyhedral formula, expressed as an alternating count of the bounding faces, edges and vertices of any polyhedron, V – E + F = 2, is a fundamental concept in several branches of mathematics. Obviously, it is important in geometry, but it is also well known in topology, where a similar telescoping sum is known as the Euler characteristic χ of any finite space. The value of χ can also be computed for the unit polyhedra (such as the unit cell, the asymmetric unit or Dirichlet domain) which build, in a symmetric fashion, the infinite crystal lattices in all space groups. In this application χ has a modified form (χ m ) and value because the addends have to be weighted according to their symmetry. Although derived in geometry (in fact in crystallography), χ m has an elegant topological interpretation through the concept of orbifolds. Alternatively, χ m can be illustrated using the theorems of Harriot and Descartes, which predate the discovery made by Euler. Those historical theorems, which focus on angular defects of polyhedra, are beautifully expressed in the formula of de Gua de Malves. In a still more general interpretation, the theorem of Gauss–Bonnet links the Euler characteristic with the general curvature of any closed space. This article presents an overview of these interesting aspects of mathematics with Euler's formula as the leitmotif. Finally, a game is designed, allowing readers to absorb the concept of the Euler characteristic in an entertaining way.

97 MATHEMATICS AND COMPUTING↗

Energetics of hydroxylbastnäsite solid solutions, La 1-$\chi$ Nd $\chi$ CO 3 OH

Bastnäsites (LnCO 3 (F,OH)) are a group of common rare earth elements (REE)-bearing minerals and are one of the primary global sources of REE. Due to the chemical similarities among REE, bastnӓsites tend to occur as solid solutions instead of end members in REE containing ores. To better understand the processes and the mechanisms of formation of such deposits, it is essential to determine the thermodynamic properties of bastnӓsites, including hydroxylbastnӓsite (LnCO 3 OH) solid solutions. In this work, we performed detailed structural and calorimetric investigations on synthetic hexagonal La–Nd hydroxylbastnӓsite (La 1-$\chi$ NdCO 3 OH, $\chi$ = 0, 0.25, 0.5, 0.75, 1) solid solutions. X-ray diffraction confirms the crystal structure of the solid solution series in the $\ P$6 space group, and pair distribution function (PDF) analysis reveals local bonding environments characterized by three different types of 9-coordinated metal-oxygen polyhedra. Unit cell parameters of La1–xNdxCO3OH exhibit a nearly linear relation with the Nd content x, suggesting a random distribution of La and Nd in the structure. Their standard enthalpies of formation (Δ$\ H$° f ) were determined by high temperature oxide melt drop solution calorimetry, from which the enthalpies of mixing (Δ$\ H$ mix ) were derived. The Δ$\ H$ mix can be fitted by a regular solution model with an interaction parameter of 12.58 ± 0.16 kJ/mol, suggesting enthalpic metastability of La1–xNdxCO3OH relative to the two endmembers. Combining entropy and enthalpy, we further estimated the Gibbs free energies of mixing (Δ$\ G$ mix ) at relevant temperatures, revealing favorable temperatures under which the intermediate La 1-$\chi$ NdCO 3 OH phases can be stabilized. Such entropy-driven stabilization, as is consistent with our geochemical modeling results, may explain the enhancement of thermal stability of the solid solutions in nature. Additionally, the temperature range constrained from this study may be used to estimate the thermal history of REE bastnӓsite deposit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Confocal Raman Microscopy Investigation of Phospholipid Monolayers Deposited on Nitrile-Modified Surfaces in Porous Silica Particles

Phospholipid bilayers deposited on a variety of surfaces offer models for investigation of the lipid membrane structure and supports for biocompatible sensors. Hybrid-supported phospholipid bilayers (HSLBs) are stable membrane models for these investigations, typically prepared by self-assembly of a lipid monolayer over an n-alkane-modified surface. HSLBs have been prepared on n-alkyl chain-modified silica and used for lipophilicity-based chromatographic separations. The structure of these hybrid bilayers differs from vesicle membranes where the lipid head group spacing is greater due to interdigitation of the lipid acyl chains with the underlying n-alkyl chains bound to the silica surface. This interdigitated structure exhibits a broader melting transition at a higher temperature due to strong interactions between the lipid acyl chains and the immobile n-alkyl chains bound to silica. In the present work, we seek to reduce the interactions between a lipid monolayer and its supporting substrate by self-assembly of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) on porous silica functionalized with nitrile-terminated surface ligands. The frequency of Raman scattering of the surface -C≡N stretching mode at the lipid–nitrile interface is consistent with an n-alkane-like environment and insensitive to lipid head group charge, indicating that the lipid acyl chains are in contact with the surface nitrile groups. The head group area of this lipid monolayer was determined from the within-particle phospholipid concentration and silica specific surface area and found to be 54 ± 2 Å 2 , equivalent to the head group area of a DMPC vesicle bilayer. The structure of these nitrile-supported phospholipid monolayers was characterized below and above their melting transition by confocal Raman microscopy and found to be nearly identical to DMPC vesicle bilayers. Their narrow gel-to-fluid-phase melting transition is equivalent to dispersed DMPC vesicles, indicating that the acyl chain structure on the nitrile support mimics the outer leaflet structure of a vesicle membrane.

36 MATERIALS SCIENCE↗

Nucleation and Growth According to Lysozyme

How does one take a molecule, strongly asymmetric in both shape and charge distribution, and assemble it into a crystal? We propose a model for the nucleation and crystal growth process for tetragonal lysozyme that may be very germane to other monomeric proteins. The first species formed is postulated to be a dimer. Through repeating associations involving the same intermolecular interactions this becomes the 4(sub 3) helix, that in turn serves as the basic unit for nucleation and crystal growth. High salt attenuates surface charges while promoting hydrophobic interactions. Symmetry facilitates helix self-association. Assembly stability is enhanced when a four helix structure is obtained, with each bound to two neighbors. Only two unique interactions are required. The first are those for helix formation, where the dominant interaction is the intermolecular bridging anion. The second is the anti-parallel side-by-side helix-helix interaction, guided by alternating pairs of symmetry related salt bridges along each side. At this stage all eight unique positions of the P4(sub 3)2(sub 1)2(sub 1) unit cell are filled. From the above, the process is one of a) attenuating the most strongly interacting groups, such that b) the molecules begin to self-associate in defined patterns, so that c) symmetry is obtained, which d) propagates as a growing crystal. Simple and conceptually obvious in hindsight, this tells much about what we are empirically doing when we crystallize macromolecules. By adjusting the solution parameters we are empirically balancing the intermolecular interactions, preferentially attenuating the dominant strong (for lysozyme the charged groups) while strengthening the lesser strong (hydrophobic) interactions. Lysozyme is atypical in the breadth of its crystallization conditions; many proteins only crystallize under narrowly defined conditions, pointing to the criticality of the empirical balancing process. Lack of a singularly defined association pathway leads to formation of multiple species, i.e., amorphous precipitation. Weak interactions, such as hydrogen bonds, are promiscuous, serving to strengthen rather than define specific interactions. Participation in an interaction sequesters that surface from subsequent interactions, and we expect the strongest bonds to form first. When two molecules self associate the resulting species will have an axis of symmetry. Subsequent interactions between two associated species having equivalent interactions will also have symmetry. Only a few unique sets of interactions are required to give any of the commonly found space groups for monomeric proteins. This model and what it suggests will be discussed.

Pusey, Marc L.↗

Identification of bioprivileged molecules: expansion of a computational approach to broader molecular space

As interest in biobased chemicals grows, and their application space expands, computational tools to navigate molecule space as a complement to experimental approaches are imperative. This work expands upon previous work that identified candidate bioprivileged molecules from the C 6 H x O y (C6) subspace. It refines the framework that was developed previously to better refine the molecules according to their biological origin and applies it to three new subspaces of chemical structure: C 4 H x O y (C4), C 5 H x O y (C5), and C 7 H x O y (C7). For C5 and C7, roughly the top 100 bioprivileged candidates were identified, and the enhanced framework was applied to recast slightly the previous list of the top 100 C6 molecules. In addition, all top candidates were analyzed for their key functional moieties using a random forest model, and this algorithm was applied to compare the functional group space occupied by bioprivileged molecules of various databases of molecules with a focus on evaluating how closely the molecules were aligned with those known to biology. Furthermore, with the present work's focus on automation and data science principles, the framework can be easily expanded to include other chemical formulae to screen for bioprivileged candidates. As a result, this in turn facilitates the retrosynthesis process inherent in the framework to identify those bioprivileged intermediates in other subspaces that lead to target molecules.

42 ENGINEERING↗

Agentic framework for programmatic crystal structure generation using a fine-tuned worker–supervisor large language model

Platinum group metals (PGMs) underpin many catalytic technologies but face severe supply constraints, motivating the search for alternative materials and computational methods to accelerate discovery. While atomistic simulation tools such as Pymatgen and ASE have streamlined structure manipulation, they require detailed inputs, limiting accessibility for experimentalists and slowing early-stage exploration. Here, in this study, we present an AI-driven agentic framework that orchestrates worker–supervisor large language models (LLMs). The worker translates natural-language prompts of varying abstraction into valid crystallographic structures using a compact LLM fine-tuned with low-rank adaptation on a curated text–code–CIF dataset, emphasizing energy-efficient training. Benchmarking against the baseline CodeGen-350M-mono model shows that fine-tuning reduces hallucination rates from 100% to as low as 5% and improves structural match accuracy to up to 82% for fully specified inputs. Accuracy declines with decreasing prompt detail but remains nontrivial even when only stoichiometry and space group are provided, underscoring the LLM’s capacity for crystallographic inference. The supervisor Claude LLM evaluates the outputs and triggers iterative refinement through the worker’s built-in structure manipulation capabilities (e.g., supercell scaling, strain, vacancy, and substitution operations). We further demonstrate use cases for technologically relevant catalysts, including IrO 2 , pyrochlore Pb 2 Ir 2 O 7 , Ni 2 FeO 4 , and Ni 3 Mo, where the framework generates physically consistent structures that can be refined via geometry optimization. This work introduces a low-energy, language-driven pathway for integrating human and machine intelligence in materials design, paving the way for AI-assisted synthesis planning and high-throughput screening of complex oxides.

AI agent↗

Fleetite, Cu 2 RhIrSb 2 , a New Species of Platinum-Group Mineral from the Miass Placer Zone, Southern Urals, Russia

Fleetite, Cu 2 RhIrSb 2 , a new species of platinum-group mineral (PGM), was discovered intergrown with an Os–Ir–Ru alloy in the Miass Placer Zone (Au–PGE), southern Urals, Russia. A single grain 50 μm across was found. Osmium, ruthenium, and iridium are the main associated minerals; also present are Pt–Fe alloys, laurite, Sb-rich irarsite, Rh-rich tolovkite, kashinite, anduoite, ferronickelplatinum, heazlewoodite, PGE-bearing pentlandite and digenite, as well as micrometric inclusions of forsterite (Fo 93.7 ), chromite–magnesiochromite, and Mg-rich edenite. In reflected light, fleetite is light gray; it is opaque, isotropic, non-pleochroic, and non-bireflectant. We report reflectance values measured in air. A mean of seven point-analyses (wavelength-dispersive spectrometry) gave Cu 13.93, Ni 8.60, Fe 0.10, Ir 28.07, Rh 7.91, Ru 1.96, Sb 39.28, total 99.85 wt.%, corresponding to (Cu 1.41 Ni 0.58 Fe 0.01 ) Σ2.00 (Rh 0.49 Ni 0.36 Ru 0.12 ) Σ0.97 Ir 0.95 Sb 2.08 on the basis of six atoms per formula unit, taking into account the structural results. The calculated density is 10.83 g/cm 3 . Single-crystal X-ray studies show that fleetite is cubic, space group Fdm (#227), a = 11.6682(8) Å, V = 1588.59(19) Å 3 , and Z = 16. A least-squares refinement of X-ray powder-diffraction data gave a = 11.6575(5) Å and V = 1584.22(19) Å 3 . The strongest five reflections in the powder pattern [d in Å(I)(hkl)] are: 6.70(75)(111), 4.13(100)(220), 3.52(30)(311), 2.380(50)(422), 2.064(40)(440). Results of synchrotron micro-Laue diffraction experiments are consistent [a = 11.66(2) Å]. The crystal structure of fleetite was solved and refined to R = 0.0340 based upon 153 reflections with F o > 4σ(F o ). It is isotypic with Pd 11 Bi 2 Se 2 and best described as intermetallic, with all metal atoms in 12-fold coordination. Fleetite and other late exotic phases were formed by reaction of the associated alloy phases with a fluid phase enriched in Sb, As, and S in circulation in the cooling ophiolite source-rock. The mineral is named after Michael E. Fleet (1938–2017) in recognition of his significant contributions to the Earth Sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling topology through targeted composite symmetry manipulation in magnetic systems

The possibility of selecting magnetic space groups by orienting the magnetization direction or tuning magnetic orders offers a vast playground for engineering symmetry-protected topological phases in magnetic materials. In this work, we study how selective tuning of symmetry and magnetism can influence and control the resulting topology in a two-dimensional magnetic system, and we illustrate such a procedure in the ferromagnetic monolayer MnPSe 3 . Density functional theory calculations reveal a symmetry-protected accidental semimetallic (SM) phase for out-of-plane magnetization, which becomes an insulator when the magnetization is tilted in-plane, reaching band-gap values close to 100 meV. We identify an order-2 composite antiunitary symmetry and threefold rotational symmetry that induce the band crossing, and we classify the possible topological phases using symmetry analysis, which we support with tight-binding and k · p models. Breaking of inversion symmetry opens a gap in the SM phase, giving rise to a Chern insulator. We demonstrate this explicitly in the isostructural Janus compound Mn 2 ⁢P 2 ⁢S 3 ⁢Se 3 , which naturally exhibits Rashba spin-orbit coupling that breaks inversion symmetry. Our results map out the phase space of topological properties of ferromagnetic transition-metal phosphorus trichalcogenides, and they demonstrate the potential of the magnetization-dependent metal-to-insulator transition as a spin switch in integrated two-dimensional electronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , a New Mineral Species from the Sisim Placer Zone, Eastern Sayans, Russia, and the Torryweiserite–Ferrotorryweiserite Series

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , occurs as small grains (≤20 µm) among droplet-like inclusions (up to 50 μm in diameter) of platinum-group minerals (PGM), in association with oberthürite or Rh-bearing pentlandite, laurite, and a Pt-Pd-Fe alloy (likely isoferroplatinum and Fe-Pd-enriched platinum), hosted by placer grains of Os-Ir alloy (≤0.5 mm) in the River Ko deposit. The latter is a part of the Sisim placer zone, which is likely derived from ultramafic units of the Lysanskiy layered complex, southern Krasnoyarskiy kray, Russia. The mineral is opaque, gray to brownish gray in reflected light, very weakly bireflectant, not pleochroic to weakly pleochroic (grayish to light brown tints), and weakly anisotropic. The calculated density is 5.93 g·cm –3 . Mean results (and ranges) of four WDS analyses are: Ir 18.68 (15.55–21.96), Rh 18.34 (16.32–20.32), Pt 0.64 (0.19–1.14), Ru 0.03 (0.00–0.13), Os 0.07 (0.02–0.17), Fe 14.14 (13.63–14.64), Ni 13.63 (12.58–14.66), Cu 4.97 (3.42–6.41), Co 0.09 (0.07–0.11), S 29.06 (28.48–29.44), and total 99.66 wt.%. They correspond to the following formula calculated for a total of 31 atoms per formula unit: (Rh 3.16 Ir 1.72 Pt 0.06 Ru 0.01 Os 0.01 ) Σ 4.95 (Fe 4.48 Ni 4.11 Cu 1.38 Co 0.03 ) Σ10.00 S 16.05 . The results of synchrotron micro-Laue diffraction studies indicate that ferrotorryweiserite is trigonal; its probable space group is $R\bar{3}m$ (#166) based on its Ni-analog, torryweiserite. The unit-cell parameters refined from 177 reflections are a = 7.069 (2) Å, c = 34.286 (11) Å, V = 1484 (1) Å 3 , and Z = 3. The c:a ratio is 4.8502. The strongest eight peaks in the X-ray diffraction pattern derived from results of micro-Laue diffraction study [d in Å(hkil)(I)] are 2.7950 ($20\bar{2}5$) (100); 5.7143 (0006) (60); 1.7671 ($22\bar{4}0$) (44.4); 3.0486 ($20\bar{2}1$) (39.4); 5.7650 ($10\bar{1}2$) (38.6); 2.5956 ($20\bar{2}7$) (37.8); 3.0058 ($11\bar{2}6$) (36.5); and 1.5029 ($4\bar{2}\bar{2}12$) (35.3). Ferrotorryweiserite and the associated PGM crystallized from microvolumes of residual melt at late stages of crystallization of grains of Os- and Ir-dominant alloys occurred in lode zones of chromitites of the Lysanskiy layered complex. In a particular case, the residual melt is disposed peripherally around a core containing a disequilibrium association of magnesian olivine (Fo 72.9–75.6 ) and albite (Ab 81.6–86.4 ), with the development of skeletal crystals of titaniferous augite: Wo 40.8–43.2 En 26.5–29.3 Fs 20.3–22.6 Aeg 6.9–9.5 (2.82–3.12 wt.% TiO 2 ). Ferrotorryweiserite represents the Fe-dominant analog of torryweiserite. We also report occurrences of ferrotorryweiserite in the Marathon deposit, Coldwell Complex, Ontario, Canada, and infer the existence of the torryweiserite–ferrotorryweiserite solid solution in other deposits and complexes.

58 GEOSCIENCES↗

Symmetry-driven persistent spin texture for the two-dimensional nonsymmorphic CdTe and ZnTe crystal structures

In this paper, two nonsymmorphic two-dimensional structures of CdTe and ZnTe are modeled, and using state-of-the-art density functional theory with the group theory of solids, their symmetry-enforced electronic properties are studied. The in-plane ferroelectricity coupled with strong spin-orbit coupling induces a unidirectional out-of-plane Rashba spin-orbit field that can host a momentum-independent uniform spin configuration known as persistent spin texture (PST) at the Brillouin zone center. PST in these structures is found to be robust against external perturbations such as strain, structural distortion, and independent of layer thickness. These unprecedented intrinsic spin transport properties hold utmost importance in spintronics, as the experimental stringent condition of equal Rashba and Dresselhaus constants [Phys. Rev. Lett. 90, 146801 (2003)] is eliminated. The calculated persistent spin helix wavelength of <~5 nm paves the way for developing next-generation nanosized nonballistic spin field-effect transistors compared with micrometer-sized GaAs/AlGaAs quantum wells. Further, these materials exhibit finite spin Hall conductivity at the band edges and hence can be used in ferromagnet-free spin Hall transistors. Although CdTe and ZnTe systems have been widely studied for photocatalysis and solar cell applications over the past few decades, their potential application in spintronic devices has not been explored. Mono/few layers of CdTe and ZnTe synthesized from (110) facets of bulk zinc-blende crystals [Nat. Commun. 3, 1057 (2012)] satisfy all symmetry operations of the nonsymmorphic space group and hence can be considered ideal materials to verify our theoretical results experimentally.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Venturing into Unexplored Phase Space: Synthesis, Structure, and Properties of MgCo 3 B 2 Featuring a Rumpled Kagomé Network

MgCo 3 B 2 , a novel ternary boride in a previously unexplored phase space, was synthesized using the hydride route. In situ powder X-ray diffraction and DFT calculations aided in the discovery of this compound, whose structure was then determined by single-crystal X-ray diffraction. Like the closely related CeCo 3 B 2 , MgCo 3 B 2 crystallizes in centrosymmetric space group P6/mmm (a = 4.883(2) Å, c = 2.926(2) Å at 210 K, Z = 1). Unlike CeCo 3 B 2 , however, it adopts a disordered structure that features a rumpled Kagomé network of Co atoms, and Mg atoms fill the channels of a Co–B framework. Although the structural disorder leads to motifs that are similar to those observed in MgNi 3 B 2 and other related ternary borides, no evidence of an ordered superstructure was found by single-crystal X-ray diffraction or high-resolution powder X-ray diffraction. In the case of CeCo 3 B 2 , boron atoms occupy the center of regular Co 6 trigonal prisms; in MgCo 3 B 2 , boron atoms are shifted from the center of the prism to form B–B dimers with roughly the same length as those found in MgNi 3 B 2 . Magnetic susceptibility data exhibit an unusual temperature dependence that cannot be convincingly modeled by the modified Curie–Weiss equation, consistent with DFT calculations predicting a nonmagnetic ground state. Intrinsic susceptibility at 300 K is 1.42 × 10 –3 emu/mol Oe, which is comparable to that of paramagnetic YCo 3 B 2 and CeCo 3 B 2 with a similar structure and composition. Here, this study showcases the efficacy of combining several methodologies to discover new solids in unexplored phase spaces. This approach includes in situ PXRD data to monitor reactions of precursors upon heating, a diffusion-enhanced synthesis method, and DFT assessment of compound stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stimuli‐Responsive Emission from Hybrid Metal Halides

Abstract Stimuli‐responsive photoluminescent (PL) materials have attracted considerable attention in recent years owing to their potential applications in anti‐counterfeiting, information encryption, and sensing. Further investigations of the transformation mechanism and potential applications of stimulus‐responsive PL materials are considerably important. In the current study, an organic–inorganic metal halide, C 9 H 15 N 3 SbCl 5 ([C 9 H 13 N 3 ] 2+ is a 1‐(2‐pyridyl) piperazine cation) is obtained, which exhibits a 0D structure withP‐1 space group. At room temperature, when excited by UV light, the C 9 H 15 N 3 SbCl 5 single crystals exhibit unimodal blue light emission at 405 nm, and grinding or hydrostatic pressure induces double‐peak emissions at 405 and 650 nm. Interestingly, double‐emission samples can be restored to single‐emission samples by short annealing or storage in air for 2 weeks, and this process is reversible. Luminescence response to mechanical stimuli can also be achieved in the presence of hydrochloric acid and water. Spectral analysis and the analysis of the microstructural changes revealed that the structural modifications of the inorganic group play a pivotal role in the response to the stimulus. Finally, a composite film device based on C 9 H 15 N 3 SbCl 5 is prepared to demonstrate the potential of these smart materials in anti‐counterfeiting and sensing applications.

Chemistry↗

Strain‐Driven Stabilization of a Room‐Temperature Chiral Multiferroic with Coupled Ferroaxial and Ferroelectric Order

Noncollinear ferroic materials are sought after as testbeds to explore the intimate connections between topology and symmetry, which result in electronic, optical, and magnetic functionalities not observed in collinear ferroic materials. For example, ferroaxial materials have rotational structural distortions that break mirror symmetry and induce chirality. When ferroaxial order is coupled with ferroelectricity arising from a broken inversion symmetry, it offers the prospect of electric-field-control of the ferroaxial distortions and opens up new tunable functionalities. However, chiral multiferroics, especially ones stable at room temperature, are rare. A strain-stabilized, room-temperature chiral multiferroic phase in single crystals of BaTiS 3 is reported here. Using first-principles calculations, the stabilization of this multiferroic phase having P6 3 space group for biaxial tensile strains exceeding 1.5% applied on the basal ab-plane of the room temperature P6 3 cm phase of BaTiS 3 is predicted. The chiral multiferroic phase is characterized by rotational distortions of TiS 6 octahedra around the long c-axis and polar displacement of Ti atoms along the c-axis. Furthermore, the ferroaxial and ferroelectric distortions and their domains in P6 3 -BaTiS 3 are directly resolved using atomic resolution scanning transmission electron microscopy. Landau-based phenomenological modeling predicts a strong coupling between the ferroelectric and the ferroaxial order making P6 3 -BaTiS 3 an attractive test bed for achieving electric-field-control of chirality.

Chalcogenide↗

Nonequilibrium Lattice Dynamics in Photoexcited 2D Perovskites

Abstract Interplay between structural and photophysical properties of metal halide perovskites is critical to their utility in optoelectronics, but there is limited understanding of lattice response upon photoexcitation. Here, 2D perovskites butylammonium lead iodide, (BA) 2 PbI 4 , and phenethylammonium lead iodide, (PEA) 2 PbI 4 , are investigated using ultrafast transient X‐ray diffraction as a function of optical excitation fluence to discern structural dynamics. Both powder X‐ray diffraction and time‐resolved photoluminescence linewidths narrow over 1 ns following optical excitation for the fluence range studied, concurrent with slight redshifting of the optical bandgaps. These observations are attributed to transient relaxation and ordering of distorted lead iodide octahedra stimulated mainly by electron–hole pair creation. The c axis expands up to 0.37% over hundreds of picoseconds; reflections sampling the a and b axes undergo one tenth of this expansion with the same timescale. Post‐photoexcitation appearance of the (110) reflection in (BA) 2 PbI 4 would suggest a transient phase transition, however, through new single‐crystal XRD, reflections are found that violate glide plane conditions in the reported Pbca structure. The static structure space group is reassigned as P 2 1 2 1 2 1 . With this, a nonequilibrium phase transition is ruled out. These findings offer increased understanding of remarkable lattice response in 2D perovskites upon excitation.

36 MATERIALS SCIENCE↗

Infrared Optical Anisotropy in Quasi‐1D Hexagonal Chalcogenide BaTiSe 3

Polarimetric infrared (IR) detection bolsters IR thermography by leveraging the polarization of light. Optical anisotropy, i.e., birefringence and dichroism, can be leveraged to achieve polarimetric detection. Recently, giant optical anisotropy is discovered in quasi-1D narrow-bandgap hexagonal perovskite sulfides, A 1+x TiS 3 , specifically BaTiS 3 and Sr 9/8 TiS 3 . In these materials, the critical role of atomic-scale structure modulations in the unconventional electrical, optical, and thermal properties raises the broader question of the nature of other materials that belong to this family. To address this issue, for the first time, high-quality single crystals of a largely unexplored member of the A 1+x TiX 3 (X = S, Se) family, BaTiSe 3 are synthesized. Single-crystal X-ray diffraction determined the room-temperature structure with the P31c space group, which is a superstructure of the earlier reported P6 3 /mmc structure. The crystal structure of BaTiSe 3 features antiparallel c-axis displacements similar to but of lower symmetry than BaTiS 3 , verified by the polarization dependent Raman spectroscopy. Fourier transform infrared (FTIR) spectroscopy is used to characterize the optical anisotropy of BaTiSe 3 , whose refractive index along the ordinary (E ⊥ c) and extraordinary (E ‖ c) optical axes is quantitatively determined by combining ellipsometry studies with FTIR. With a giant birefringence Δn ∼ 0.9, BaTiSe 3 emerges as a new candidate for miniaturized birefringent optics for mid-wave infrared to long-wave infrared imaging.

optical anisotropy↗

Ferromagnetic Double Perovskite Semiconductors with Tunable Properties

Abstract The authors successfully dope the magnetically silent double perovskite semiconductor Sr 2 GaSbO 6 to induce ferromagnetism and tune its bandgap, with Ga 3+ partially substituted by the magnetic trivalent cation Mn 3+ , in a rigid cation ordering with Sb 5+ . The new ferromagnetic semiconducting Sr 2 Ga 1− x Mn x SbO 6 double perovskite, which crystallizes in tetragonal symmetry (space group I 4/ m ) and has tunable ferromagnetic ordering temperature and bandgap, suggests that magnetic ion doping of double perovskites is a productive avenue toward obtaining materials for application in next‐generation oxide‐based spintronic devices.

36 MATERIALS SCIENCE↗

Pressure‐Induced Structural and Magnetic Evolution in Layered Antiferromagnet YbMn 2 Sb 2

Electronic states under pressure exhibit unconventional spin and charge dynamics that provide a powerful route to uncover exotic phases in quantum materials. Here, we present the structural, magnetic, and electronic evolution of YbMn 2 Sb 2 under pressure. Single-crystal X-ray diffraction reveals a pressure-induced structural transition from the space group trigonal P$\overline{3}$m1 to the monoclinic P2 1 /m phase near 3.5 GPa, which remains stable up to 10 GPa. Magnetization measurements display an anomalously weak net magnetic moment and the absence of Curie–Weiss behavior up to 400 K, suggesting the formation of short-range Mn moment pairs that cancel macroscopically and subsequently evolve into long-range order upon cooling. Temperature-dependent resistivity shows semiconducting behavior with a transition at ∼119 K at ambient pressure, while pressure induces a dramatic suppression of resistance and the emergence of metallic-like temperature dependence, stabilized beyond 5 GPa. This pressure-driven semiconductor-metal transition is consistent with our density functional theory calculations, confirming the closing of the band gap under compression. Neutron diffraction under pressure identifies an incommensurate magnetic structure with antiparallel correlations between paired spins. Together, these results demonstrate how pressure-driven structural tuning and competing exchange interactions stabilize unconventional magnetic states in this low-dimensional magnetic semiconductor.

antiferromagnetic semiconductor↗

Stress‐Induced Domain Wall Motion in a Ferroelastic Mn 3+ Spin Crossover Complex

Abstract Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single‐crystal X‐ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn 3+ compound [Mn(3,5‐diBr‐sal 2 (323))]BPh 4 , 1. The first at 250 K, involves the space group change Cc → Pc and is thermodynamically continuous, while the second, Pc → P 1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress‐induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc ‐ P 1 transition

Jakobsen, Vibe B.↗