Neutron Powder Diffraction Measurements Research Articles

Contrasting Magnetic Structures in the Quaternary Sulfides Ba2FeMS5 (M = Sb, Bi).

Ba2FeSbS5 and Ba2FeBiS5 are two isostructural quaternary sulfides that crystallize in the Pnma space group with four formula units per unit cell. Ba2FeSbS5 has lattice parameters a = 12.08609(3) Å, b = 8.83426(2) Å, and c = 8.89114(2) Å, and Ba2FeBiS5 has a = 12.09610(3) Å, b = 8.89281(2) Å, and c = 8.82437(2) Å at room temperature. They comprise infinite [FeMS5]4- (M = Sb, Bi) chains, where Fe3+ is present in FeS4 tetrahedra and M3+ ions reside in edge-sharing MS6 distorted octahedra, each of which shares an edge with an FeS4 tetrahedron. Powder neutron diffraction measurements confirm the presence of long-range antiferromagnetic order of the Fe3+ moments in both materials, where Fe-S···S-Fe super-superexchange interactions which act along the direction of the [FeMS5]4- (M = Sb, Bi) chains are the driving force for this antiferromagnetic order. The magnetic Bragg reflections reside on a k-vector with k = (1/2 0 1/2), and the relative orientations of the moments are similar in the two cases One significant difference is that the moments are aligned along the crystallographic b-axis in Ba2FeSbS5, whereas in Ba2FeBiS5 they lie along the longer crystallographic a-axis, reflecting the weak directional preference of the Fe3+ moments. Furthermore, an additional incommensurately modulated ordering of the Fe3+ moments is suggested for Ba2FeSbS5 (but not Ba2FeBiS5) by the appearance of small additional magnetic Bragg peaks in the neutron diffraction data, which may be a consequence of greater magnetic frustration in Ba2FeSbS5.

Spin reorientation and the interplay of magnetic sublattices in Er2CuMnMn4O12.

Through a combination of magnetic susceptibility, specific heat, and neutron powder diffraction measurements we have revealed a sequence of four magnetic phase transitions in the columnar quadruple perovskite Er2CuMnMn4O12. A key feature of the quadruple perovskite structural framework is the complex interplay of multiple magnetic sublattices via frustrated exchange topologies and competing magnetic anisotropies. It is shown that in Er2CuMnMn4O12, this phenomenology gives rise to multiple spin-reorientation transitions driven by the competition of easy-axis single ion anisotropy and the Dzyaloshinskii-Moriya interaction; both within the manganese B-site sublattice. At low temperature, one Er sublattice orders due to a finite f-d exchange field aligned parallel to its Ising axis, while the other Er sublattice remains non-magnetic until a final, symmetry-breaking phase transition into the ground state. This non-trivial low-temperature interplay of transition metal and rare-earth sublattices, as well as an observed k = (0, 0, ½) periodicity in both manganese spin canting and Er ordering, raises future challenges to develop a complete understanding of the R2CuMnMn4O12 family.

Ferrimagnetic structures with rare-earth induced spin-reorientation in the Mn self-doped perovskite (Er0.7Mn0.3)MnO3

The search for spin-reorientation (SR) phase transitions, a spontaneous rotation of ordered magnetic moments, in ferrimagnetic (FiM) materials, which carry a net magnetization, is of fundamental and practical interest for applications in the field of spintronics. In this work, we have investigated Mn self-doped (Er0.7Mn0.3)MnO3 solid solution with GdFeO3-type Pnma perovskite structure by combining specific heat, magnetic susceptibility and neutron powder diffraction measurements. We provide experimental evidence for FiM order below TC = 104 K, and a spontaneous SR transition at TSR = 11 K. A FiM structure appears in all (R1-xMnx)MnO3 compounds with R = Dy–Lu for x ≥ 0.2. But in this structural family, R = Er is the only material with a SR transition. FiM order in (Er0.7Mn0.3)MnO3 appears with ferromagnetic (FM) ordering of Mn3+ and Mn4+ cations at the B site along the a-direction, which are antiferromagnetically (AFM) coupled with Er3+ and Mn2+ cations at the A site. At TSR, ordered Er3+ change direction from the magnetically harder a-axis to the magnetically easy b-axis and induce a change of the whole FiM structure, including the direction of all Mn spins from the irreducible representation mGM3+ to mGM4+. We calculated the crystal-field (CF) anisotropy for Ho3+ in (Ho0.8Mn0.2)MnO3 and Er3+ in (Er0.7Mn0.3)MnO3, based on the point charge model; the results revealed large magnetic anisotropies. For the FiM structure of (Ho0.8Mn0.2)MnO3, the magnetically easy a-axis of Ho3+ keeps the high-temperature magnetic directions along the a-axis and gives rise to a pronounced magnetization reversal effect at low temperature because of a significant rise of Ho3+ ordered moments. On the other hand, for the FiM structure of (Er0.7Mn0.3)MnO3, the magnetically easy b-axis of Er3+ gives rise to a SR phase transition at TSR, which does not lead to magnetization reversal even though Er3+ ordered moments rise significantly at low temperatures.

Effects of Fe substitution for Mn on structural, magnetic and magnetocaloric properties of TbMn2-xFexSi2

The structural and magnetic properties of TbMn2-xFexSi2 compounds (x = 0.0–0.4) have been investigated in details by high-resolution synchrotron x-ray and neutron powder diffraction, specific heat, and dc magnetization measurements. The replacement of Fe for Mn in TbMn2-xFexSi2 does not change the crystal structure but leads to a significant contraction of the unit cell (dV/dx ∼ - 6 Å3) and modification of three magnetic phase transition temperatures – the Curie temperatures Tc1, Tc2 and the Néel temperature TN. For example, the Tc1, Tc2 and TN values of TbMn2Si2 decrease from Tc1 = 50 K, Tc2 = 64 K and TN = 500 K to Tc1 = 27 K, Tc2 = 37 K and TN = 440 K for TbMn1.6Fe0.4Si2. Detailed neutron diffraction investigations have allowed us to determine the magnetic structures and construct the magnetic phase diagram as well as confirm the presence of magnetoelastic coupling effects. The significantly different responses of Tc1 and Tc2 to applied magnetic fields (e.g. dTc1/dB = 0.52 K/T and dTc2/dB = 4.7 K/T for TbMn1.6Fe0.4Si2), leads to expansion of the temperature region (ΔT = Tc2- Tc1) for the canted ferromagnetic state Fmc-ii between Tc1 and Tc2. In the case of TbMn1.6Fe0.4Si2, ΔT increases from ΔT = 9 K for applied magnetic field B = 0.2 T to ΔT = 36 K for B = 6 T, resulting in plateau-like behaviour of magnetic entropy change and enhances the relative cooling power (RCP) in this system. Under a change of magnetic field of 0 T – 5 T, the maximum value of the magnetic entropy changes -ΔSmax and adiabatic temperature change, ΔTad are derived to be -ΔSmax = 13.1 J/kg K and ΔTad = 8.4 K with the RCP = 411 J/kg for x=0.4 sample. The plateau-like magnetocaloric effect and relatively large RCP make these materials potentially suitable for application in cryogenic magnetic refrigeration.

Magnetic structures in R5Pt2In4 (R = Tb-Tm) investigated by neutron powder diffraction.

Results of the neutron powder diffraction measurements carried out for R5Pt2In4 (R = Tb-Tm) are reported. The compounds crystallize in an orthorhombic crystal structure of the Lu5Ni2In4-type with the rare earth atoms occupying three different sublattices. Neutron diffraction data reveal that at low temperatures the rare earth magnetic moments order below the critical temperature equal to 105, 93, 28, 12 and 3.8 K for R = Tb, Dy, Ho, Er and Tm, respectively. With decreasing temperature the rare earth magnetic moments at the 2a and 4g2 sites order first, while the moments at the 4g1 site order at lower temperatures. Ferrimagnetic order along the c axis, described by the propagation vector k1 = [0, 0, 0], develops in Tb5Pt2In4 below the Curie temperature (TC = 105 K). At lower temperatures, an antiferromagnetic component in the ab plane appears. The component is incommensurate with the crystal structure (k2 = [0, 0.66, ½]), but it turns into a commensurate one (k3 = [0, 0, ½]) with decreasing temperature. Antiferromagnetic order along the c axis, described by k4 = [½, 0, 0], is found in Dy5Pt2In4 below the Néel temperature (TN = 93 K). The k4-related component disappears below 80 K and the magnetic structure transforms into a ferro/ferrimagnetic one described by k1 = [0, 0, 0]. Further decrease in temperature leads to the appearance of an incommensurate antiferromagnetic component within the ab plane below 10 K (k2 = [0, 0.45, ½]), which finally turns into a commensurate one (k5 = [0, ½, ½]). In Ho5Pt2In4, a sine-modulated magnetic structure with moments parallel to the c axis (k6 = [⅓,0,0]) is observed below 28 K. With a decrease in temperature, new components, related to k1 = [0, 0, 0] (bc plane) and k4 = [½, 0, 0] (c axis), appear. The coexistence of two orderings - in the ab plane (k1 = [0, 0, 0]) and a modulated one with moments along the b axis (k7 = [kx, 0, 0]) - is found in Er5Pt2In4 below 12 K. Decreasing temperature leads to the order-order transformation of the k1-related component to another one with magnetic moments still constrained to the ab plane and preserved value of the propagation vector (i.e. k1 = [0, 0, 0]). Tm5Pt2In4 orders antiferromagnetically below TN = 3.8 K. Thulium magnetic moments lie in the ab plane, while the magnetic structure is described by k5 = [0, ½ , ½]. The direction of magnetic moments depends on the rare earth element involved and indicates an influence of single ion anisotropy resulting from interaction with the crystalline electric field.

Crystal structure, magnetic and electrical transport properties of titanium-doped half-Heusler alloys Ni1−xTixMnSb

Ni[Formula: see text]TixMnSb polycrystalline alloys in the range [Formula: see text] were synthesized employing the standard solid-phase synthesis method. The crystal, magnetic, as well as electrical properties of the alloys were investigated using neutron powder diffraction and magneto-resistance measurements. The results reveal that the substitution of Ti for Ni within the temperature range of 2.5–300 K does not induce alterations in the crystal and magnetic structures of NiMnSb. The ordered Ni magnetic moment approaches zero. The study of the electrical transport properties of the Ni[Formula: see text]TixMnSb alloys, where [Formula: see text], has demonstrated a half-metallic state at low temperatures and metallic conductivity for temperatures exceeding 160 K. A semiconductor state manifests at titanium concentrations of x = 0.2 and was observed at temperatures below 21 K. The obtained experimental results are elucidated through first-principles theoretical calculations.

A comparative study of magnetic behaviours in bulk and ribbon samples of PrMn2Ge2 compound

The magnetic properties of PrMn2Ge2 samples in both the as-cast bulk and melt-spun ribbon forms have been investigated in detail by a comprehensive set of x-ray and neutron powder diffraction, magnetic and heat capacity measurements and corresponding sets of data analyses. Thermal expansion measurements indicate the presence of magnetoelastic coupling effects around all transition temperatures in the bulk sample. The bulk modulus K0 = 42.0 GPa and its first derivative K0’ = 18.7 have been derived from the pressure-volume data. The Curie temperature from the intralayer antiferromagnetism (AFl) of PrMn2Ge2 to a canted spin structure (Fmc) is TCinter = 332 K for the bulk sample, decreasing to TCinter = 320 K for the ribbon sample. The critical components γ, β and δ of this second order magnetic transition as determined from Kouvel-Fisher analyses, indicate long range magnetic interactions around TCinter. Based on these critical exponents the magnetization, field and temperature data around TCinter collapse onto two curves obeying the single scaling equation M(H,ε)=εβf±(Hεβ+γ). The Debye temperatures and the density of states at the Fermi level are θD=306K and N(EF)=3.47state/eVatom for the bulk sample and θD=320K and (EF)=2.18state/eVatom for the ribbon sample with the nuclear specific heat coefficient for bulk PrMn2Ge2 derived from the splitting of the nuclear hyperfine levels as CN = 517 mJ mol−1 K−1. With a field change of ΔB = 5 T, the maximum values of the magnetic entropy changes -ΔSmax in the region around TCinter are -ΔSmax = 3.00 J/kg K and 2.35 J/kg K for the bulk and ribbon samples respectively, while the relative cooling power (RCP) for the ribbon-spun sample, RCP = 135.9 J/kg, is significantly higher than the value of RCP = 116.6 J/kg for the bulk sample. These findings indicate that PrMn2Ge2 could be a promising candidate for magnetic refrigeration applications in the room temperature region.

Pressure-tuned quantum criticality in the large-D antiferromagnet DTN

Strongly correlated spin systems can be driven to quantum critical points via various routes. In particular, gapped quantum antiferromagnets can undergo phase transitions into a magnetically ordered state with applied pressure or magnetic field, acting as tuning parameters. These transitions are characterized by z = 1 or z = 2 dynamical critical exponents, determined by the linear and quadratic low-energy dispersion of spin excitations, respectively. Employing high-frequency susceptibility and ultrasound techniques, we demonstrate that the tetragonal easy-plane quantum antiferromagnet NiCl2 ⋅ 4SC(NH2)2 (aka DTN) undergoes a spin-gap closure transition at about 4.2 kbar, resulting in a pressure-induced magnetic ordering. The studies are complemented by high-pressure-electron spin-resonance measurements confirming the proposed scenario. Powder neutron diffraction measurements revealed that no lattice distortion occurs at this pressure and the high spin symmetry is preserved, establishing DTN as a perfect platform to investigate z = 1 quantum critical phenomena. The experimental observations are supported by DMRG calculations, allowing us to quantitatively describe the pressure-driven evolution of critical fields and spin-Hamiltonian parameters in DTN.

Direct Ethylene Purification from Cracking Gas via a Metal–Organic Framework Through Pore Geometry Fitting

The direct one-step separation of polymer-grade C2H4 from complex light hydrocarbon mixtures has high industrial significance but is very challenging. Herein, an ethylene-adsorption-weakening strategy is applied for precise regulation of the pore geometry of four tailor-made metal–organic frameworks (MOFs) with pillar-layered structures, dubbed TYUT-10/11/12/13. Based on its pore geometry design and functional group regulation, TYUT-12 exhibits exceptional selective adsorption selectivity toward C3H8, C3H6, C2H6, C2H2, and CO2 over C2H4; its C2H6/C2H4 adsorption selectivity reaches 4.56, surpassing the record value of 4.4 by Fe2(O2)(dobdc) (dobdc4− = 2,5-dioxido-1,4-benzenedicarboxylate). The weak π–π stacking binding affinity toward C2H4 in TYUT-12 is clearly demonstrated through a combination of neutron powder diffraction measurements and theoretical calculations. Breakthrough experiments demonstrate that C2H4 can be directly obtained from binary, ternary, quaternary, and six-component light hydrocarbon mixtures with over 99.95% purity.

Unveiling exotic magnetic phase diagram of a non-Heisenberg quasicrystal approximant

A magnetic phase diagram of the non-Heisenberg Tsai-type 1/1 Au-Ga-Tb approximant crystal (AC) has been established across a wide electron-per-atom (e/a) range via magnetization and powder neutron diffraction measurements. The diagram revealed exotic ferromagnetic (FM) and antiferromagnetic (AFM) orders that originate from the unique local spin icosahedron common to icosahedral quasicrystals (iQCs) and ACs; The noncoplanar whirling AFM order is stabilized as the ground state at the e/a of 1.72 or less whereas a noncoplanar whirling FM order was found at the larger e/a of 1.80, with magnetic moments tangential to the Tb icosahedron in both cases. Moreover, the FM/AFM phase selection rule was unveiled in terms of the nearest neighbour (J1) and next nearest neighbour (J2) interactions by numerical calculations on a non-Heisenberg single icosahedron. The present findings will pave the way for understanding the intriguing magnetic orders of not only non-Heisenberg FM/AFM ACs but also non-Heisenberg FM/AFM iQCs, the latter of which are yet to be discovered.

High-density, spontaneous magnetic biskyrmions induced by negative thermal expansion in ferrimagnets.

Magnetic skyrmions are topologically protected quasiparticles that are promising for applications in spintronics. However, the low stability of most magnetic skyrmions leads to either a narrow temperature range in which they can exist, a low density of skyrmions, or the need for an external magnetic field, which greatly limits their wide application. In this study, high-density, spontaneous magnetic biskyrmions existing within a wide temperature range and without the need for a magnetic field were formed in ferrimagnets owing to the existence of a negative thermal expansion of the lattice. Moreover, a strong connection between the atomic-scale ferrimagnetic structure and nanoscale magnetic domains in Ho(Co,Fe)3 was revealed via in situ neutron powder diffraction and Lorentz transmission electron microscopy measurements. The critical role of the negative thermal expansion in generating biskyrmions in HoCo3 based on the magnetoelastic coupling effect is further demonstrated by comparing the behavior of HoCo2.8Fe0.2 with a positive thermal expansion.

Synthesis, structure and canted antiferromagnetism of layered cobalt hydroxide sorbate

Layered hybrid organic–inorganic compounds of the transition metal hydroxides, in which part of the hydroxide ions are exchanged for organic ligands that act as spacers of the 2-dimensional inorganic layers, elicit new or enhanced properties. The interlayer ligands enable fine-tuning of the physicochemical properties of the metal hydroxide layers, including their magnetism. Specifically, within the Co(OH)2 family of transition ion hydroxides, this approach has been leveraged to stabilize antiferromagnetic and ferrimagnetic ground states for pillared and layered complexes, respectively. Here, we further investigate the effects of changing dimensionality, local Co coordination, and interlayer spacing on the magnetic ground state of brucite-like β-Co(OH) layered complexes. We report the hydrothermal synthesis of a new crystalline material, Co(OH)(sorb), where the inorganic layers are spaced by monotopic, doubly unsaturated sorbate ligands (sorb = [C6H7O2]−). The material was structurally characterized using powder X-ray and neutron diffraction measurements and the crystal structure was solved ab initio from powder diffraction data and refined using the Rietveld method. The magnetic susceptibility and magnetization measurements reveal canted antiferromagnetic ordering with TN = 41.7 K. This report augments our understanding of tuning magnetism through dimensionality in layered complexes and represents a step forward in the design of new 2D layered hybrid compounds.

Unusually large magnetic moment and tricritical behavior of the CMR compound NaCr2O4 revealed with high resolution neutron diffraction and SR

The mixed valence Cr3+/Cr4+ compound NaCr2O4, hosts a plethora of unconventional electronic properties. In the present study, muon spin rotation/relaxation (SR) and high-resolution time-of-flight neutron powder diffraction measurements were carried out on high-quality samples to clarify the complex magnetic ground state of this unique material. We identified a commensurate canted antiferromagnetic order (C-AFM) with a canting angle of the Cr spin axial vector equal to , and an estimated Cr moment . Such an unusually large value of is compatible with the existence of high-spin Cr sites created by the presence of an unconventional negative charge transfer state in NaCr2O4. In addition to the C-AFM structure, a novel magnetic supercell was also revealed. Such supercell display an incommensurate (IC)-AFM propagation vector (0 0 ), having a Cr moment . It is suggested that the C-AFM and IC-AFM modulations have two different electronic origins, being due to itinerant and localized contributions to the magnetic moment respectively. Finally, the direct measurement of the magnetic order parameter for the C-AFM structure provided a value of the critical exponent , suggesting a non conventional critical behavior for the magnetic phase transition in NaCr2O4.

Synthesis and anisotropic magnetic properties of LiCrTe single crystals with a triangular-lattice antiferromagnetic structure

We report on the synthesis of LiCrTe single crystals and on their anisotropic magnetic properties. We have obtained these single crystals by employing a Te/Li-flux synthesis method. We find LiCrTe to crystallize in a TlCdS -type structure with cell parameters of a = 3.9512(5) Å and c = 6.6196(7) Å at T = 175 K. The content of lithium in these crystals was determined to be neary stoichiometric by means of neutron diffraction. We find a pronounced magnetic transition at = 144 K and = 148 K, respectively. These transition temperatures are substantially higher than earlier reports on polycrystalline samples. We have performed neutron powder diffraction measurements that reveal that the long-range low-temperature magnetic structure of single crystalline LiCrTe is an A-type antiferromagnetic structure. Our DFT calculations are in good agreement with these experimental observations. We find the system to be easy axis with moments oriented along the c-direction experimentally as well as in our calculations. Thereby, the magnetic Hamiltonian can be written as with K (where ). We find LiCrTe to be highly anisotropic, with a pronounced metamagnetic transition for with a critical field of (5 K) ≈ 2.5 T. Using detailed orientation-dependent magnetization measurements, we have determined the magnetic phase diagram of this material. Our findings suggest that LiCrTe is a promising material for exploring the interplay between crystal structure and magnetism, and could have potential applications in spin-based 2D devices.

Relationship between magnetoresistance behavior and magnetic states in intercalated compounds FexTiS2

Temperature and field-dependent neutron powder diffraction (NPD) measurements have been performed to reveal the nature of the unusual evolution of the magnetoresistance behavior with increasing Fe content in the intercalated compounds ${\mathrm{Fe}}_{x}{\mathrm{TiS}}_{2}$ (with $x=0.25,0.33,0.50,0.55$) synthesized by solid-phase reaction method with prolonged homogenization heat treatment. As derived from neutron diffraction measurements, both the ${\mathrm{Fe}}_{0.25}{\mathrm{TiS}}_{2}$ and the ${\mathrm{Fe}}_{0.50}{\mathrm{TiS}}_{2}$ compound exhibit an antiferromagnetic (AFM) order below their respective N\'eel temperatures ${T}_{N}\ensuremath{\approx}52$ K and ${T}_{N}\ensuremath{\approx}140\phantom{\rule{4pt}{0ex}}\mathrm{K}$, which results in the presence of a large magnetoresistance accompanying the field-induced phase transition from AFM to the ferromagnetic (FM) state. At low temperatures, this AFM-FM transition is irreversible, confirmed by the irreversibility of changes in the NPD patterns and the presence of remnant magnetoresistance. In contrast, ${\mathrm{Fe}}_{0.33}{\mathrm{TiS}}_{2}$ shows short-range magnetic order at ${T}_{f}\ensuremath{\approx}44$ K due to a triangular network of intercalated Fe atoms and frustrations of exchange interactions with a field-induced FM alignment of Fe magnetic moments in an applied magnetic field as revealed by NPD measurements. The field-induced transformations of the cluster glass magnetic state in this compound lead to a significant decrease in electrical resistivity. According to NPD data, a reduced impact of an external magnetic field on the electrical resistivity of the compound ${\mathrm{Fe}}_{0.55}{\mathrm{TiS}}_{2}$ can be ascribed to the presence of ferromagnetic or ferrimagnetic order in compounds with the Fe concentrations above $x=0.50$. The results obtained indicate that the distribution of the Fe atoms, along with their concentration in ${\mathrm{Fe}}_{x}{\mathrm{TiS}}_{2}$ layered compounds, plays a decisive role in the formation of the magnetic state and the behavior of the magnetoresistance.

Evolution of the magnetic structure in overdoped antiferromagnetic La1−xCaxMnO3(0.51≤x≤0.69) manganites: A neutron diffraction study

The ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Ca}}_{x}{\mathrm{MnO}}_{3}$ series of compounds with antiferromagnetic ground states ($x\ensuremath{\ge}1/2$) have been extensively studied due to the novel spin, orbital, and charge-ordering states observed when the calcium concentration is a simple fraction ($x=1/2,\phantom{\rule{0.28em}{0ex}}2/3$, and 3/4). The ground states of these compositions have been explained by the Goodenough charge, orbital, and spin ordering model. An important issue remaining is the elucidation of how the ground state changes when $x$ is not a simple number. Here we study the magnetic structure of ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Ca}}_{x}{\mathrm{MnO}}_{3}$ for $0.51\ensuremath{\le}x\ensuremath{\le}0.69$ using powder neutron diffraction measurements supported by magnetization data. For compositions with $0.51\ensuremath{\le}x\ensuremath{\le}0.56$, the magnetic structure, which we term as an incommensurate charge exchange (CE) structure can be described by two propagation vectors ${\mathbf{k}}_{\mathrm{C}}=[1/2,0,1/2]$ and ${\mathbf{k}}_{\mathrm{E}}=[{\ensuremath{\varepsilon}}_{\mathrm{E}},0,1/2]$. In the second one, the component parallel to the ${\mathbf{a}}^{*}$ axis of the reciprocal lattice changes with the ${\mathrm{Mn}}^{4+}$ concentration $x$ as ${\ensuremath{\varepsilon}}_{\mathrm{E}}\ensuremath{\approx}x\ensuremath{-}1/2$ providing, thus, an unambiguous signature of the adoption of an incommensurate magnetic structure. As $x$ gradually increases, the diffraction data reveal that two magnetic phases---one adopting the incommensurate CE, and one adopting the commensurate ``2/3'' magnetic structure--co-exist in the concentration regime of $0.57\ensuremath{\le}x\ensuremath{\le}0.61$. Around the simple fraction $x=2/3$, the magnetic structure can be also described by three propagation vectors, the commensurate ${\mathbf{k}}_{\mathrm{E}}=[0,0,1/2]$, ${\mathbf{k}}_{\mathrm{C}}=[1/2,0,1/2]$, and an incommensurate ${\mathbf{k}}_{2/3}=[1/3+{\ensuremath{\varepsilon}}_{2/3},0,1/2]$ propagation vector with ${\ensuremath{\varepsilon}}_{2/3}$ taking negative/zero/positive values for $x$ smaller than/equal to/larger than 2/3, respectively. Our experimental results for $0.51\ensuremath{\le}x\ensuremath{\le}0.56$ are neither in favor of a stripe structure consisting of a fine mixture of $x=1/2$ and $x=2/3$ phases (phase separation) nor of a defect structure in which an appropriate amount of ${\mathrm{Mn}}^{3+}$-O sheets have been replaced by ${\mathrm{Mn}}^{4+}$-O sheets (defect structure). A sinusoidal modulated structure has been used as a possible candidate in explaining the experimental neutron diffraction magnetic Bragg peaks. This result may be linked to the presence of a mixed orbital state of the manganese ions.

Characterizing the ZrBe2Hx Phase Diagram via Neutron Scattering Methods

Since the initial assessment four decades ago of zirconium diberyllide, ZrBe2, as a potential hydride-forming intermetallic for hydrogen-storage applications, structural and dynamical studies to date have been chiefly limited to the hydride composition, ZrBe2H1.5, which exists as a single-phase disordered hydride with hexagonal P6/mmm symmetry that undergoes hydrogen sublattice ordering below ~200 K (~235–250 K for ZrBe2D1.5). It is desirable from both fundamental and technological viewpoints to have a more complete understanding of the ZrBe2Hx phase diagram. In the present study, both neutron powder diffraction and neutron vibrational spectroscopy measurements of ZrBe2Hx at lower hydrogen contents (x < 1.5) indicate that at least two other ordered phases exist at low temperatures, coinciding with respective nominal x values of 1 and 0.67. Compared to ZrBe2H1.5, these more-hydrogen-dilute phases possess different structural symmetries (orthorhombic) with different H-sublattice orderings and undergo much-higher-temperature order-disorder transitions at ≈ 460 K (x = 1) and ≈ 490 K (x = 0.67) to the characteristic H-disordered hexagonal P6/mmm structure associated with ZrBe2H1.5.

Magnetic interactions in the one-dimensional spin-chain metal-organic compounds M(N2H5)2(SO4)2 (M=Cu, Co, Mn)

Materials with one-dimensional (1D) chains of magnetic ions with reduced spin provide a platform for enhanced quantum behavior. Coordination polymers, or equivalently magnetic metal-organic frameworks (MOFs), with both organic and inorganic building blocks offer the ability to design these tailored structural motifs due to the versatility and predictability of organic chemistry. Here we focus on a series of compounds $M{({\mathrm{N}}_{2}{\mathrm{H}}_{5})}_{2}{({\mathrm{SO}}_{4})}_{2}$, where $M$ is the transition metal ion ${\mathrm{Cu}}^{2+}$, ${\mathrm{Co}}^{2+}$, or ${\mathrm{Mn}}^{2+}$, that forms isolated 1D spin chains within the bulk crystalline lattice. The behavior of the S = 1/2 Cu compound is compared with higher spin Mn and Co based materials through low temperature elastic and inelastic neutron scattering measurements. These provide insights into the magnetic interactions and structure in these materials. In addition, polarized neutron powder diffraction measurements were utilized to determine the site susceptibility tensor in all compounds that provides further insight into the magnetic interactions.

Lithiated Prussian blue analogues as positive electrode active materials for stable non-aqueous lithium-ion batteries

Prussian blue analogues (PBAs) are appealing active materials for post-lithium electrochemical energy storage. However, PBAs are not generally suitable for non-aqueous Li-ion storage due to their instability upon prolonged cycling. Herein, we assess the feasibility of PBAs with various lithium content for non-aqueous Li-ion storage. We determine the crystal structure of the lithiated PBAs via neutron powder diffraction measurements and investigate the influence of water on structural stability and Li-ion migration through operando X-ray diffraction measurements and bond valence simulations. Furthermore, we demonstrate that a positive electrode containing Li2-xFeFe(CN)6⋅nH2O (0 ≤ x ≤ 2) active material coupled with a Li metal electrode and a LiPF6-containing organic-based electrolyte in coin cell configuration delivers an initial discharge capacity of 142 mAh g−1 at 19 mA g−1 and a discharge capacity retention of 80.7% after 1000 cycles at 1.9 A g−1. By replacing the lithium metal with a graphite-based negative electrode, we also report a coin cell capable of cycling for more than 370 cycles at 190 mA g−1 with a stable discharge capacity of about 105 mAh g−1 and a discharge capacity retention of 98% at 25 °C.

Spin-singlet ground state of the coupled Jeff = 12 alternating chain system Sr2Co(SeO3)3

We report a detailed study of the structural, magnetic, thermodynamic, and electronic properties of a coupled ${J}_{\mathrm{eff}}$ = $\frac{1}{2}$ alternating chain ${\mathrm{Sr}}_{2}\mathrm{Co}{({\mathrm{SeO}}_{3})}_{3}$ compound using magnetic susceptibility $\ensuremath{\chi}(T)$, magnetic specific heat ${C}_{\mathrm{m}}(T)$, magnetization, and neutron diffraction measurements along with first-principles calculations. The first-principles calculations based on the density functional theory suggest that ${\mathrm{Sr}}_{2}\mathrm{Co}{({\mathrm{SeO}}_{3})}_{3}$ forms a quasi-one-dimensional chain with bond alternation and interchain interactions. $\ensuremath{\chi}(T), {C}_{\mathrm{m}}(T),$ and neutron powder diffraction measurements confirm that no long-range magnetic ordering occurs down to 100 mK. Instead, a maximum in $\ensuremath{\chi}(T)$ and ${C}_{\mathrm{m}}(T)$ and an exponential drop of $\ensuremath{\chi}(T)$ and ${C}_{p}(T)$ as $T\ensuremath{\rightarrow}0$ K point to a spin-singlet ground state. The analysis of $\ensuremath{\chi}(T)$ and ${C}_{\mathrm{m}}(T)$ based on a ${J}_{1}\text{\ensuremath{-}}{J}_{2}$ alternating Heisenberg model shows the bond alternation $\ensuremath{\alpha}={J}_{2}/{J}_{1}\ensuremath{\approx}0.7$ and a spin gap of $\mathrm{\ensuremath{\Delta}}\ensuremath{\approx}3$ K. Our work demonstrates that ${\mathrm{Sr}}_{2}\mathrm{Co}{({\mathrm{SeO}}_{3})}_{3}$ is a coupled alternating chain system based on spin-orbit entangled ${J}_{\mathrm{eff}}$ = $\frac{1}{2}$.