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Herein we report the second transition-metal-only triple perovskite Mn3MnTa2O9, from high pressure-high temperature transformation of Mn4Ta2O9. It shows 1 : 2 Mn : Ta B-site order and a complex antiferromagnetic behavior with a collinear structure that modulates into a spin density wave. The high pressure phase presents a 25% band gap reduction compared to its multiferroic precursor, recoverable above 625 °C.

Several different mechanisms of magnetoresistance (MR) have been observed in 1111 LnMnAsO1–xFx oxypnictides (Ln = lanthanide) as a result of magnetic coupling between the Mn and Ln. Such phases als...

We report the results of magnetization, heat capacity, and neutron diffraction measurements on (Mo2/3RE1/3)(2)AlC with RE = Dy and Tb. Temperature and field-dependent magnetization as well as heat capacity were measured on a powder sample and on a single crystal allowing the construction of the magnetic field-temperature phase diagram. To study the magnetic structure of each magnetic phase, we applied neutron diffraction in a magnetic field up to 6 T. For (Mo2/3Dy1/3)(2)AlC in zero field, a spin density wave is stabilized at 16 K, with antiferromagnetic ordering at 13 K. Furthermore, we identify the coexistence of ferromagnetic and antiferromagnetic phases induced by magnetic fields for both RE = Tb and Dy. The origin of the field induced phases is resulting from the competing ferromagnetic and antiferromagnetic interactions. Funding Agencies|Knut and AliceWallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation [KAW 2020.0033]; Deutsche Forschungsgemeinschaft (DFG)German Research Foundation (DFG) [CRC/TRR 270, 405553726]; ANR projectFrench National Research Agency (ANR) [ANR-18-CE09-0041]; government of the Russian Federation [075-15-2019-1886]; Flag-ERA JTC 2017

Transition metal compounds can feature different types of magnetic anisotropy. By studying a honeycomb-lattice material with disconnected transition-metal octahedra, the authors reveal the crucial role of the single-ion anisotropy term that arises despite the nominally quenched orbital moment of the ${d}^{3}$ magnetic ion. Their findings suggest that the effect of single-ion anisotropy should not be ignored when searching for signatures of Kitaev interactions in spin-3/2 honeycomb magnets.

Ozone oxidation has allowed the stabilization of a very high iron oxidation state in the FeSr2YCu2O7.85 cuprate, in which a long-range magnetic ordering of the high valent iron cations coexists with the superconducting interactions (magnetic ordering temperature TN = 110 K > superconducting critical temperature Tc = 70 K). The somewhat unexpected A-type AFM structure, with a μ(Fe) ∼ 2 μB magnetic saturation moment associated with the hypervalent iron sublattice, suggests an unusual low spin state for the iron cations, while the low dimensionality of the magnetic structure results in a soft switching toward ferromagnetism under small external magnetic fields. The role of the crystal structure and of the high charge concentration in the stabilization of this unusual electronic configuration for the iron cations is discussed.

High resolution and high intensity neutron powder diffraction are used to determine the temperature dependence of the crystallographic and magnetic structure of the orthoferrite CeFeO3. The high temperature G x -type magnetic coupling of the Fe-sublattice described by the Γ4 (G x A y F z ) irreducible representation changes at the spin reorientation temperature T SR = 228 K to a G y -type coupling of Γ1 (A x G y C z ). The spin reorientation is of first order and sees a hysteresis of about 2.5 K at T SR. Below 35 K faint magnetic peaks reflecting C z type magnetic coupling appear and are argued to be related to the Ce-sublattice. Magnetic moments at 2 K amount to μ Fe = 4.15 μ B and μ Ce = 0.11 μ B. CeFeO3 is only the second RFeO3 compound after DyFeO3 showing this ground state magnetic structure of the Fe-sublattice. The orthorhombic structure Pbnm is kept over the whole temperature range.

The most common MXene composition Ti3C2Tx(T = F, O) shows outstanding stability as anode for sodium ion batteries (100% of capacity retention after 530 cycles with charge efficiency >99.7%). However, the reversibility of the intercalation/deintercalation process is strongly affected by the synthesis parameters determining, in turn, significant differences in the material structure. This study proposes a new approach to identify the crystal features influencing the performances, using a structural model built with a multitechnique approach that allows exploring the short-range order of the lamella. The model is then used to determine the long-range order by inserting defective elements into the structure. With this strategy it is possible to fit the MXene diffraction patterns, obtain the structural parameters including the stoichiometric composition of the terminations (neutron data), and quantify the structural disorder which can be used to discriminate the phases with the best electrochemical properties.

The first triple perovskite with Mn in A- and 1 : 2 B-site order Mn3MnNb2O9, prepared using high pressure phase transformation of the magnetodielectric Mn4MnNb2O9, is reported herein. It has a complex magnetic behaviour with a transition from a collinear AFM into an evolving incommensurate spin density wave (SDW) further stabilised into a lock-in structure dictated by the B-site order.

The R 3TiSb5 ternary compounds, with R a light rare earth (La to Sm) have been reported to crystallize with the anti-Hf5CuSn3-type hexagonal structure (Pearson’s symbol hP18; space-group P63/mcm, N. 193). An early article that reported possible superconductivity in some of these intermetallic phases (namely those with R = La, Ce, and Nd) caught our attention. In this work, we have now refined the crystal structure of the R 3TiSb5 compounds with R = Ce, Pr and Nd by Rietveld methods using high-resolution neutron powder diffraction data. The magnetic ground states of these intermetallics have been investigated by low-temperature magnetization and high-intensity neutron diffraction. We find two different magnetic transitions corresponding to two related magnetic structures at T N1 = 4.8 K (k 1 = [0, 1/2, 1/8]) and T N2 = 3.4 K (k 2 = [0, 0, 1/8]), respectively for Ce3TiSb5. However, the magnetic ordering appears to occur following a peculiar hysteresis: the k 2-type magnetic structure develops only after the k 1-type phase fraction has first slowly ordered with time and the size of the ordered Ce3+ magnetic moment has become large enough to induce the second magnetic transition. At T = 1.5 K the maximum amplitude of the Ce moment in the coexisting phases amounts to μ Ce = 2.15 μ B. For Nd3TiSb5 an antiferromagnetic ordering below T N = 5.2 K into a relatively simpler commensurate magnetic structure with a magnetic moment of μ Nd = 2.14(3) μ B and magnetic propagation vector of k = [0, 0, 0], was determined. No evidence of superconductivity has been found in Nd3TiSb5. Finally, Pr3TiSb5 does not show any ordering down to 1.5 K in neutron diffraction while an antiferromagnetic ground state is detected in magnetization measurements. There is no sign of magnetic contribution from Ti atoms found in any of the studied compounds.

We report muon spin rotation (mu SR) and neutron diffraction on the rare-earth-based magnets (Mo2/3RE1/3)2AlC, also predicted as parent materials for two-dimensional (2D) derivatives, where the rare earth (RE) = Nd, Gd (only mu SR), Tb, Dy, Ho, and Er. By crossing information between the two techniques, we determine the magnetic moment (m), structure, and dynamic properties of all compounds. We find that only for RE = Nd and Gd the moments are frozen on a microsecond timescale. Out of these two, the most promising compound for a potential 2D high m magnet is the Gd variant, since the parent crystals are pristine with m = 6.5 +/- 0.5 mu B, Neel temperature of 29 +/- 1 K, and the magnetic anisotropy between out-of- and in-plane coupling is smaller than 10-8. This result suggests that magnetic ordering in the Gd variant is dominated by in-plane magnetic interactions and should therefore remain stable when exfoliated into 2D sheets. Funding Agencies|Israel Atomic Energy Commission Pazy Foundation grant; Knut and Alice Wallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation; Flag-ERA JTC 2017 project "MORE-MXenes"

High resolution and high intensity neutron powder diffraction is used to study the ground state magnetic order and the spin reorientation transition in the orthoferrite DyFeO3. The transition from the high temperature k = 0 Γ4 (G x A y F z ) to the low temperature Γ1 (A x G y C z ) type order of the Fe-sublattice is found at T SR = 73 K and does not show any thermal hysteresis. Below T N2 = 4 K the Dy-sublattice orders in an incommensurate magnetic structure with k = [0, 0, 0.028] while the Fe-sublattice keeps its commensurate Γ1 type order. DyFeO3 is the first orthoferrite RFeO3 to possess an incommensurate magnetic order of the rare earth sublattice under zero field conditions; an important piece of information neglected in the recent discussion of its multiferroic properties.

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International audience; Mn11Ta4O21 is presented as the first Hexagonal A-site Manganite. Based on simple rules, the structure is compatible with a 14Hlayer (cchchch)2 stacking sequence; related to BaVO3 and BaCrO3 high pressure polymorphs. The A-site over-stoichiometry is explained through difference in ionic radii sizes between Ba and Mn. Magnetic properties show two transitions at TN1 = 88 K and TN2 = 56 K. Neutron powder diffraction evidence two magnetic structures with purely antiferromagnetic and ferrimagnetic orders below TN1 and TN2 respectively. A complementary description with 14H-(hhccccc)2 sequence of only Mn octahedra provides a direct comparison with BaMnO3-δ hexagonal perovskites and naturally explains the AFM order. Below TN2 a magneto-elastic coupling along with uniaxial negative thermal expansion are observed.

We report magnetic properties of a $3{d}^{9}$ $({\mathrm{Cu}}^{2+})$ magnetic insulator ${\mathrm{Cu}}_{2}{\mathrm{OSO}}_{4}$ measured on both powder and single crystal. The magnetic atoms of this compound form layers whose geometry can be described either as a system of chains coupled through dimers or as a kagome lattice where every third spin is replaced by a dimer. Specific heat and DC susceptibility show a magnetic transition at 20 K, which is also confirmed by neutron scattering. Magnetic entropy extracted from the specific heat data is consistent with an $S=1/2$ degree of freedom per ${\mathrm{Cu}}^{2+}$, and so is the effective moment extracted from DC susceptibility. The ground state has been identified by means of neutron diffraction on both powder and single crystal and corresponds to an $\ensuremath{\sim}{120}^{\ensuremath{\circ}}$ spin structure in which ferromagnetic intradimer alignment results in a net ferrimagnetic moment. No evidence is found for a change in lattice symmetry down to 2 K. Our results suggest that ${\mathrm{Cu}}_{2}{\mathrm{OSO}}_{4}$ represents a type of model lattice with frustrated interactions where interplay between magnetic order, thermal and quantum fluctuations can be explored.

Several previous studies reported that a one-dimensional Heisenberg chain model is inadequate in describing the magnetic properties of the low-dimensional quantum antiferromagnet $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{CuV}}_{2}{\mathrm{O}}_{6}$, but the origin for this observation has remained unclear. We have reinvestigated the magnetic properties of $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{CuV}}_{2}{\mathrm{O}}_{6}$ and found that our anisotropic magnetic susceptibility, neutron-powder diffraction, and electron paramagnetic spin-resonance measurements are in good agreement with extensive density-functional theory ($\mathrm{DFT}+U$) total energy calculations which indicate that the correct spin lattice model for $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{CuV}}_{2}{\mathrm{O}}_{6}$ is rather a $S=1/2$ 2D-Heisenberg antiferromagnetic lattice. The magnetic susceptibility data are well described by a rectangular Heisenberg antiferromagnet with anisotropy ratio $\ensuremath{\alpha}\ensuremath{\sim}$ 0.7 consistent with the DFT results. Quantum Monte Carlo simulations of the magnetic susceptibilities for a rectangular lattice Heisenberg antiferromagnet were performed in the anisotropy range 0.5 $\ensuremath{\le}\ensuremath{\alpha}\ensuremath{\le}$ 1.0. The results of the Quantum Monte Carlo calculations were cast into a Pad\'e approximant which was used to fit the temperature-dependent magnetic susceptibility data. Neutron-powder-diffraction measurements were used to conclusively solve the collinear antiferromagnetic structure of $\ensuremath{\alpha}\text{\ensuremath{-}}{\mathrm{CuV}}_{2}{\mathrm{O}}_{6}$ below the N\'eel temperature of $\ensuremath{\sim}22.4$ K.

Oxide ion and proton conductors, which exhibit high conductivity at intermediate temperature, are necessary to improve the performance of ceramic fuel cells. The crystal structure plays a pivotal role in defining the ionic conduction properties, and the discovery of new materials is a challenging research focus. Here, we show that the undoped hexagonal perovskite Ba7Nb4MoO20 supports pure ionic conduction with high proton and oxide ion conductivity at 510 °C (the bulk conductivity is 4.0 mS cm−1), and hence is an exceptional candidate for application as a dual-ion solid electrolyte in a ceramic fuel cell that will combine the advantages of both oxide ion and proton-conducting electrolytes. Ba7Nb4MoO20 also showcases excellent chemical and electrical stability. Hexagonal perovskites form an important new family of materials for obtaining novel ionic conductors with potential applications in a range of energy-related technologies. Fast oxide ion and proton conductors at intermediate temperature are required to improve the performance of ceramic fuel cells. An undoped hexagonal perovskite Ba7Nb4MoO20 electrolyte with high proton and oxide ion conductivity (4.0 mS cm−1) at 510 °C is now reported.

The GaV$_4$S$_{8-y}$Se$_y$ $(y = 0$ to $8)$ family of materials have been synthesized in both polycrystalline and single crystal form, and their structural and magnetic properties thoroughly investigated. Each of these materials crystallizes in the $F\bar{4}3m$ space group at ambient temperature. However, in contrast to the end members GaV$_4$S$_8$ and GaV$_4$Se$_8$, that undergo a structural transition to the $R3m$ space group at 42 and 41 K respectively, the solid solutions $(y = 1$ to $7)$ retain cubic symmetry down to 1.5 K. In zero applied field the end members of the family order ferromagnetically at 13 K (GaV$_4$S$_8$) and 18 K (GaV$_4$Se$_8$), while the intermediate compounds exhibit a spin-glass-like ground state. We demonstrate that the magnetic structure of GaV$_4$S$_8$ shows localization of spins on the V cations, indicating that a charge ordering mechanism drives the structural phase transition. We conclude that the observation of both structural and ferromagnetic transitions in the end members of the series in zero field is a prerequisite for the stabilization of a skyrmion phase, and discuss how the absence of these transitions in the $y = 1$ to $7$ materials can be explained by their structural properties., Main text: 14 pages, 5 figures, 1 table. Supplementary information: 10 pages, 6 figures, 6 tables

Spin liquids are highly correlated yet disordered states formed by the entanglement of magnetic dipoles$^1$. Theories typically define such states using gauge fields and deconfined quasiparticle excitations that emerge from a simple rule governing the local ground state of a frustrated magnet. For example, the '2-in-2-out' ice rule for dipole moments on a tetrahedron can lead to a quantum spin ice in rare-earth pyrochlores - a state described by a lattice gauge theory of quantum electrodynamics$^{2-4}$. However, f-electron ions often carry multipole degrees of freedom of higher rank than dipoles, leading to intriguing behaviours and 'hidden' orders$^{5-6}$. Here we show that the correlated ground state of a Ce$^{3+}$-based pyrochlore, Ce$_2$Sn$_2$O$_7$, is a quantum liquid of magnetic octupoles. Our neutron scattering results are consistent with the formation of a fluid-like state of matter, but the intensity distribution is weighted to larger scattering vectors, which indicates that the correlated degrees of freedom have a more complex magnetization density than that typical of magnetic dipoles in a spin liquid. The temperature evolution of the bulk properties in the correlated regime below 1 Kelvin is well reproduced using a model of dipole-octupole doublets on a pyrochlore lattice$^{7-8}$. The nature and strength of the octupole-octupole couplings, together with the existence of a continuum of excitations attributed to spinons, provides further evidence for a quantum ice of octupoles governed by a '2-plus-2-minus' rule. Our work identifies Ce$_2$Sn$_2$O$_7$ as a unique example of a material where frustrated multipoles form a 'hidden' topological order, thus generalizing observations on quantum spin liquids to multipolar phases that can support novel types of emergent fields and excitations.

In the heavy-fermion system $Yb_2Pd_2In_{1-x}Sn_x$, the interplay of crystal-field splitting, Kondo effect, and Ruderman-Kittel-Kasuya-Yosida interactions leads to complex chemical-, pressure-, and magnetic-field phase diagrams, still to be explored in full detail. By using a series of techniques, we show that even modest changes of parameters other than temperature are sufficient to induce multiple quantum-critical transitions in this highly susceptible heavy-fermion family. In particular, we show that, above $\sim 10$ kbar, hydrostatic pressure not only induces an antiferromagnetic phase at low temperature, but it likely leads to a reorientation of the Yb magnetic moments and/or the competition among different antiferromagnetic configurations.

International audience; We report a perovskite oxide with a new type of polar structure, CuNbO3, thanks to the use of high-pressure and high-temperature synthesis. The perovskite-type CuNbO3 was previously obtained under high-pressure and high-temperature conditions, but its crystal structure has not been solved yet. Our structural analysis reveals that CuNbO3 perovskite crystallizes in a polar monoclinic space group (Pc) with a root 2 a(pc) x root 2 a(pc ) x 2a(pc) unit cell (a(pc) being the pseudo-cubic lattice parameter), which VT, is one maximal nonisomorphic subgroup of the polar rhombohedral space group, R3c. This compound exhibits a remarkable "noncollinear ferrielectric" structure due to parallel displacements of Cu+ and antiparallel displacements of Nb5+ along different axes, representing a new type of polar phase in the perovskite structure. We also observe that the noncollinear ferrielectric Pc s tructure transforms around 470 K into the collinear ferroelectric R3c structure that features parallel displacements of Cu+ and Nb5+ in the same direction. The present work extends the accessible composition range of the perovskite niobate series and demonstrates the role of A-O covalency in determining their crystal structures.

Frustrated magnetic materials can show unconventional correlations such as quantum spin liquid states and monopole excitations in spin ices. These phenomena are observed on uniformly frustrated lattices such as triangular, kagome or pyrochlore types, where all nearest neighbour interactions are equivalent. Here we report incommensurate long-range spin amplitude waves in the spinels Fe2GeO4 and γ-Fe2SiO4 at low temperatures, which indicate that the degree of frustration may itself be a fluctuating quantity that can spontaneously order without a lattice distortion as a ‘frustration wave’. Fe2GeO4 with propagation vector (2/3 + δ 2/3 + δ 0) has ordered Fe2+ moments that vary between fully saturated 4 μB and 0 values, consistent with a frustration wave order. γ-Fe2SiO4 has a more complex (¾ + δ ¾ + δ 0) order that coexists with an ordered spin ice phase. Dynamic orbital fluctuations are proposed to give rise to locally correlated patterns of ferromagnetic and antiferromagnetic interactions consistent with the observed orders.

Acknowledgements We acknowledge the University of Aberdeen for provision of a studentship for Harriet Hopper and the Higher Education Commission of Pakistan for providing a visiting fellowship for Dr. Falak Sher.

The perovskite system Pb(Fe1-xMnx)2/3W1/3O3 (0 ≤ x ≤ 1, PFMWO) has been prepared by conventional solid-state reaction under different sintering conditions. Structures and phase composition as well as thermal, magnetic and dielectric properties of the compounds have been systematically investigated experimentally and by first-principles density functional calculations. A clean perovskite phase is established at room temperature for compositions 0 ≤ x ≤ 0.4. Rietveld refinements of X-ray and neutron powder diffraction patterns demonstrate that the compounds crystallize in space group Pm-3m (0 ≤ x ≤ 0.4). The degree of ordering of the Fe and W/Mn cations was found to depend on the concentration of Mn. First-principles calculations suggest that the structural properties of PFMWO are strongly influenced by the Jahn-Teller effect. The PFMWO compounds behave as relaxor ferroelectrics at weak Mn-doping with a dielectric constant that rapidly decreases with increasing Mn content. A low temperature antiferromagnetic G-type order with propagation vector k = (1/2,1/2,1/2) is derived from neutron powder diffraction data for the samples with x ≤ 0.4. However with increasing doping concentration, the magnetic order is perturbed. First-principles calculations show that the dominant exchange coupling is antiferromagnetic and occurs between nearest neighbor Fe atoms. When the system is doped with Mn, a relatively weak ferromagnetic (FM) interaction between Fe and Mn atoms emerges. However, due to the presence of this FM interaction, the correlation length of the magnetic order is greatly shortened already at rather low doping levels.

We study magnetic behavior of the ${\mathrm{Yb}}^{3+}$ ions on a frustrated pyrochlore lattice in the spinel ${\mathrm{CdYb}}_{2}{\mathrm{Se}}_{4}$. The crystal-electric-field parameters deduced from high-energy inelastic neutron scattering reveal a well-isolated ytterbium ground-state doublet with a weakly Ising character. Magnetic order studied by powder neutron diffraction evolves from the XY-type antiferromagnetic ${\mathrm{\ensuremath{\Gamma}}}_{5}$ state to a splayed icelike ferromagnet (both with $\mathbf{k}=0$) in applied magnetic field with ${B}_{c}=3\phantom{\rule{0.28em}{0ex}}\mathrm{T}$. Low-energy inelastic neutron scattering identifies weakly dispersive magnetic bands around 0.72 meV starting at $|\mathbf{Q}|=1.1\phantom{\rule{4pt}{0ex}}{\AA{}}^{\ensuremath{-}1}$ at zero field, which diminish with field and vanish above 3 T. We explain the observed magnetic behavior in framework of the nearest-neighbor anisotropic exchange model for effective $S=\frac{1}{2}$ Kramers doublets on the pyrochlore lattice. The estimated exchanges position the ${\mathrm{CdYb}}_{2}{\mathrm{Se}}_{4}$ spinel close to the phase boundary between the ${\mathrm{\ensuremath{\Gamma}}}_{5}$ and splayed ferromagnet states, similar to the Yb pyrochlores, suggesting an important role of the competition between these phases.

In 2017, we discovered quaternary i-MAX phases atomically layered solids, where M is an early transition metal, A is an A group element, and X is C-with a ((M2/3M1/32)-M-1)(2)AC chemistry, where the M-1 and M-2 atoms are in-plane ordered. Herein, we report the discovery of a class of magnetic i-MAX phases in which bilayers of a quasi-2D magnetic frustrated triangular lattice overlay a Mo honeycomb arrangement and an Al Kagome lattice. The chemistry of this family is (Mo2/3RE1/3)(2)AlC, and the rare-earth, RE, elements are Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The magnetic properties were characterized and found to display a plethora of ground states, resulting from an interplay of competing magnetic interactions in the presence of magnetocrystalline anisotropy. Funding Agencies|Knut and Alice Wallenberg (KAW) Foundation [KAW 2015.0043]; Swedish Research Council [642-2013-8020, 2015-00607, 621-2014-4890]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; DFG [SA 3095/2-1]; IAEC Pazy Foundation Grant; NSF [DMR-1740795]

We report the growth of mm-sized Pmnb-Li2FeSiO4 single crystals by means of the optical floating-zone method at high argon pressure and describe the conditions required for a stable growth process. The crystal structure is determined and refined by single-crystal X-ray diffraction. The lattice constants amount to a = 6.27837(3) A, b = 10.62901(6) A and c = 5.03099(3) A at 100 K. In addition, we present high-resolution neutron powder diffraction data that suggest that the slight Li-Fe site exchange seems to be intrinsic to this material. High quality of the crystal is confirmed by very sharp anomalies in the static magnetic susceptibility and in the specific heat associated with the onset of long-range antiferromagnetic order at TN = 17.0(5) K and pronounced magnetic anisotropy for the three crystallographic axes. Furthermore, magnetic susceptibility excludes the presence of sizable amounts of magnetic impurity phases.

The topotactic nitridation of cation ordered, tetragonal Sr2FeMoO6 in NH3 at moderate temperatures leads to cubic, Fm[3 with combining macron]m double perovskite oxynitride Sr2FeMoO4.9N1.1 where double-exchange interactions determine ferromagnetic order with TC ≈ 100 K. Substitution of oxide by nitride induces bond asymmetries and local electronically driven structural distortions, which combined with Fermi level lowering restricts charge itinerancy to confined regions and preclude spontaneous long-range magnetic order. Under a magnetic field, ferromagnetic correlations expand, favoring charge delocalization and a negative magnetoresistance is observed., This work was supported by the Spanish Ministerio de Ciencia, Universidades e Investigación, Spain (Projects MAT2017-86616-R, MAT2017-85232-R, MAT2015-71664-R, MAT2015-67593-P and ENE2015-63969) and by Generalitat de Catalunya (2017SGR1377, 2017SGR581). ICMAB acknowledges financial support from MINECO through the Severo Ochoa Program (SEV-2015-0496). We thank the Institut Laue Langevin (ILL) and Alba synchrotron for the provision of beam time., We acknowledge support of the publication fee by the CSIC Open Access Support Initiative through its Unit of Information Resources for Research (URICI)

Room-temperature multiferroism in polycrystalline antiferromagnetic Fe perovskites is reported for the first time. In the perovskite-type oxides RE1.2Ba1.2Ca0.6Fe3O8 (RE = Gd, Tb), the interplay of layered ordering of Gd(Tb), Ba, and Ca atoms with the ordering of FeO4-tetrahedra (T) and FeO6-octahedra (O) results in a polar crystal structure. The layered structure consists of the stacking sequence of RE/Ca-RE/Ca-Ba-RE/Ca layers in combination with the TOOT sequence in a unit cell. A polar moment of 33.0 μC/cm2 for the Gd-oxide (23.2 μC/cm2 for the Tb one) is determined from the displacements of the cations, mainly Fe, and oxygen atoms along the b-axis. These oxides present antiferromagnetic ordering doubling the c-axis, and the magnetic structure in the Tb compound remains up to 690 K, which is one of the highest transition temperatures reported in Fe perovskites.

The substitution of Mn for Fe on the sub-lattice in LaFeAsO has a remarkable impact on both structural and magnetic properties; for example, the structural and magnetic transition temperatures decrease of ~20 K in samples with a Mn-content as low as x = 0.01. Such a dramatic effect results from the high stability of the substituting Mn2+ ion (3d 5) in its high-spin state, which opposes any variation to its electronic state (configuration), perturbing thereby interactions within the Fe sub-lattice between the Fe ions surrounding the substituent. Several investigations ascertained that the structural transformation in LnFeAsO compounds (Ln: lanthanide) cannot be ascribed to lattice degrees of freedom, but rather to electronic or spin ones. In this context, even an extremely low concentration of Mn2+ ions diluted in the Fe sub-lattice produces a reduction of the electronic degree of freedom of the system, thus hindering the structural transformation and the magnetic transition.

We have investigated the magnetic properties of a polycrystalline sample of NdOs2Al10 using neutron diffraction and inelastic neutron scattering, magnetic susceptibility and heat capacity measurements. The magnetic susceptibility data reveal an antiferromagnetic transition at T N1 = 2.2 K while the heat capacity data which extend to lower temperatures show a further transition at T N2 = 1.1 K. The INS measurements detect four well-resolved crystal field excitations at 7.4, 12.4, 17.6 meV and 19.2 meV at 5 K. The positions and intensities of the observed CEF excitations and the temperature dependence of previously published single crystal susceptibility data are analysed based on the orthorhombic CEF model of the J = 9/2 ground state multiplet of Nd3+ ion. The neutron diffraction study reveals the magnetic structure at T = 1.6 K to be of sine wave type (κ = [0, 0.723, 0]) with an ordered state moment of μ Nd 3+ = 1.59(1) μ B aligned along the a-axis in agreement with the single ion crystal field anisotropy. This indicates that the magnetism of NdOs2Al10 is governed by the RKKY interactions in agreement with other RT 2Al10 (R = Nd, Sm, Tb, T = Fe, Ru and Os), but different to that of R = Ce based compounds where anisotropic two ions interaction as well as Kondo interaction govern the anomalous direction of the ordered state moment.

We have carried out detailed investigations of magnetic ordering and the origin of exchange-bias phenomenology in polycrystalline 154Sm0.4Ca0.6MnO3 perovskite compound by employing dc and ac magnetizations, neutron depolarization, and neutron diffraction techniques. The neutron diffraction study reveals a broad charge ordering transition in the temperature range of 275–150 K, manifested by gradually varying structural distortions. DC magnetization and neutron diffraction studies infer a magnetic ordering around 110 K. Below ∼40 K, this compound exhibits a large enhancement of the magnetization and an exchange-bias effect (∼18 kOe at 5 K). The exchange-bias effect shows a characteristic temperature and cooling field dependence and a training effect. The compound undergoes a CE-type (checker-board type) antiferromagnetic (AFM) ordering of Mn3+/Mn4+ spins below 110 K. The large magnetization below ∼40 K arises from the ferrimagnetic (FIM) ordering of a minority (∼5 vol. %) non-perovskite phase of Mn3O4. The appearance of exchange bias is ascribed due to the presence of an interface, formed between the FIM (Mn3O4) phase and the main AFM perovskite phase. Our study has implications in giving new directions in the search of large exchange-bias effects in mixed FIM/AFM bulk systems.

We report on the magnetoelectric properties of Er2CoMnO6. This compound adopts the structure of a double perovskite with a strong monoclinic distortion. Our specimen exhibits a nearly perfect Co-Mn order. It undergoes a ferromagnetic transition at TC~70 K due to the Co2+-O-Mn4+ ferromagnetic superexchange interaction. Below 30 K, the Er3+ moments start to order antiferromagnetically to the Co/Mn sublattice. Pyroelectric measurements reveal electrical polarization at low temperature but its strong dependence on the heating rate indicates the lack of a spontaneous ferroelectricity. Instead, electric polarization is derived from thermally stimulated depolarization currents.

The crystal structures of monoclinic samarium and cubic europium sesquioxide, Sm2O3 and Eu2O3, were reinvestigated by powder diffraction methods (laboratory X-ray, synchrotron, neutron). Rietveld analysis yields more precise structural parameters than previously known, especially for oxygen atoms. Interatomic distances d(Sm–O) in Sm2O3 range from 226.3(4) to 275.9(2) pm [average 241.6(3) pm] for the monoclinic B type Sm2O3 [space group C2/m, a = 1418.04(3) pm, b = 362.660(7) pm, c = 885.48(2) pm, β = 100.028(1)°], d(Eu–O) in Eu2O3 from 229.9(2) to 238.8(2) pm for the cubic bixbyite (C) type [space group Ia3̅, a = 1086.87(1) pm]. Neutron diffraction at 50 K and 2 K did not show any sign for magnetic ordering in Sm2O3. Isotopically enriched 154Sm2O3 and 153Eu2O3 were used for the neutron diffraction work because of the enormous absorption cross section of the natural isotopic mixtures for thermal neutrons. The isotopic purity was determined by inductively coupled plasma – mass spectrometry to be 98.9% for 154Sm and 99.8% for 153Eu. Advanced analysis of the neutron diffraction data suggest that the bound coherent scattering lengths of 154Sm and 153Eu need to be revised. We tentatively propose b c(154Sm) = 8.97(6) fm and b c(153Eu) = 8.85(3) fm for a neutron wavelength of 186.6 pm to be better values for these isotopes, showing up to 8% deviation from accepted literature values. It is shown that inaccurate scattering lengths may result in severe problems in crystal structure refinements causing erroneous structural details such as occupation parameters, which might be critically linked to physical properties like superconductivity in multinary oxides.

The NiAs-type structure is one of the most common structures in solids, but metal order has been almost exclusively limited to chalcogenides. The synthesis of HfMnSb2 is reported with a novel metal-ordered NiAs-type structure. HfMnSb2 undergoes a conical spin order below 270 K, in marked contrast to conventional magnetic order observed in NiAs-type pnictides. We argue that the layered arrangement of Hf and Mn makes it a quasi 2D magnet, where the Mn layers with localized magnetic moments (Mn(2+) ; S=5/2) can interact only through RKKY interactions, instead of metal-metal bonding that is otherwise dominant for typical NiAs-type pnictides. This result suggests that controlling order-disorder in NiAs-type pnictides enables a study of 2D-to-3D crossover behavior in itinerant magnetic system.

The crystal structure of the technologically relevant, high-temperature proton conductor BaZr0.7Ce0.2Y0.1O3−δ (BZCY72) has been studied by high-resolution neutron powder diffraction performed on a deuterated sample in the temperature range 10–1173 K, complemented with synchrotron X-ray diffraction in the range RT-1173 K. A volume discontinuity on heating indicates a first-order phase transition from orthorhombic (space group Imma) to rhombohedral symmetry (R3̅c) between 85 and 150 K. A further transition to cubic symmetry (Pm3̅m) takes place at ∼570 K, indicated to be second order from the temperature dependence of the octahedral tilt angle. The stability field of the cubic phase was extended on cooling in the dehydrated state to 85 K. Expansion/contraction of the unit-cell volume on heating in low vacuum and air, respectively observed by neutron diffraction and synchrotron X-ray diffraction, was described with a point-defect model involving the temperature dependence of the water content and thermal expansion. Isotropic strain in the hydrated state is apparent on analysis of the broadening of the neutron-diffraction reflections during heating and cooling cycles. Rietveld refinement of the low-temperature neutron data and Fourier nuclear-density maps were employed to locate the deuterium position at a distance of ∼0.90 Å from the bonding oxygen at 10 K. Fil: Mather, Glenn C.. Instituto de Ceramica y Vidrio de Madrid; España Fil: Heras Juaristi, Gemma. Instituto de Ceramica y Vidrio de Madrid; España Fil: Ritter, Clemens. Institut Laue Langevin; Francia Fil: Fuentes, Rodolfo Oscar. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Chinelatto, Adilson L.. Universidade Estadual de Ponta Grossa; Brasil Fil: Pérez Coll, Domingo. Instituto de Ceramica y Vidrio de Madrid; España Fil: Amador, Ulises. Universidad CEU San Pablo; España

In a recent work we have reported the formation and the crystal structure of the new family of compounds R3Pd5 (R = Sc, Y, Gd–Lu; Pu3Pd5-type, oS32, spacegroup 63, Cmcm). DFT calculations for Gd3Pd5 and heat capacity and magnetic measurements for Tb3Pd5, Dy3Pd5, Ho3Pd5 and Er3Pd5 were able to discriminate at least two distinct antiferromagnetic transitions at low temperatures; at the same time these data suggested these separate magnetic orderings to be likely associated to the two structurally different rare earth sublattices (4c and 8e, respectively). The magnetic structures of the R3Pd5 compounds, with R = Tb, Dy, Ho, Er, have been now investigated in this work. High-resolution and high-intensity neutron powder diffraction data were recorded for the four compounds of the series. The results reveal that the magnetic structures adopted are significantly diverse and their temperature dependence more complex than originally deduced from magnetic and heat capacity measurements. Tb3Pd5 is in fact the only of the four compounds where the rare earth sublattices order independently with two different magnetic propagation vectors on the two sites (k1 = [1 0 ½] for Tb2 and k2 = [kx 0 0] or k3 = [1 0 0] for Tb1). In Dy3Pd5 both sublattices follow the propagation vector k = [kx 0 0], with the second transition corresponding to a spin reorientation. In Ho3Pd5 ordering of both sublattices follow the k = [1 0 0] propagation vector; the second transition seen in the magnetic and heat capacity data corresponds to an accelerated increase in the magnetic moment of the Ho2 sublattice. The case of Er3Pd5 is special as it is the sole case where one of the rare earth sublattices does not order down to T = 1.5 K; here the second transition determined from the magnetic data corresponds to a change of the magnetic propagation vector from k1 = [kx 0 kz] to k2 = [1 0 0], both only acting on the Er2 sublattice. Irrespectively of the very similar structures not even two of the four studied R3Pd5 compounds show identical magnetic structures on either of the two sublattices. These strong variations have to be connected to changes in the RKKY interactions induced by the progressive filling of the f-orbitals of the heavy rare earth ions and the concomitant changes of the crystal electric fields.

International audience; The new phase Co2ScSbO6 and Ni2-xCoxScSbO6 solid solutions adopt the polar Ni3TeO6-type structure and order magnetically below 60 K. A series of long-period lock-in [0 0 1/3n] spin structures with n = 5, 6, 8 and 10 is discovered, coexisting with a ferrimagnetic [0 0 0] phase at high Co-contents. The presence of electrical polarisation and spontaneous magnetisations offers possibilities for multiferroic properties.

Magnetic behavior of BaMoP$_2$O$_8$ with the spatially anisotropic triangular arrangement of the $S=1$ Mo$^{4+}$ ions is explored using thermodynamic measurements, neutron diffraction, and density-functional band-structure calculations. A broad maximum in the magnetic susceptibility around 46\,K is followed by the stripe antiferromagnetic order with the propagation vector ${\mathbf k}=(\frac{1}{2},\frac{1}{2},\frac{1}{2})$ formed below $T_N\simeq 21$ K. This stripe phase is triggered by a pronounced one-dimensionality of the spin lattice, where one of the in-plane couplings, $J_2\simeq 4.6$ meV, is much stronger than its $J_1\simeq 0.4$ meV counterpart, and stabilized by the weak easy-axis anisotropy. The ordered moment of 1.42(9) $\mu_B$ at 1.5 K is significantly lower than the spin-only moment of 2 $\mu_B$ due to a combined effect of quantum fluctuations and spin-orbit coupling.

Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr_{2}Se_{4} is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy_{2}Ti_{2}O_{7}. In this Letter we use diffuse neutron scattering to show that both CdEr_{2}Se_{4} and CdEr_{2}S_{4} support a dipolar spin ice state-the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy_{2}Ti_{2}O_{7}, i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er^{3+} ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr_{2}X_{4} (X=Se, S) are primarily due to much faster monopole hopping. Our work suggests that CdEr_{2}X_{4} offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

We present the results of the investigation of magnetic properties of the Er 2 Ti 2 − x Sn x O 7 series. For small doping values, the ordering temperature decreases linearly with x , while the moment configuration remains the same as in the x = 0 parent compound. Around x = 1.7 doping level, we observe a change in the behavior, where the ordering temperature starts to increase and new magnetic Bragg peaks appear. For the first time, we present evidence of a long-range order (LRO) in Er 2 Sn 2 O 7 ( x = 2.0 ) below T N = 130 mK. It is revealed that the moment configuration corresponds to a Palmer-Chalker type with a value of the magnetic moment significantly renormalized compared to x = 0 . We discuss our results in the framework of a possible quantum phase transition occurring close to x = 1.7 .

Magnetic systems with spins sitting on a lattice of corner sharing regular tetrahedra have been particularly prolific for the discovery of new magnetic states for the last two decades. The pyrochlore compounds have offered the playground for these studies, while little attention has been comparatively devoted to other compounds where the rare earth $R$ occupies the same sublattice, e.g., the spinel chalcogenides $\mathrm{Cd}{R}_{2}{X}_{4}$ ($X=\mathrm{S}$ or $\mathrm{Se}$). Here, we report measurements performed on powder samples of this series with $R=\mathrm{Yb}$ using specific heat, magnetic susceptibility, neutron diffraction, and muon-spin-relaxation measurements. The two compounds are found to be magnetically similar. They long-range order into structures described by the ${\mathrm{\ensuremath{\Gamma}}}_{5}$ irreducible representation. The magnitude of the magnetic moment at low temperature is 0.77 (1) and 0.62 (1) ${\ensuremath{\mu}}_{\mathrm{B}}$ for $X=\mathrm{S}$ and $\mathrm{Se}$, respectively. Persistent spin dynamics is present in the ordered states. The spontaneous field at the muon site is anomalously small, suggesting magnetic moment fragmentation. A double spin-flip tunneling relaxation mechanism is suggested in the cooperative paramagnetic state up to 10 K. The magnetic space groups into which magnetic moments of systems of corner-sharing regular tetrahedra order are provided for a number of insulating compounds characterized by null propagation wave vectors.

Multiferroic materials exhibit two or more ferroic orders and have potential applications as multifunctional materials in the electronics industry. A coupling of ferroelectricity and ferromagnetism is hereby particularly promising. We show that the synthetic melanostibite mineral MnFeSbO (R (Formula presented.) space group) with ilmenite-type structure exhibits cation off-centering that results in alternating modulated displacements, thus allowing antiferroelectricity to occur. Massive magnetoelectric coupling (MEC) and magnetocapacitance effect of up to 4000 % was detected at a record high temperature of 260 K. The multiferroic behavior is based on the imbalance of cationic displacements caused by a magnetostrictive mechanism, which sets up an unprecedented example to pave the way for the development of highly effective MEC devices operational at or near room temperature., The authors thank MINECO for funding through projects MAT2013‐44964‐R, MAT2013‐41099‐R, MAT2015‐71070‐REDC, MAT2014‐52405‐C02‐02, CTQ2015‐67755‐C2‐1‐R (MINECO/FEDER) and FPI (BES‐2013‐066112) and Ramon y Cajal (RyC‐2010–06276) fellowships, and Comunidad de Madrid through S‐2013/MIT‐2753 grant.

The crystal structure, magnetic ground state, and the temperature-dependent microscopic spin-spin correlations of the frustrated honeycomb lattice antiferromagnet $\mathrm{N}{\mathrm{a}}_{2}\mathrm{C}{\mathrm{o}}_{2}\mathrm{Te}{\mathrm{O}}_{6}$ have been investigated by powder neutron diffraction. A long-range antiferromagnetic (AFM) ordering has been found below ${T}_{\mathrm{N}}\ensuremath{\sim}24.8\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. The magnetic ground state, determined to be zigzag antiferromagnetic and characterized by a propagation vector $\mathbf{k}=(1/200)$, occurs due to the competing exchange interactions up to third-nearest neighbors within the honeycomb lattice. The exceptional existence of a limited magnetic correlation length along the $c$ axis (perpendicular to the honeycomb layers in the $ab$ planes) has been found even at 1.8 K, well below the ${T}_{\mathrm{N}}\ensuremath{\sim}24.8\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. The observed limited correlation along the $c$ axis is explained by the disorder distribution of the Na ions within the intermediate layers between honeycomb planes. The reduced ordered moments ${m}_{\mathrm{Co}(1)}=2.77(3)\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}}/\mathrm{C}{\mathrm{o}}^{2+}$ and ${m}_{\mathrm{Co}(2)}=2.45(2)\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}}/\mathrm{C}{\mathrm{o}}^{2+}$ at 1.8 K reflect the persistence of spin fluctuations in the ordered state. Above ${T}_{\mathrm{N}}\ensuremath{\sim}24.8\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, the presence of short-range magnetic correlations, manifested by broad diffuse magnetic peaks in the diffraction patterns, has been found. Reverse Monte Carlo analysis of the experimental diffuse magnetic scattering data reveals that the spin correlations are mainly confined within the two-dimensional honeycomb layers ($ab$ plane) with a correlation length of $\ensuremath{\sim}12\phantom{\rule{0.16em}{0ex}}\AA{}$ at 25 K. The nature of the spin arrangements is found to be similar in both the short-range and long-range ordered magnetic states. This implies that the short-range correlation grows with decreasing temperature and leads to the zigzag AFM ordering at $T\ensuremath{\le}{T}_{\mathrm{N}}$. The present study provides a comprehensive picture of the magnetic correlations over the temperature range above and below the ${T}_{\mathrm{N}}$ and their relation to the crystal structure. The role of intermediate soft Na layers on the magnetic coupling between honeycomb planes is discussed.

In this Letter we report high-resolution synchrotron X-ray powder diffraction and transmission electron microscope analysis of Mn-substituted LaFeAsO samples, demonstrating that a static incommensurate modulated structure develops across the low-temperature orthorhombic phase, whose modulation wave-vector depends on the Mn content. The incommensurate structural distortion is likely originating from a charge-density-wave instability, a periodic modulation of the density of conduction electrons associated with a modulation of the atomic positions. Our results add a new component in the physics of Fe-based superconductors, indicating that the density wave ordering is charge-driven., Comment: To be published in the Physical Review Letters

An investigation on the ground state magnetism of CeScSi, CeScGe (tetragonal CeScSi-type, tI12, space group I4/mmm) by temperature-dependent powder neutron diffraction has been carried out, as debated and controversial data regarding the low temperature magnetic behaviours of these two compounds were reported. Our studies reveal that, while cooling, long-range magnetic ordering in CeScSi and CeScGe takes place by a two-step process. A first transition leads to a magnetic structure with the Ce moments aligned ferromagnetically onto two neighbouring tetragonal basal a-b planes of the CeScSi-type structure; the double layers are then antiferromagnetically coupled to each other along the c-axis. The transition temperature associated with the first ordering is T N ~ 26 K and T N ~ 48 K for the silicide and the germanide, respectively. Here the spin directions are rigorously confined to the basal plane, with values of the Ce magnetic moments of μ Ce = 0.8-1.0 μ B. A second magnetic transition, which takes place at slightly lower temperatures, results in a canting of the ordered magnetic moments out of the basal plane which is accompanied by an increase of the magnetic moment value of Ce to μ Ce = 1.4-1.5 μ B. Interestingly, the second magnetic transition leads to a structural distortion in both compounds from the higher-symmetry tetragonal space group I4/mmm to the lower-symmetry and triclinic I-1 (non-standard triclinic). Magnetic symmetry analysis shows that the canted structure would not be allowed in the I4/mmm space group; this result further confirms the structural transition. The transition temperatures T S from I4/mmm to I-1 are about 22 K in CeScSi and 36 K in CeScGe, i.e. well below the temperature of the first onset of antiferromagnetic order observed in this work (or below the ordering temperature, previously reported as either T C or T N). This result, along with the synchronism of the magnetic and structural transitions, suggests a magnetostructural origin of this structural distortion. We have also carried out powder neutron diffraction for LaScSi as a non-magnetically-ordering reference compound and compared the results with those of CeScSi and CeScGe compounds.

The commensurate crystal structure of the magnetic phase occurring below 7 K of the multiferroic Pb2MnWO6 perovskite has been solved by the introduction of the superspace approach. This lead based double perovskite is characterized by a complex ferrielectric non-centrosymmetric nuclear structure with orthorhombic symmetry stable in a wide temperature range. As indicated from the analysis of powder neutron diffraction data, the low temperature antiferromagnetic structure showing a propagation vector k 1/4 [1/4 0 0] is stabilized by a multi-step process involving the evolution from incommensurate to commensurate spin ordering with a concomitant change of the magnetic symmetry. The determination of the Pb2MnWO6 magnetic structure offers a meaningful example of the superspace application and provides a detailed phase diagram of the involved magnetic states. Nowadays this ordered perovskite could be considered as a new type of multiferroic material combining ferrielectric properties and a long period antiferromagnetic structure.

La2−xSrxCoTiO6 (0.6 ≤ x ≤ 1.0) compound series is prepared by Sr-substitution in the A-site of the perovskite by a modified Pechini procedure under air. Charge compensation as Sr2+ content increase occurs by Co2+ oxidation to Co3+. Reduced samples are obtained by further treatment under 5%H2/Ar and characterized by Neutron Powder Diffraction. Upon redution, Co3+ to Co2+ reduction and oxygen vacancies creation are detected. Dependence of total conductivity with temperature and pO2 exhibits a typical p-type semiconducting behaviour. Results show that the higher the Sr content, the higher holes (Co3+) concentration and consequently, La2−xSrxCoTiO6 (x = 1.0) shows the highest conductivity (13.23 S/cm at 1073 K in air). The negligible reactivity with YSZ, used as the electrolyte, of symmetrical cells under oxidant conditions and the moderate thermal expansion found by XRD point to their possible use as SOFC cathodes. Thus, La1.2Sr0.8CoTiO6-based cathodes display polarization resistance of 0.9 Ω cm2 at 1073 K in oxygen, only slightly above than the current state-of-the-art.

Using a high-pressure reaction, we successfully synthesized $\mathrm{BaF}{\mathrm{e}}_{2}\mathrm{S}{\mathrm{e}}_{2}\mathrm{O}$ with a uniform stack of $[\mathrm{F}{\mathrm{e}}_{2}\mathrm{S}{\mathrm{e}}_{2}\mathrm{O}]$ layers. Magnetic susceptibility, heat capacity, M\"ossbauer spectroscopy, and neutron-diffraction measurements revealed that $\mathrm{BaF}{\mathrm{e}}_{2}\mathrm{S}{\mathrm{e}}_{2}\mathrm{O}$ undergoes antiferromagnetic order at 106 K with a 2-$k$ spin structure where each Fe moment points to a neighboring oxide anion. The same spin structure has been observed in the related iron oxyselenides but with a staggered stack of $[\mathrm{F}{\mathrm{e}}_{2}\mathrm{C}{\mathrm{h}}_{2}\mathrm{O}]$ (where Ch represents chalcogen) layers $(\mathrm{Ch}\phantom{\rule{0.16em}{0ex}}=\phantom{\rule{0.16em}{0ex}}\mathrm{S},\mathrm{Se})$. We propose that the strong uniaxial anisotropy inferred from the 2-$k$ structure originates from spin-orbit coupling (SOC) induced by a $\mathit{trans}\ensuremath{-}\mathrm{Fe}{\mathrm{O}}_{2}\mathrm{S}{\mathrm{e}}_{4}$ octahedron, which provides a quasilinear coordination environment as often found in single molecule magnetic complexes. A first-principles calculation with inclusion of SOC supports the stabilization of the 2-$k$ spin structure, giving an unquenched orbital momentum of $0.1\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}}/\mathrm{Fe}$. The present paper provides an idea of how to design magnetic lattices of uniaxial anisotropy using oxychalcogenides and more generally mixed-anion compounds.

In this study, the reactivity of bulk lattice nitrogen within the filled β-Mn structured Ni2Mo3N phase has been investigated by application of powder neutron diffraction and heterolytic nitrogen isotopic exchange measurements. In contrast to CoMo3N, despite the similarity in the N immediate local environment comprising NMo6 octahedra, its reactivity is found to be limited and this lower reactivity was maintained upon the introduction of a significant proportion of cobalt to yield its filled β-Mn structured CoNi2Mo3N quaternary nitride counterpart.