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DOE OSTI2022

Double Paddle‐Wheel Enhanced Sodium Ion Conduction in an Antiperovskite Solid Electrolyte

Abstract Antiperovskite structure compounds (X 3 AB, where X is an alkali cation and A and B are anions) have the potential for highly correlated motion between the cation and a cluster anion on the A or B site. This so‐called “paddle‐wheel” mechanism may be the basis for enhanced cation mobility in solid electrolytes. Through combined experiments and modeling, the first instance of a double paddle‐wheel mechanism, leading to fast sodium ion conduction in the antiperovskite Na 3− x O 1− x (NH 2 ) x (BH 4 ), is shown. As the concentration of amide (NH 2 − ) cluster anions is increased, large positive deviations in ionic conductivity above that predicted from a vacancy diffusion model are observed. Using electrochemical impedance spectroscopy, powder X‐ray diffraction, synchrotron X‐ray diffraction, neutron diffraction, ab initio molecular dynamics simulations, and NMR, the cluster anion rotational dynamics are characterized and it is found that cation mobility is influenced by the rotation of both NH 2 − and BH 4 − species, resulting in sodium ion conductivity a factor of 10 2 higher at x = 1 than expected for the vacancy mechanism alone. Generalization of this phenomenon to other compounds could accelerate fast ion conductor exploration and design.

25 ENERGY STORAGE↗

DOE OSTI2025

Advancing Sodium-Ion Battery Cathodes: A Low-Cost, Eco-Friendly Mechanofusion Route from TiO 2 Coating to Ti 4+ Doping

Layered oxide battery cathodes often require extra stabilization strategies, such as surface coating or doping, to mitigate side reactions and enhance longevity. Conventional methods such as aqueous deposition and atomic layer deposition are costly and environmentally unfriendly and even damage the original structure, especially for air-sensitive sodium-ion battery (SIB) cathodes. Herein, we introduce an all-dry mechanofusion technique that modifies hydroxide precursors with TiO 2 coating before sintering with a sodium source. Using advanced characterizations including X-ray diffraction, neutron diffraction, and solid-state nuclear magnetic resonance for structural insights, X-ray absorption spectroscopy to study metal valence states, and transmission X-ray microscopy for nanoscale visualization of nickel oxidation states, we verified that postsintering transforms TiO 2 surface coating into Ti doping, leading to improved Ni-oxidation homogeneity, modified charge compensation, and enhanced thermal stability. Electrochemical tests reveal superior performance in capacity retention, rate capability, and air stability for these modified cathodes, with pouch cells maintaining over 85% capacity after 650 cycles. This method presents a sustainable, cost-effective route for advanced SIB cathode development.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Fermi surface reconstruction due to orthorhombic distortion in the Dirac semimetal YbMnSb 2

A Dirac semimetal with magnetic atoms as constituents delivers an interesting platform to investigate the interplay of Fermi surface (FS) topology, electron correlation, and magnetism. One such family of semimetals is YbMn⁢ 𝑃⁢𝑛 2 (𝑃⁢𝑛 = Sb,Bi), which is being actively studied due to the intertwined spin and charge degrees of freedom. Here, in this study, we investigate the relationship between the magnetic/crystal structures and FS topology of YbMnSb 2 using single crystal x-ray diffraction, neutron scattering, magnetic susceptibility, magnetotransport measurements, and complimentary density functional theory (DFT) calculations. Contrary to previous reports, the x-ray and neutron diffraction reveal that YbMnSb 2 crystallizes in an orthorhombic 𝑃⁢𝑛⁢𝑚⁢𝑎 structure with a notable antiphase displacement of the magnetic Mn ions that increases in magnitude upon cooling. As a result of this orthorhombicity, first-principles DFT calculation reveals a reduced Brillouin zone and more anisotropic FS of YbMnSb 2 compared to YbMnBi 2 . Moreover, the hole-type carrier density drops by two orders of magnitude as YbMnSb 2 orders antiferromagnetically, indicating band folding in a magnetic ordered state. In addition, the Landau level fan diagram yields a nontrivial nature of the Shubnikov–de Haas quantum oscillation frequency arising from the Dirac-like Fermi pocket. These results imply that YbMnSb 2 is an ideal platform to explore the interplay of subtle lattice distortion, magnetic order, and topological transport arising from relativistic quasiparticles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Spin-orbital correlations from complex orbital order in MgV 2⁢ O 4

MgV 2 ⁢O 4 is a spinel based on magnetic V 3+ ions, which host both spin (𝑆 = 1) and orbital (𝑙 eff = 1) moments. Owing to the underlying pyrochlore coordination of the magnetic sites, the spins in MgV 2 ⁢O 4 only antiferromagnetically order once the frustrating interactions imposed by the 𝐹⁡𝑑⁢$\overline{3}$⁢𝑚 lattice are broken through an orbitally-driven structural distortion at T 𝑆 ≃ ⁢60 K. Consequently, a Néel transition occurs at T 𝑁 ≃ ⁢40 K. Low-temperature spatial ordering of the electronic orbitals is fundamental to both the structural and magnetic properties; however, considerable discussion on whether it can be described by complex or real orbital ordering is ambiguous. We apply neutron spectroscopy to resolve the nature of the orbital ground state and characterize hysteretic spin-orbital correlations using x-ray and neutron diffraction. Neutron spectroscopy finds multiple excitation bands and we parametrize these in terms of a multilevel (or excitonic) theory based on the orbitally degenerate ground state. Meaningful for the orbital ground state, we report an “optical-like” mode at high energies that we attribute to a crystal-field-like excitation from the spin-orbital 𝑗 eff = 2 ground-state manifold to an excited 𝑗 eff =1 energy level. We parametrize the magnetic excitations in terms of a Hamiltonian with spin-orbit coupling and local crystalline electric field distortions resulting from deviations from perfect octahedra surrounding the V 3+ ions. We suggest that this provides compelling evidence for complex orbital order in MgV 2⁢ O 4 . We then apply the consequences of this model to understand hysteretic effects in the magnetic diffuse scattering where we propose that MgV 2⁢ O 4 displays a high-temperature orbital memory of the low-temperature spin order.

Frustrated magnetism↗

NASA NTRS1990

Phase compatibilities of YBa2Cu3O(9-delta) type structure in quintenary systems Y-Ba-Cu-O-X (impurity)

Electrical transport properties of the oxidic high T(sub c) superconductors are significantly affected by the presence of minor amounts of various elements adventing as impurities, e.g., from the chemical environment during manufacturing. YBa2Cu3O(9-delta) is prone to an extinction of the superconductivity on (partial) substitution of all four elemental components. E.g., Pr (for Y), La (for Ba), Zn (for Cu) or peroxygroup (for O) substituents will alter some of the superconductivity preconditions, like mixed valence state in Cu3O7/O(9-delta) network or structural distortion of the network. Although various pseudoternary chemical equilibrium phase diagrams of the Y(O)-Ba(O)-Cu(O) system now are available, no consensus is generally shown, however, this is partly due to lack of compatible definitions of the equilibrium conditions. Less information is available about the phase compatibilities in the appropriate quaternary phase diagram (including oxygen) and virtually no information exists about any pentenary phase diagrams (including one impurity). Unfortunately, complexity of such systems, stemming both from number of quaternary or pentenary compounds and from visualizing the five-component phase system, limits this presentation to more or less close surroundings of the YBa2Cu3O(9-delta) type phase in appropriate pseudoquaternary or pseudopseudoternary diagrams, involving Y-Ba-Cu and O, O-CO2, alkaline metals, Mg and alkaline earths, and Sc and most of the 3-d and 4-f elements. The systems were investigated by means of x ray diffraction, neutron diffraction and chemical analytical methods on samples prepared by sol-gel technique from citrates. The superconductivity was characterized by measuring the diamagnetic susceptibility by SQUID.

Karen, P.↗

DOE OSTI2023

Adaptive sampling for accelerating neutron diffraction-based strain mapping *

Abstract Neutron diffraction is a useful technique for mapping residual strains in dense metal objects. The technique works by placing an object in the path of a neutron beam, measuring the diffracted signals and inferring the local lattice strain values from the measurement. In order to map the strains across the entire object, the object is stepped one position at a time in the path of the neutron beam, typically in raster order, and at each position a strain value is estimated. Typical dwell times at neutron diffraction instruments result in an overall measurement that can take several hours to map an object that is several tens of centimeters in each dimension at a resolution of a few millimeters, during which the end users do not have an estimate of the global strain features and are at risk of incomplete information in case of instruments outages. In this paper, we propose an object adaptive sampling strategy to measure the significant points first. We start with a small initial uniform set of measurement points across the object to be mapped, compute the strain in those positions and use a machine learning technique to predict the next position to measure in the object. Specifically, we use a Bayesian optimization based on a Gaussian process regression method to infer the underlying strain field from a sparse set of measurements and predict the next most informative positions to measure based on estimates of the mean and variance in the strain fields estimated from the previously measured points. We demonstrate our real-time measure-infer-predict workflow on additively manufactured steel parts—demonstrating that we can get an accurate strain estimate even with 30%–40% of the typical number of measurements—leading the path to faster strain mapping with useful real-time feedback. We emphasize that the proposed method is general and can be used for fast mapping of other material properties such as phase fractions from time-consuming point-wise neutron measurements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2023

Structure and magnetism of the triangular lattice material YbBO 3

Abstract YbBO 3 is a member of the orthoborate family of materials which contains a triangular arrangement of Yb 3+ ions. Here we study the physical properties of YbBO 3 with neutron diffraction, inelastic neutron scattering, specific heat, and ac susceptibility measurements. The neutron diffraction measurements confirm that our samples of YbBO 3 crystallize in the monoclinic space group C 2 / c (#15) which contains two crystallographically distinct Yb 3+ sites decorating a slightly distorted triangular lattice. Heat capacity and ac susceptibility measurements indicate a potential transition to magnetic order at 0.4 K. In agreement with these observations, neutron diffraction measurements at 0.044 K observe magnetic Bragg peaks which can be indexed by a propagation vector of (0 0 1). Although determining a unique spin configuration corresponding to the observed magnetic Bragg peaks is not possible, model refinements indicate that the ordered moments are likely in the range of 0.4–0.9 μ B and, notably, require moments on both Yb sites. In addition to the magnetic Bragg peaks, diffuse scattering at low Q is observed indicating that the transition does not correspond to complete long range magnetic order. The two-site picture for YbBO 3 is further evidenced by the number of crystal field excitations observed by inelastic neutron scattering measurements. Together these results show that YbBO 3 is a two-site triangular lattice material with signatures of long-range order as well as shorter ranged spin correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

The role of ternary alloying elements in eutectoid transformation of U-10Mo alloy part II. In and Ex-situ Neutron diffraction-based assessment of eutectoid phase transformation kinetics in U-9.8Mo-0.2X alloy (X = Cr, Ni or Co)

HExploring the effects of minor ternary alloying additions, typically impurity elements, on the phase stability of U-10Mo is important for preventing undesirable phase decomposition during processing or during service. This work examines the influence small ternary additions of Cr, Ni, and Co. Both in-situ and ex-situ neutron diffraction measurements made during and after high temperature (450 – 525°C) exposures were used to better define the influence of these elements on the time-temperature-transformation (TTT) behavior of U-10Mo, providing information which is complementary to electron microscopy investigations of the same alloy systems performed in the first part of this work. Minor additions of Ni and Co decrease the ?-phase stability at all temperatures investigated. Signatures of U6X (X = Ni or Co) compounds were shown to be present in amounts of up to 6 wt% in the heat treated alloys, suggesting that the initial precipitation of this phase may catalyze further ?-phase decomposition. On the other hand, the Cr containing alloys were observed to have nearly the same, and in some cases slower, phase transformation kinetics when compared to the binary U-10Mo control samples. The results of the study have enabled preliminary estimates of the TTT curves for the ternary alloys.

phase transformation, kinetics, discontinuous prec↗

DOE OSTI2020

Structural, magnetic, and electronic evolution of the spin-ladder system BaFe 2 S 3-x Se x with isoelectronic substitution

We reWe report experimental studies of a series of BaF e 2 S 3 - x Se x ( 0 ≤ $x$ ≤ 3 ) single crystals and powder specimens using x-ray diffraction, neutron-diffraction, muon-spin-relaxation, and electrical transport measurements. A structural transformation from $C$ $mcm$ ( BaFe 2 Se 3 ) to $P$ $nma$ ( BaFe 2 Se 3 ) was identified around $x$ = 0.7 - 1 . Neutron-diffraction measurements on the samples with $x$ = 0.2, 0.4, and 0.7 reveal that the Néel temperature of the stripe antiferromagnetic order is gradually suppressed from ~120 to 85 K, while the magnitude of the ordered Fe 2+ moments shows very little variation. Similarly, the block antiferromagnetic order in BaFe 2 Se 3 remains robust for 1.5 ≤ $x$ ≤ 3 with negligible variation in the ordered moment and a slight decrease of the Néel temperature from 250 K ( $x$ = 3 ) to 225 K ( $x$ = 1.5 ). The sample with $x$ = 1 near the $C$ $mcm$ and $P$ $nma$ border shows coexisting, two-dimensional, short-range stripe- and block-type antiferromagnetic correlations. The system remains insulating for all $x$ , but the thermal activation gap shows an abrupt increase when traversing the boundary from the $C$ $mcm$ stripe phase to the $P$ $nma$ block phase. The results demonstrate that the crystal structure, magnetic order, and electronic properties are strongly coupled in the BaFe 2 S 3-x Se x system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2026

Noncollinear spin order, field-induced transitions, and short-range correlations in Cu 4 ⁢SO 4 ⁢(OH) 6

We report a comprehensive study of spin-$\frac{1}{2}$ quantum magnet brochantite, Cu 4 ⁢SO 4 ⁢(OH) 6 , combining high-field thermodynamic measurements, polarized neutron diffraction, inelastic neutron scattering, and nuclear magnetic resonance spectroscopy. Using bulk magnetization and specific heat measurements we construct the magnetic 𝐻−𝑇 phase diagram for magnetic fields applied along main crystallographic directions up to 24.1 T. Polarized neutron diffraction reveals a noncollinear magnetic ground state confined to the 𝑎⁢𝑏 plane. A field-induced transition is observed for magnetic fields in the 𝑎⁢𝑏 plane whose critical field and character evolve continuously with field direction in the 𝑎⁢𝑏 plane. While the transition for 𝐻 ∥ 𝑏 might be a spin-flop-like transition, the one for 𝐻 ∥ 𝑎 resembles the short-range correlated state above 𝑇 N , suggesting a magnetic configuration related to the quasi-two-dimensional correlations in the 𝑏⁢𝑐 planes. The experimental results demonstrate that the ground-state and field-induced phases cannot be explained by a simple XXZ model with a single dominant exchange interaction and that weaker interchain and anisotropic interactions have to be taken into account. Our work establishes brochantite as a low-symmetry Cu-based quantum magnet with noncollinear order and complex field-induced behavior.

Prokhnenko, Oleksandr [Helmholtz-Zentrum Berlin (H↗

DOE OSTI2021

Canted antiferromagnetic order and spin dynamics in the honeycomb-lattice compound Tb 2 Ir 3 Ga 9

Here, single-crystal neutron diffraction, inelastic neutron scattering, bulk magnetization measurements, and first-principles calculations are used to investigate the magnetic properties of the honeycomb lattice Tb 2 Ir 3 Ga 9 . While the R ln 2 magnetic contribution to the low-temperature entropy indicates a J eff = 1 / 2 moment for the lowest-energy crystal-field doublet, the Tb 3 + ions form a canted antiferromagnetic structure below 12.5 K. Due to the Dzyaloshinskii-Moriya interactions, the Tb moments in the a b plane are slightly canted towards b with a canted moment of 1.22 μ B per formula unit. A minimal x x z spin Hamiltonian is used to simultaneously fit the spin-wave frequencies along the high-symmetry directions and the field dependence of the magnetization along the three crystallographic axes. Long-range magnetic interactions for both in-plane and out-of-plane couplings up to the second nearest neighbors are needed to account for the observed static and dynamic properties. The z component of the exchange interactions between Tb moments is larger than the x and y components. This compound also exhibits bond-dependent exchange with negligible nearest-neighbor exchange coupling between moments parallel and perpendicular to the 4 f orbitals. Despite the J eff = 1 / 2 moments, the spin Hamiltonian is denominated by a large in-plane anisotropy K z ~ – 1 meV . DFT calculations confirm the antiferromagnetic ground state and the substantial interplane coupling at larger Tb-Tb distances.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Magnetic properties of the quasi-XY Shastry-Sutherland magnet ER 2 Be 2 SiO 7

Polycrystalline and single-crystal samples of the insulating Shastry-Sutherland compound Er 2 ⁢Be 2 ⁢SiO 7 were synthesized via a solid-state reaction and the floating zone method, respectively. The crystal structure, Er single-ion anisotropy, zero-field magnetic ground state, and magnetic phase diagrams along high-symmetry crystallographic directions were investigated with bulk measurement techniques, x-ray and neutron diffraction, and neutron spectroscopy. Here, we establish that Er 2 ⁢Be 2 ⁢SiO 7 crystallizes in a tetragonal space group with planes of orthogonal Er dimers and a strong preference for the Er moments to lie in the local plane perpendicular to each dimer bond. We also find that this system has a noncollinear ordered ground state in zero field with a transition temperature of 0.841 K consisting of antiferromagnetic dimers and in-plane moments. Finally, we mapped out the H-T phase diagrams for Er 2 ⁢Be 2 ⁢SiO 7 along the directions H ∥ [001], [100], and [110]. While an increasing in-plane field simply induces a phase transition to a field-polarized phase, we identify three metamagnetic transitions in the H ∥ [001] case. Single-crystal neutron diffraction results reveal that the H ∥ [001] phase diagram can be explained predominantly by the expected field-induced behavior of classical, anisotropic moments, although the microscopic origin of one phase requires further investigation.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Search for octupolar order in NpO 2 by neutron powder diffraction

The magnetic structure of neptunium dioxide (NpO 2 ) remains a mystery despite decades of research. We revisited the search for magnetic ordering in NpO 2 by performing a powder neutron diffraction experiment at low temperatures and relatively large values of Q. Diffraction data were collected for 300 MK, 15 K, and 35 K to understand the phase transition near 25 K. However, no significant changes in the neutron diffraction pattern were identified. Using the octupolar magnetic form factor j 6 , the maximum theoretical expected value of the magnetic moment (3.27 μ B ), the calculated magnetic Bragg peak intensities would not be observable in neutron powder diffraction data. This value is much larger than the previously estimated magnetic moment of ~0.1 μ B . In conclusion, supported by experimental results, these calculations suggest that unpolarized neutron powder diffraction is unsuitable for measuring octupolar ordering in NpO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Neutron powder diffraction, Mossbauer Spectroscopy and Optical Spectroscopy to study magnetic and nuclear lattices in Fe-based oxychlorides Ca2FeO3Cl, Sr2FeO3Cl and Sr3Fe2O5Cl2

Data for Neutron Diffraction, Mossbauer Spectoscopy and Optical Spectroscopy are contained on all three samples (Ca2FeO3Cl, Sr2FeO3Cl, and Sr3Fe2O5Cl2). Mossbauer data are in the folder "MossbauerSpectroscopy". This contains details of files and examples to read the data. The Optical Spectroscopy are in the folder "AbsorptionData", this contains one file with explanatory headers. The neutron diffraction data are in the "NeutronDiffractionData" folder. The data was collected on the HB-2A powder diffractometer at HFIR. The autoreduced files are corrected using a vanadium standard and are in arbitrary intensity units. The RawData folder contains the uncorrected data with metadata for motor positions and temperature. All measurements were collected with a constant neuton wavelength of 2.41 Angstrom. An excel spreadsheet "NeutronDiffractionData_IPTS-29118_summary" contains details for each scan. Sr3Fe2O5Cl2 data were collected at only room temperature. Ca2FeO3Cl and Sr2FeO3Cl data were collected at 4K and room temperature. The autoreduced .dat fileformat is three columns corresponding to: Two-theta, Intensity and Intensity_error.

fe-based oxychlorides↗

NASA NTRS2004

In situ x-ray and neutron powder diffraction study of LaNi5-xSnx-H systems

This paper will present results of in situ XRD measurements of LaNi4.75Sn0.25 .during the initial absorption-desorption cycle, These measurements were performed under a similar condition to that for LaNi4.75Al0.25 previously reported [1]. The data were analyzed by the Rietveld method. Lattice parameter change and strain formation accompanying hydride phase formation and decomposition will be discussed. In addition, results of in situ neutron diffraction of LaNi4.78Sn0.22, focusing on hydrogen occupation in the hydride phase, will be presented.

metal hydrides↗

DOE OSTI2021

Evolution of magnetic interactions in Sb-substituted MnBi 2 Te 4

The Mn(Bi 1–x Sb x ) 2 Te 4 series is purported to span from an antiferromagnetic (AF) topological insulator at x = 0 to a trivial AF insulator at x = 1. Here we report on neutron diffraction and inelastic neutron scattering studies of the magnetic interactions across this series. All compounds measured possess ferromagnetic (FM) triangular layers and we find a crossover from AF to FM interlayer coupling near x = 1 for our samples. The large spin gap at x = 0 closes rapidly and the average FM exchange interactions within the triangular layer increase with Sb substitution. Similar to a previous study of MnBi 2 Te 4 , we find severe spectral broadening which increases dramatically across the compositional series. In addition to broadening, we observe an additional sharp magnetic excitation in MnSb 2 Te 4 that may indicate the development of local magnetic modes originating from antisite disorder between Mn and Sb sublattices. Here, the results suggest that both substitutional and antisite disorder contribute substantially to the magnetism in Mn(Bi 1–x Sb x ) 2 Te 4 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Structural Distortions and Uniaxial Negative Thermal Expansion in the Polar Dion–Jacobson Oxide RbNdTa 2 O 7

We provide deeper insight into the crystal structures, sequential structural phase transitions (I2cm → Cmce → I4/mcm → P4/mmm), thermal expansion, and electronic properties of the n = 2 Dion–Jacobson polar oxide RbNdTa 2 O 7 , through X-ray powder diffraction, neutron powder diffraction, Raman studies, and density functional theory calculations. We observed a uniaxial negative thermal expansion (NTE) across the first-order transition, I2cm → Cmce, where the unit cell contracts along the c-axis, which is driven by a contraction of the NdTa 2 O 6 layer. Here, this NTE occurs within the temperature range of the first-order phase transition and contrasts with the corkscrew mechanism typically observed in Ruddlesden–Popper phases. In RbNdTa 2 O 7 , the I2cm (hybrid improper ferroelectric) → Cmce (antipolar) transition involves crucial changes in the bond lengths of Nd and Ta polyhedra, coupled with polar to antipolar displacement of the Nd ions, leading to a net contraction in the NdTa 2 O 6 layer along the c-axis, while preserving the overall octahedral tilting magnitude. This transition highlights the intricate interplay between the Nd and Ta coordination and the associated TaO 6 distortions. Temperature-dependent Raman spectra analysis further confirms the first-order structural transition and associated NTE, providing evidence for increased bond stiffness across this transition. Additionally, using neutron powder diffraction, we have determined that the transition I4/mcm → P4/mmm occurs at approximately 1150 K. Finally, we have calculated from DFT + U, the partial density of states, the energy bandgaps, and effective masses of the charge carriers of the polar ground structure.

Chemical structure↗

DOE OSTI2022

Bond valence sum analysis of pyrochlore oxides including the novel dielectric Te 6+ pyrochlores: A Bi M TeO 7-y ( A = Cd, Ca; M = Cr, Ga, Sc, In, Fe)

Bond valence sum analysis is a powerful tool used in evaluating and validating crystal structures; especially when those structures are complex in nature. The pyrochlore structure type is versatile in not only the unique bonding that it exhibits, but also in the properties that results from the structure. Here this paper aims to center the discussion of evaluating the pyrochlore structure using the bond valence sum method. In this study, novel quaternary pyrochlores with a general stoichiometry of ABiMTeO 7 (A = Cd, Ca; M = Cr, Ga, Sc, In, Fe) were synthesized and characterized for their structural, magnetic, and dielectric properties. Two representative compounds within this series of pyrochlores, BiCaFeTeO7 and BiCdFeTeO 7 , were structurally characterized utilizing a combination of high-resolution synchrotron X-ray diffraction and neutron diffraction revealing oxygen deficient pyrochlore systems which were off from the expected stoichiometry with respect to the M site. The A site of both pyrochlores were found to be moved off-center from the expected 16d site to the 96h displaced position at a magnitude of 0.25 Å and 0.22 Å for the Bi/Ca and Bi/Cd systems, respectively. These structures were evaluated using the bond valence sum method and compared with trends in the literature. The properties are also reported for the Bi/Ca system for the first time, showing relatively high dielectric constants with a low dielectric loss which are primarily independent of frequency and temperature. The magnetic measurements for the Bi/Ca system for the magnetic substitutions reveal a paramagnet and antiferromagnetic properties for the Fe and Cr analogs, respectively. The novel BiCaMTeO 7 quaternary pyrochlore system shows great promise as an emerging dielectric material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗