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At least 631 records · Page 35

Magnetic Navigation for GPS-Denied Airborne Applications

Most current flight systems are dependent on GPS for navigation. Recently, however, navigation in GPS-denied environments has become an area of intensive research. Additional navigation sensor data can be obtained from visual observations (stars or terrain), inertial measurement units, radar, measurements of the local magnetic field, or perhaps even gravity. Absolute and relative positioning via magnetic field measurements have been shown to be viable in many applications including ground navigation, low altitude aircraft flight, and spaceflight. There is greater variability in the magnetic field over shorter distances when flying at low altitude and in ground applications, leading to more accurate positioning. However, ground-based magnetic navigation is often heavily influenced by man-made structures, especially in urban environments. This is not the case for airborne magnetic navigation since the influence of buildings, roads, etc. is negligible for typical aircraft altitudes. For absolute magnetic navigation, the positioning accuracy decreases as altitude increases for a given vehicle velocity, but the observed time variability in the field can be reclaimed by traveling faster through the field. Thus, navigation accuracy becomes a balance of speed and altitude since the higher altitude can be counterbalanced by higher velocity. To understand these effects quantitatively, we explored various techniques to aid a simulated inertial measurement unit with magnetic information. Using a technique known as two-dimensional magnetic map matching, we simulated the performance of airborne magnetic navigation at fixed speed while varying the altitude, flight direction, magnetometer data collection time, reference magnetic map bias error, and type of trajectory (over land or over ocean).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Acceptance Testing of the Scorpius Sweep Magnet

A beam-dump magnet for Scorpius has been defined by LANL and designed and built by Radiabeam Technologies. Initial verification of the Radiabeam design used a magnetic field model provided by Radiabeam and analyzed by LANL tools during September 2021. Simulations indicated that the design was sufficient to meet deflection requirements to protect sensitive equipment in the case of a failed target. In January 2022, the magnet was fabricated and Radiabeam conducted measurements of the magnetic field as a function of position. The measurements deviate somewhat from the simulation. In particular, the peak magnetic field is 10-15% smaller in magnitude than expected from simulation. This note compares the magnetic field measurements to simulation and to measurements of the existing DARHT magnet, which was designed for the same purpose. We show a comparison of the measured beam deflection performance between Scorpius and DARHT and show updated results of LANL’s electron beam tracking code using the Scorpius measurements. Using field measurements we find that the DARHT magnet will deflect a 19.6 MeV electron beam by 46.6° and the Scorpius magnet will deflect by 44.6°. These results show that the as-built Scorpius magnet has met design requirements for beam deflection.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Design and Prototyping of a Novel Toroid Magnet System for the MOLLER Experiment at Jefferson Lab

The Thomas Jefferson National Accelerator Facility (JLab) has designed a unique spectrometer system to measure the weak interaction between electrons. The experiment ?Measurement of Lepton-Lepton Electroweak Reaction? (MOLLER) requires leveraging the recent 12 GeV electron beam upgrade and will run in JLab for 3 years. Focusing the signal for the MOLLER experiment requires five water-cooled toroidal magnets, each with unique geometry and with 7-fold symmetry. This system of magnets provides the magnetic field required to separate the incident beam electrons scattered from the target electrons (Møller scattering) and protons (elastic e-p scattering) in a liquid hydrogen target. The conceptual design was developed by the MOLLER collaboration and was given to JLab in the form of amp turns and physical location, with additional physics requirements. This paper presents prototyping of the coils and magnet support system and discusses the lessons learned during the process along with the plans for full magnet testing and installation. The JLab Magnet Group along with the MOLLER collaboration developed the specification document that includes keep out zones to design the set of magnets. JLab contracted the design of the first toroid magnet in the magnet (TM0) to Massachusetts Institute of Technology. The other four toroid magnets (TM1 through TM4) have been designed by JLab and are in the process of fabrication and assembly. Prototype coils of TM1-TM4 have been fabricated by Everson-Tesla Incorporated, PA (USA). The manuscript presents the unique challenges of the design, alignment, high current density, operating range, high radiation dose, and vacuum environment.

Kashy, David↗

Re-assembly and test of COMB dipole magnet with STAR® wires

Fermilab is developing the Conductor on Molded Barrel (COMB) magnet technology that works well with round REBCO conductors. COMB-STAR-1 magnet based on STAR wire by AMPeers was fabricated and tested in liquid nitrogen in 2023. The magnet demonstrated >90 Ic retention in the coils (before/after winding). Even though the magnet was not originally designed for operation at lower than 77 K temperatures, it was decided to test it in liquid helium to: - check the instrumentation and the DAQ system; - check the ability to detect resistive transitions or quenches and to protect the magnet; - gather the information on possible magnet design chances and upgrades of the test facility for future testing of HTS magnets. The magnet was re-assembled with a larger iron yoke and the axial supports and tested in liquid helium in 2024 at Fermilab s Vertical Magnet Test Facility (VMTF). It was the first HTS magnet test at that facility ever.

Kashikhin, Vadim↗

Measurement of the thermal effects in the dispersion relation of the dust acoustic wave in the presence of a magnetic field

This award supported an experimental study of the properties of the dust acoustic wave, low-frequency, l ongitudinal wave mode that propagates through the dust component of a dusty plasma system and is self-excited by the free energy from the ion streaming p ast the dust, in the presence of a high magnetic fiel d. In particular, this project measured the thermal state of dusty plasma system by measuring the dispersi on relation of the dust acoustic wave while varying (1) the strength and direction of the magnetic field relative to the propagation direction of the wave and (2) the neutral gas pressure. By exploiting the unique ability of the MDPX facility to generate a dusty plasma in a high magnetic field environment, it is possible to create a preferential ion flow along the magnetic field lines as the ions become magnetized. In this way, the magnetic field strength can be used to control t he strength of the ion flow through the dust cloud an d provide insight into the contribution that one of the physical mechanisms, a two-stream ion-dust instability, thought to be responsible for high temperatures that have been previously observed might have. This work was completed over two, one-week long runs o n the Magnetized Dusty Plasma eXperiment (MDPX) in the Magnetized Plasma Research Laboratory at Auburn University and supported by work at Wittenberg University (development of an electrode system that would allow for the wave mode to propagate in th e direction of gravity as the orientation of the magnetic field is changed by rotating the magnets on the M DPX device, analysis of data acquired during the experimental campaigns, testing alternative strategies to form a dust cloud based on what was learned the first experimental campaign, etc.).

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Non-Equilibrium Effects in Quantum Magnets

While most often the state of a material will tend toward an equilibrium determined by its environment, there are many cases of scientific and technological interest where materials are manipulated to be or are found in non-equilibrium configurations. For example, data can be stored in hard drives by deliberately altering the magnetic orientation in a material to store information in non-equilibrium pattern. In this project, the main goals were studies of non-equilibrium properties of quantum magnets using neutron scattering as the primary experimental method. Neutron scattering allows characterization of magnetic correlation lengths sensitive to the presence of defects. It can also be used to distinguish equilibrium from non-equilibrium states via energy transfer rates. Typical bulk state magnetization relaxation times are too short to perform many neutron scattering measurements of interest. To enable the study of non-equilibrium conditions, materials with longer magnetic relaxation times were targeted. CoNb 2 O 6 was used in two experiments related to non-equilibrium physics. In the first, evidence for defects created via the Kibble-Zurek mechanism (KZM) was sought by quenching across a magnetic field-dependent phase transition. Somewhat unexpectedly, clear evidence for KZM-induced defects was absent. Additional measurements of CoNb 2 O 6 were made to better characterize its crystal field and other properties to provide a better theoretical understanding to enable more effective non-equilibrium physics measurements. In another project, LiHo 0.45 Y 0.55 F 4 was used to compare a quantum annealing protocol to a thermal annealing one since magnetic fields can be used to control the thermal fluctuations in LiHo 0.45 Y 0.55 F 4 . In addition, a new pulsed magnet power supply and new techniques were developed suitable for neutron scattering experimental environments to enable faster magnetic field changes for producing non-equilibrium conditions. The power supply developed for this project has wider technological applications in addition to faster magnetic field ramps.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Additive manufacturing of amorphous metal soft magnetic composites

Soft magnet alloys are used as magnetic cores for electric motors, transformers, wind turbines and other power generation systems. Soft magnetic cores are expensive and time consuming to manufacture in the complex shapes required for next-generation devices using conventional press and sinter powder metallurgy. The objective of this effort is to additively manufacture high performance soft magnets, with reduced cost and reduced material waste and 10x lower energy (core) loss at the high operating frequencies of many electric machines. Laser powder bed fusion additive manufacturing is used as the fabrication method. Electrical steel and amorphous alloys atomized powders are used as a feedstock materials. Magnetic cores are printed in topology optimized structures such as the Hilbert curve because this has been shown to reduce energy losses by minimizing the eddy currents that circulate within the magnet at high frequencies. In our project, we succeed in printing FeSi 3.5wt% and FeSi 6.5wt% electrical steels, and iron-based soft magnetic amorphous alloys in the shape of Hilbert and Peano curve topology optimized structures. We found that the Peano curve has a higher cut-off frequency than the Hilbert curve, and that amorphous alloys have high cut-off frequencies and higher mechanical hardness than electrical steels. Processing conditions such as laser power, scan speed, and hatching pattern were optimized to achieve high density prints, and optimize magnetic performance. We find that the printing of amorphous alloy soft magnetic cores may be technoeconomically feasible for large scale applications such as transformers, for which supply chain issues and the labor costs of manual fabrication of magnetic cores is prohibitive in some cases.

36 MATERIALS SCIENCE↗

Methods and apparatus for making magnetic skyrmions

A system and a method for the deterministic generation of magnetic skyrmions includes a magnetic strip configured to store and transport skyrmions. The magnetic strip includes one or more spatial inhomogeneities configured to generate a skyrmion at known locations when excited by a current pulse. A current pulse generator is used to inject current pulses into the magnetic strip via contact pads electrically coupled to both the current pulse generator and the magnetic strip. The system also includes a magnetic field source to apply an out-of-plane magnetic field across the magnetic strip to facilitate generation of skyrmions. Skyrmions can be generated by applying an out-of-plane magnetic field to the magnetic strip and injecting a current pulse with sufficient current density towards the spatial inhomogeneities. Once a skyrmion is generated, another current pulse with sufficient current density can be injected to move the skyrmion.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Understanding magnetic phase coexistence in Ru 2 Mn 1-x Fe x Sn Heusler alloys: A neutron scattering, thermodynamic, and phenomenological analysis

The random substitutional solid solution between the antiferromagnetic (AFM) full-Heusler alloy Ru 2 MnSn and the ferromagnetic (FM) full-Heusler alloy Ru 2 FeSn provides a rare opportunity to study FM-AFM phase competition in a near-lattice-matched, cubic system, with full solubility. At intermediate x in Ru 2 Mn 1-x Fe x Sn this system displays suppressed magnetic ordering temperatures, spatially coexisting FM and AFM order, and strong coercivity enhancement, despite rigorous chemical homogeneity. Here, we construct the most detailed temperature- and x-dependent understanding of the magnetic phase competition and coexistence in this system to date, combining wide-temperature-range neutron diffraction and small-angle neutron scattering with magnetometry and specific heat measurements on thoroughly characterized polycrystals. A complete magnetic phase diagram is generated, showing FM-AFM coexistence between x ≈ 0.30 and x ≈ 0.70. Furthermore, important insight is gained from the extracted length scales for magnetic phase coexistence (25–100 nm), the relative magnetic volume fractions and ordering temperatures, and remarkable x-dependent trends in magnetic and electronic contributions to specific heat. An unusual feature in the magnetic phase diagram (an intermediate FM phase) is also shown to arise from an extrinsic effect related to a minor Ru-rich secondary phase. The established magnetic phase diagram is then discussed with the aid of phenomenological modeling, clarifying the nature of the mesoscale phase coexistence with respect to the understanding of disordered Heisenberg models.

36 MATERIALS SCIENCE↗

Magnetic‐Field‐Switchable Laser via Optical Pumping of Rubrene

Abstract Volumetric optical imaging of magnetic fields is challenging with existing magneto‐optical materials, motivating the search for dyes with strong magnetic field interactions, distinct emission spectra, and an ability to withstand high photon flux and incorporation within samples. Here, the magnetic field effect on singlet‐exciton fission is exploited to demonstrate spatial imaging of magnetic fields in a thin film of rubrene. Doping rubrene with the high‐quantum yield dye dibenzotetraphenylperiflanthene (DBP) is shown to enable optically pumped, slab waveguide lasing. This laser is magnetic‐field‐switchable: when operated just below the lasing threshold, application of a 0.4 T magnetic field switches the device between nonlasing and lasing modes, accompanied by an intensity modulation of +360%. This is thought to be the first demonstration of a magnetically switchable laser, as well as the largest magnetically induced change in emission brightness in a singlet‐fission material to date. These results demonstrate that singlet‐fission materials are promising materials for magnetic sensing applications and could inspire a new class of magneto‐optical modulators.

36 MATERIALS SCIENCE↗

Quantum Disordered State of Magnetic Charges in Nanoengineered Honeycomb Lattice

Abstract A quantum magnetic state due to magnetic charges is never observed, even though they are treated as quantum mechanical variables in theoretical calculations. Here, the occurrence of a novel quantum disordered state of magnetic charges in a nanoengineered magnetic honeycomb lattice of ultra‐small connecting elements is demonstrated. The experimental research, performed using spin resolved neutron scattering, reveals a massively degenerate ground state, comprised of low integer and energetically forbidden high integer magnetic charges, that manifests cooperative paramagnetism at low temperature. The system tends to preserve the degenerate configuration even under large magnetic field application. It exemplifies the robustness of disordered correlation of magnetic charges in a 2D honeycomb lattice. The realization of quantum disordered ground state elucidates the dominance of exchange energy, which is enabled due to the nanoscopic magnetic element size in nanoengineered honeycomb. Consequently, an archetypal platform is envisaged to study quantum mechanical phenomena due to emergent magnetic charges.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Magneto-Transport Properties of Cr 1/3 TaS 2 with Chiral Magnetic Solitons

Cr 1/3 TaS 2 —a candidate of chiral magnet—has been reported as a trivial ferromagnetic material. In contrast, the Cr 1/3 TaS 2 single crystals exhibit a chiral helimagnetic (CHM) transition near 140 K. The magnetic moment versus magnetic field curves reveal a CHM—chiral soliton lattice (CSL)—forced ferromagnetic (FFM) transition in the magnetic ordered state. The conducting electrons interact with the CHM and CSL orders, giving rise to the nontrivial magnetoresistance (MR) in the Cr 1/3 TaS 2 single crystals. The normalized magnetic moment and normalized MR fit well with the analytical functions for chiral soliton density. The magnetic phase diagrams constructed from the magnetic moment data and MR data suggest a possible tri-critical point. Compared with the isostructural Cr 1/3 NbS 2 , the CHM transition temperature of Cr 1/3 TaS 2 is 13 K higher, the CSL—FFM transition field is about 10 times larger, and the Dzyaloshinskii-Moriya interaction strength is 3 times bigger. The latter two likely originate from the strong spin-orbit coupling (SOC) of Cr 1/3 TaS 2 . This work clarifies that high-quality Cr 1/3 TaS 2 single crystals are chiral magnets and Cr 1/3 (Nb,Ta)S 2 could serve as an intriguing platform for the flexible engineering of chiral magnetic solitons with tunable SOC.

36 MATERIALS SCIENCE↗

Development of rare-earth-free bulk magnets with energy product up to 12 MGOe in field annealed Mn–Bi–Mg–In–Sb alloys

A treatment consisting of annealing in a moderately strong, ≤30 kOe, magnetic field was applied to arc-melted ingots and compacted melt-spun alloys with composition Mn 50 Bi 50-x-y-z Mg x In y Sb z . The high degree of texture of the magnetic α phase induced with annealing of the ingot samples (except the Mn–Bi–Sb one) allowed for accurate determination of the phase anisotropy field. Alloying was found to increase the anisotropy field from 45 kOe in the Mn 50 Bi 50 alloy to 65 kOe in the Mn 50 Bi 45 Mg 3 In 0.5 Sb 1.5 alloy. In the compacted melt-spun alloys subjected to field annealing, a higher degree of texture could be achieved after compaction which had involved less heating, when a smaller fraction of the metastable β' phase had been converted into the α phase; compaction at room temperature allowed for the highest degree of texture in the Mn 50 Bi 45 Mg 3 In 0.5 Sb 1.5 magnet. The addition of indium was found to decrease the solidus temperatures of the alloys, facilitating the development of the α phase during the field annealing and modifying the properties of the resulting magnets. Introduction of indium resulted in a higher coercivity H c of the Mn–Bi–Mg–In magnets and in a better texture of the Mn–Bi–Mg–Sn–In magnets. The former effect allowed, in particular, for a viable maximum energy product ( BH ) max of 10 MGOe to be developed in the Mn 50 Bi 46.5 Mg 3 In 0.5 magnet through annealing in a relatively low field of 15 kOe, whereas the latter effect allowed for an excellent combination of ( BH ) max = 11.6 MGOe and H c = 8.5 kOe in the Mn 50 Bi 45 Mg 3 In 0.5 Sb 1.5 magnet. The highest ( BH ) max of 12 MGOe was realized in the Mn 50 Bi 46 Mg 3 In 0.5 Sb 0.5 magnet.

36 MATERIALS SCIENCE↗

Transition from an incommensurate spin density wave to a commensurate magnetic order in a triangular lattice compound Ho 2 PdAl 6 Ge 4

Rare-earth (RE) intermetallics on a triangular lattice are promising candidates for generating interesting magnetic phases due to the complex interplay between Ruderman-Kittel-Kasuya-Yoshida (RKKY) interaction and geometrical frustration. Here, in this work, we report the exotic magnetic structure of a layered compound Ho 2 PdAl 6 Ge 4 with triangular lanthanide nets. Magnetization and heat capacity measurements in zero magnetic field reveal two magnetic phase transitions at T N1 = 10.8 K and T N2 = 6.0 K. Neutron powder diffraction demonstrates a commensurate antiferromagnetic phase with k 1 = (0, 0, 1.5) below T N2 . With increasing temperature, another incommensurate vector appears and therefore, the magnetic structure of the intermediate state is identified as an unusual incommensurate spin density wave with two propagation vectors k 1 = (0, 0, 1.5) and k 2 = (0.0492, 0.0492, 1.5). The magnetic moments in the intermediate state rotate continuously and form an unusual S-shaped wave arrangement in the ab plane, sharing similarities with typical cycloid and helix magnetic orders. These results identify Ho 2 PdAl 6 Ge 4 as a candidate for exploring field-induced topological magnetic phases such as skyrmions, opening the way for further investigations on the family of RE 2 PdAl 6 Ge 4 materials.

36 MATERIALS SCIENCE↗

Evolution of Structure and Magnetism in FeCl 2 and FeCl 3 : From Clusters to Monolayers

In this work, we address one of the most fundamental questions in cluster science─how do the structure and properties evolve from clusters to crystals? Using density functional theory (DFT), we focus our study on the evolution of structure and magnetism in iron-chloride systems, from clusters to monolayers. The choice of this system is motivated by the recent experimental confirmation of one of the author’s earlier theoretical prediction that the FeCl 2 cluster is magnetic with a spin magnetic moment of 4 μ B localized at the Fe site, while its dimer, Fe 2 Cl 4 , is antiferromagnetic. Similarly, FeCl 3 cluster is magnetic with a total spin magnetic moment of 5 μ B , with 4 μ B localized at the Fe site and 1 μ B distributed over the Cl sites. The dimer clusters Fe 2 Cl 4 and Fe 2 Cl 6 have an antiferromagnetic ground state, and upon Li-functionalization, both can be magnetically transformed from antiferromagnetic to ferromagnetic states. In contrast, FeCl 2 and FeCl 3 monolayers exhibit different magnetic ground states in their periodic forms: FeCl 2 is ferromagnetic (FM), but in FeCl 3 , the antiferromagnetic (AFM) and FM states are energetically nearly degenerate. Such a difference arises due to the different chemical coordination of the Fe atoms with the Cl atoms, caused by their different oxidation states, which is +2 in FeCl 2 and +3 in FeCl 3 , respectively. Interestingly, Li-functionalization allows both FeCl 3 and FeCl 2 monolayers to be ferromagnetic. Our study highlights that several, but not all, electronic and magnetic characteristics of isolated clusters are preserved in the extended periodic structures. This systematic investigation of iron-halide clusters is expected to inspire further experimental and theoretical exploration into the magnetism of other transition metal halides.

cluster chemistry↗

Tuning the Magnetic Properties of CrI 3 Using Ni Thin Film Deposition for Applications in Spintronic Devices

Chromium triiodide (CrI 3 ), a van der Waals magnet, has recently been shown to host Ising ferromagnetism down to the monolayer limit. It is a potentially important material in 2D magnet-based applications, such as magnetic sensors and spintronic devices. Prior studies have revealed the coexistence of two different types of interlayer magnetic coupling, the antiferromagnetic (AFM) coupling near the surface and ferromagnetic (FM) coupling in the deep bulk layers, in pristine CrI 3 crystals below the Curie temperature. In this study, we used Ni thin film deposition to tune the surface magnetic states in bulk CrI 3 . A nanometer thickness (4 nm thick) of Ni was deposited on the surface of CrI 3 using electron-beam evaporation to form a Ni/CrI 3 heterostructure. The deposited Ni thin layer forms nanoclusters that completely cover the CrI 3 surface. Magnetic states of CrI 3 before and after Ni deposition are probed by ultralow-frequency magneto-Raman spectroscopy. Instead of seeing three spin wave branches in Raman scattering below 2 T, as in pristine bulk CrI 3 , in Ni/CrI 3 , we observe only a single spin wave branch, which is softened compared to that in pristine CrI 3 and displays a Zeeman shift under an out-of-plane magnetic field up to 7 T. This observation reveals that the AFM layers on pristine CrI 3 crystal surfaces transit into FM layers, so the entire CrI 3 crystal is in the FM state after Ni deposition. First-principles calculations show that Ni atoms tend to diffuse into the CrI 3 lattice, and the FM interlayer coupling has a much lower energy than AFM coupling in the presence of Ni atoms. As a result, our studies show that the magnetic state of CrI 3 can be modified through deposition of a thin metal layer on the surface, offering a route for controlling the spin degree of freedom in van der Waals magnets.

36 MATERIALS SCIENCE↗

Strong Electronic and Magnetic Coupling in M 4 (M = Ni, Cu) Clusters via Direct Orbital Interactions between Low-Coordinate Metal Centers

In this report we present an extensive study of tetranuclear transition-metal cluster compounds M 4 (NP t Bu 3 ) 4 and [M 4 (NP t Bu 3 ) 4 ][B(C 6 F 5 ) 4 ] (M = Ni, Cu; t Bu = tert -butyl), which feature low-coordinate metal centers and direct metal-metal orbital overlap. X-ray diffraction, electrochemical, magnetic, spectroscopic, and computational analysis elucidate the nature of the bonding interactions in these clusters and the impact of these interactions on the electronic and magnetic properties. Direct orbital overlap results in strongly coupled, large-spin ground states in the [Ni 4 (NP t Bu 3 ) 4 ] +/0 clusters and fully delocalized, spin-correlated electrons. Correlated electronic structure calculations confirm the presence of ferromagnetic ground states that arise from direct exchange between magnetic orbitals, and, in the case of the neutral cluster, itinerant electron magnetism similar to that in metallic ferromagnets. The cationic nickel cluster also possesses large magnetic anisotropy exemplified by a large, positive axial zero-field splitting parameter of D = +7.95 or +9.2 cm -1 , as determined by magnetometry or electron paramagnetic resonance spectroscopy, respectively. The [Ni 4 (NP t Bu 3 ) 4 ] + cluster is also the first molecule with easy-plane magnetic anisotropy to exhibit zero-field slow magnetic relaxation, and under a small applied field, it exhibits relaxation exclusively through an Orbach mechanism with a spin relaxation barrier of 16 cm -1 . The S = 1 / 2 complex [Cu 4 (NP t Bu 3 ) 4 ] + exhibits slow magnetic relaxation via a Raman process on the millisecond time scale, supporting the presence of slow relaxation via an Orbach process in the nickel analogue. Overall, this work highlights the unique electronic and magnetic properties that can be realized in metal clusters featuring direct metal-metal orbital interactions between low-coordinate metal centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mixed Nd 4+/3+ and Cluster Magnetism in Hexagonal Perovskite 12R-Ba 4 NdMn 3 O 12−γ

Hexagonal perovskite oxides with 12R stacking host well-separated face-sharing octahedral metal trimers with short metal–metal distances, leading in some cases to large degrees of magnetic frustration and cluster magnetism. Introducing magnetic ions in proximity to these trimers can influence the degree of frustration and cluster magnetism, but the extent to which the magnetism can be tuned by varying neighboring metal cations remains an open question. In this work, we test the impacts of using Nd in proximity to Mn trimers in the hexagonal perovskite 12R-Ba 4 NdMn 3 O 12−γ . Given this stoichiometry, Nd should assume the 4+ oxidation state with a spin state of S = 1, which would be the first realization of Nd 4+ in an oxide environment. Through detailed bulk magnetic, X-ray absorption spectroscopic, and powder neutron diffraction (PND) measurements, we find that Nd 4+ is realized in this material, but there is also partial reduction to Nd 3+ , which is charge-balanced by O vacancies. Magnetometry measurements indicate an antiferromagnetic ordering temperature T N ≈ 16 K, and PND measurements reveal a surprising collinear antiferromagnetic structure with magnetic space group Pc2/m (no. 10.49 in BNS notation), which has not previously been seen in this class of materials. Our results represent a comprehensive analysis of the structural, electronic, and magnetic properties of 12R-Ba 4 NdMn 3 O 12−γ , showing the first observation of partial Nd 4+ in an oxide, and demonstrating that this structural class can host a broad range of magnetic structures which are not easily predicted based on compositional trends.

14 SOLAR ENERGY↗