Magnetic Properties Research Articles

A Stable Chichibabin Diradicaloid with Near-Infrared Emission.

Conjugated molecules with multiple radical centers such as the iconic Chichibabin diradicaloid hold promise as building blocks in materials for quantum sensing and quantum information processing. However, it is a considerable challenge to design simple analogues of the Chichibabin hydrocarbon that are chemically inert, exhibit high diradical character and emit light at a distinct wavelength that may offer an optical readout of the spin state in functional ensembles. Here we describe the serendipitous discovery of the stable TTM-TTM diradicaloid, which exhibits high diradical character, a striking sky-blue color and near-infrared (NIR) emission (in solution). This combination of properties is unique among related diradicaloids and is due to the presence of hydrogen and chlorine atoms in "just the right positions", allowing a perfectly planar, yet predominantly benzenoid bridge to connect the two sterically stabilized radical centers. In-depth studies of the optical and magnetic properties suggest that this structural motif could become a mainstay building block of organic spin materials.

Ein Stabiles Chichibabin Diradikaloid mit Nahinfraroter Emission

AbstractKonjugierte Moleküle mit mehreren Radikalzentren, wie das ikonische Chichibabin‐Diradikaloid, sind vielversprechende Bausteine für Materialien für die Quantensensorik und Quanteninformationsverarbeitung. Jedoch stellt es eine große Herausforderung dar, einfache Analoga des Chichibabin‐Kohlenwasserstoffs zu entwickeln, die chemisch inert sind, einen hohen Diradikal‐Charakter aufweisen und Licht einer spezifischen Wellenlänge emittieren, was das optische Auslesen des Spinzustands in funktionalen Ensembles ermöglichen würde.

Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds.

We describe early and recent advances in the fascinating field of combined magnetic and optical properties of inorganic coordination compounds and in particular of 3d-4f single molecule magnets. We cover various applied techniques which allow for the correlation of results obtained in the frequency and time domain in order to highlight the specific properties of these compounds and the future challenges towards multidimensional spectroscopic tools. An important point is to understand the details of the interplay of magnetic and optical properties through performing time-resolved studies in the presence of external fields especially magnetic ones. This will enable further exploration of this fundamental interactions i. e. the two components of electromagnetic radiation influencing optical properties.

Charge-Transfer Complexes: Halogen-Doped Anthracene as a Case of Study.

Charge transfer (CT) crystals exhibit unique electronic and magnetic properties with interesting applications. We present a rational and easy guide which allows to foresee the effective charge transfer co-crystal production and that is based on the comparison of the frontier molecular orbital (MO) energies of a donor and acceptor couple. For the sake of comparison, theoretical calculations have been carried out by using the cheap and fast PM6 semiempirical Hamiltonian and pure HF/cc-pVTZ level of the theory. The results are then compared with experimental results obtained both by chemical (bromine and iodine were used as the acceptor) and electrochemical doping (exploiting an original experimental set-up by this laboratory: the electrochemical transistor). Infra-red vibrational experimental results and theoretically calculated spectra are compared to assess both the effective donor-acceptor (D/A) charge-transfer and transport mechanism (giant IRAV polaron signature). XPS spectra have been collected (carbon (1 s) and iodine (3d5/2)) signals, yielding further evidence of the effective formation of the CT anthracene:iodine complex.

The SF and remanence evaluation of magnetic shields based on SST for low-frequency and degaussing situation

As the dominant shielding functional material, the permalloy sheet primarily determines the static and low-frequency shielding performances of magnetically shielded room (MSR). However, the lack of measurement of shielding sheets for practical use would lead to a non-negligible evaluation error in MSR performance. Therefore, an estimation technique of shielding factor (SF) and the remanence of MSR is proposed in this paper while considering the nonlinear magnetic characteristics of the permalloy sheet tested by a single sheet tester for low-frequency field and degaussing situation (L-D-SST). First, a high-accuracy measurement system, comprising L-D-SST (for exciting magnetic field and sensing the corresponding B and H) and the control system (for applying excitation to L-D-SST and amplifying, filtering, and collecting B and H signals), is established. Weak magnetic fields at low frequencies and decaying alternating demagnetizing field excitations are separately applied to the L-D-SST for basic magnetization curves (BM curves) and an anhysteretic magnetization curve (AM curve) tests. Furthermore, the BM and AM curves are respectively integrated with the FEM algorithm for accurate and reliable estimations of the SF and remanence of MSR in an operational state. In addition, the tested magnetic properties are applied for the optimization of MSR shielding quality.

Bias correction for phase-based cr-MREPT using low resolution B1+ magnitude

Objective Full-form Magnetic Resonance Electrical Properties Tomography (MREPT) requires both B1+ magnitude and phase information. Since B1+ phase can be obtained faster and with higher SNR compared to B1+ magnitude, several phase-based methods have been developed for conductivity imaging. However, phase-based methods suffer from a concave bias due to the assumption that ∇|B1+| is negligible in the ROI. Approach In this paper, we re-derive the central equation of phase-based cr-MREPT without assuming that ∇|B1+| is negligible and thus propose a correction method directly integrated into the equation system. Main results Proposed method successfully corrects the concave bias on both simulated and experimental data and significantly increases image quality. Significance The proposed correction method depends on a very low-resolution |B1+| map, and therefore the imaging time does not increase significantly for obtaining B1+ magnitude. Moreover, correction can be achieved using simulated B1+ magnitude, hence completely removing the additional imaging requirement.

Compositional dependence of magnetostrictive effect in Ta/CoFe(B)/MgO stacks with perpendicular magnetic anisotropy

Magnetostrictive effect in Ta/Co x Fe100−x (B)[CoFe(B)]/MgO for alloy compositions spanning Fe-rich (x = 20) to Co-rich (x = 80) stacks has been studied to investigate the relation between magnetostrictive effect and the onset of perpendicular magnetic anisotropy at Ta/CoFe(B)/MgO interfaces. Interestingly, for each Co composition, a t-dependent crossover between in-plane (ip) and out-of-plane (op) magnetic anisotropy is found at a different CoFe(B) thickness (t cro)–denoted as crossover thickness, which means compositional variations of magnetic properties at the interfaces. By considering the Ta/CoFe(B) and CoFe(B)/MgO interfaces as atomistic volumes with ip and op orbital magnetizations, respectively, the relative ratio of ip to op orbital magnetization in the atomistic volumes is found to be closely related to the dependence of magnetostriction constant (λ s) on the Co composition. The findings suggest that the composition dependence of ip and op orbital magnetization at the Ta/CoFe(B)/MgO interfaces plays an important role in controlling its interfacial anisotropy and magnetostrictive effect of the stacks with the interfaces.

Probing the Band Splitting near the Γ Point in the van der Waals Magnetic Semiconductor CrSBr.

This study investigates the electronic band structure of chromium sulfur bromide (CrSBr) through comprehensive photoluminescence (PL) characterization. We clearly identify low-temperature optical transitions between two closely adjacent conduction-band states and two different valence-band states. The analysis on the PL data robustly unveils energy splittings, band gaps, and excitonic transitions across different thicknesses of CrSBr, from monolayer to bulk. Temperature-dependent PL measurements elucidate the stability of the band splitting below the Néel temperature, suggesting that magnons coupled with excitons are responsible for the symmetry breaking and brightening of the transitions from the secondary conduction band minimum (CBM2) to the global valence band maximum (VBM1). Collectively, these results not only reveal splitting in both the conduction and valence bands but also highlight a significant advance in our understanding of the interplay between the optical, electronic, and magnetic properties of antiferromagnetic two-dimensional van der Waals crystals.

Negative magnetization and magnetic ordering of rare earth and transition metal sublattices in NdFe0.5Cr0.5O3

We investigate the effect of alloying at the 3d transition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3 mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize its structural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5–320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at an unusually high temperature of about 40 K, which is corroborated by Raman measurements.

Oxime Palladacycle Supported on Magnetic Meoporous Silica: An Efficient Catalyst for Copper‐Free Acyl Sonogashira Reaction

AbstractThe catalytic activity of the supported bis(oxime palladacycle) catalyst was evaluated in the acyl Sonogashira reaction. The reaction conditions, such as solvent, base, and palladium content, were screened to achieve the best catalytic performance. Tetrahydrofuran (THF) solvent, triethylamine (Et3N) base, and the reaction temperature of 110 °C were found to be ideal for achieving high yields of the desired products. Furthermore, a catalyst loading of only 0.22 mol% palladium was sufficient to achieve good conversion. Broad ranges of aryl acetylenes and benzoyl chlorides were successfully coupled to give the desired acetylenic ketones. The reaction appeared to proceed efficiently using a small amount of catalyst. The magnetic property of the catalyst allowed for easy separation using an external magnet. The catalyst was stable and reused for multiple reaction runs without a significant deactivation. After seven cycles, the catalyst maintained over 90 % of its initial catalytic activity.

Crystal structure, properties and pressure-induced insulator-metal transition in layered kagome chalcogenides

Layered materials with kagome lattice have attracted a lot of attention due to the presence of nontrivial topological bands and correlated electronic states with tunability. In this work, we investigate a unique van der Waals (vdW) material system, A 2 M 3 X 4 (A = K, Rb, Cs; M = Ni, Pd; X = S, Se), where transition metal kagome lattices, chalcogen honeycomb lattices and alkali metal triangular lattices coexist simultaneously. A notable feature of this material is that each Ni/Pd atom is positioned in the center of four chalcogen atoms, forming a local square-planar environment. This crystal field environment results in a low spin state S= 0 of Ni2+/Pd2+. A systematic study of the crystal growth, crystal structure, magnetic and transport properties of two representative compounds, Rb2Ni3S4 and Cs2Ni3Se4, has been carried out on powder and single crystal samples. Both compounds exhibit nonmagnetic p-type semiconducting behavior, closely related to the particular chemical environment of Ni2+ ions and the alkali metal intercalated vdW structure. Additionally, Cs2Ni3Se4 undergoes an insulator-metal transition (IMT) in transport measurements under pressure up to 87.1 GPa without any structural phase transition, while Rb2Ni3S4 shows the tendency to be metalized.

Exploring the structural, morphological, and multiferroic properties of Al3+ modified (1-x) BCZT-(x) CFO ceramic composites

Multiferroics with strong magnetoelectric coupling can be created by improving the magnetostriction of the ferrite phase and combining it with the best-known piezoelectric. Herein, the ferromagnetic CoFe2O4 was modified with Al incorporation further improve the resistivity, magnetic, and magnetostrictive properties and then combined with (0.5)Ba(Zr0.2Ti0.8)O3−(0.5)(Ba0.7Ca0.3)TiO3 (BCZT) with different weight percentages. XRD results revealed the presence of a mixed spinel cubic phase for CAF (Fd-3m), whereas BCZT crystallized in a tetragonal structure (Amm2) in composite systems. The dielectric response of the materials was studied using impedance spectroscopy and it displayed a typical Maxwell–Wagner polarization of two-phase composites. The magnetic response of the CAF sample improved significantly which is attributed to the preference of Al3+ ions on tetrahedral sites. The magnetization of composites increased as the nonmagnetic BCZT component increased and the (0.75)CAF-(0.25)BCZT system had the highest saturation magnetization. We anticipate that these systems will have significantly improved magnetoelectric characteristics than unmodified CFO-BCZT systems.

Structural phase transition of G-type antiferromagnetic SrMnO3 under pressure

Perovskite SrMnO3 is a versatile material with applications in transistors, supercapacitors, and spintronic devices. This study employs the DFT+U calculations to investigate the electronic and magnetic properties of two polymorphs: 4H-SrMnO3 and 3C-SrMnO3 under isotropic pressure conditions up to 60 GPa. A novel approach based on density functional perturbation theory (DFPT) is employed to precisely determine the on-site Hubbard U value, yielding a computed value of 4.552 eV, consistent with experimental reports. Below P = 14 GPa, the G-AFM phase of 4H-SrMnO3 is the most favored stable, and transitioning to the G-AFM phase of 3C-SrMnO3 beyond 14 GPa. Notably, we observed significant changes in the band gaps, exhibiting an increasing trend under isotropic pressure, while the magnetic moments of the Mn sites exhibit a decreasing trend from ≈2.8 μ B to ≈2.3 μ B for P = 0 GPa and 60 GPa, respectively. The projected density of states (PDOS) reveals the p-d hybridization contributions between the 3d-Mn and 2p-O covalent bonds, along with d-d Mott Hubbard interactions within the localized 3d orbitals of neighboring Mn-Mn atoms. Furthermore, a decrease in the Mn1-O-Mn2 distance prompts enhanced charge transfer which was facilitated by ligand holes, leading to a noticeable decrease in the magnetic moment of the Mn site in the G-AFM phase of SrMnO3.

Structural, optoelectronic, and magnetic behaviors of Li2BeTM (TM = V, Cr, Mn, Fe) Se4 compounds using DFT investigations

In this work, we present computational investigations of the electronic, the optical and the magnetic properties of the Li2BeTMSe4(TM = V, Cr, Mn, Fe) compounds using the first-principle calculations based on the density functional theory. In this respect, we employ the generalized gradient approximation corrected by the Tran-Balaha modified Becke-Johnson exchange potential to obtain more accurate results. Among these outcomes, we first study the electronic properties such as the band energy dispersion and the state densities. Regarding this, the Li2BeTMSe4 quaternary family is found to have an indirect band gap of 1.910 eV, 1.905 eV, 2.223 eV and 1.278 eV for TM = V, Cr, Mn, and Fe, respectively. Further, an examination of the optical properties reveals that the computed optical absorption spectra cover a broad energy range in the visible and the ultraviolet spectrums. Motivated by spintronic applications, we additionally determine the total and the local magnetic moments. Then, we compute the associated Curie temperatures via a linear relation with the total magnetic moments. Among others, the Li2BeTMSe4(TM = V, Cr, Mn, Fe) materials involve acceptable temperatures showing potential applications for high temperature nano-devices activities. Comparing the obtained findings with the available ones, the acquired results indicate that the Li2BeTMSe4(TM = V, Cr, Mn, Fe) materials exhibit a wide range of applications in solar cells, optoelectronics, and other fields.

Electrostatic doping tunable magnetic transition and half-metallicity in the monolayer CrCTe3

The electrical manipulation of the magnetic transition and spin-polarized states has attracted extensive attention in the field of spintronics. In this work, we perform a detailed study on the electronic and magnetic properties of the carrier-doped monolayer CrCTe3 by using first-principles calculation. It is found that, the magnetic transition from Néel-antiferomagnetic (nAFM) to ferromagnetic (FM) is observed in the case of the electron doping, while for hole doping a magnetic transition sequence of nAFM → zigzag-AFM → FM is observed in the monolayer CrCTe3. Interestingly, the carrier doping induced FM ground state always exhibits half-metallicity with full spin polarization. Moreover, the spin polarity of the half-metallic electronic states is opposite for electron and hole doping, meaning that the spin polarization direction can be tuned by manipulating a gate voltage. The Monte Carlo calculations show that the magnetic transition temperature of the doped FM CrCTe3 is rapidly increased with the increasing doping concentration and is extremely expected to achieve room temperature at a suitable doping concentration. These findings demonstrate that the monolayer AFM system possesses a potential application in spintronic devices with electrically tunable spin polarization.

On the Origin of the Above-Room-Temperature Magnetism in the 2D van der Waals Ferromagnet Fe3GaTe2.

2D magnetic materials have attracted growing interest driven by their unique properties and potential applications. However, the scarcity of systems exhibiting magnetism at room temperature has limited their practical implementation into functional devices. Here we focus on the van der Waals ferromagnet Fe3GaTe2, which exhibits above-room-temperature magnetism (Tc = 350-380 K) and strong perpendicular anisotropy. Through first-principles calculations, we examine the magnetic properties of Fe3GaTe2 and compare them with those of Fe3GeTe2. Our calculations unveil the microscopic mechanisms governing their magnetic behavior, emphasizing the pivotal role of ferromagnetic in-plane couplings in the stabilization of the elevated Tc in Fe3GaTe2. Additionally, we predict the stability, substantial perpendicular anisotropy, and high Tc of the single-layer Fe3GaTe2. We also demonstrate the potential of strain engineering and electrostatic doping to modulate its magnetic properties. Our results incentivize the isolation of the monolayer and pave the way for the future optimization of Fe3GaTe2 in magnetic and spintronic nanodevices.

The Xe isotope nuclear resonance frequency shift of NMR angular velocity sensors due to transverse gradient magnetic fields

The nuclear magnetic resonance (NMR) angular velocity sensor detects angular velocity by measuring the shift in the nuclear spin precession frequency, which is of fundamental interest. Recent studies have revealed the parameter dependency of nuclei frequency shifts induced by non-uniformly distributed polarized pump beams, temperature, and magnetic field properties. In this study, we investigated the effect of the linear transverse gradient magnetic field on the frequency ratio shift of the Xe isotope nuclear resonance frequency in the NMR sensors. A theoretical analysis method was proposed based on the Fermi contact interaction in atomic polarization and the spin-diffusion relaxation of 129Xe and 131Xe nuclei. The frequency ratio shift of the Xe isotope under different x-axis gradient magnetic fields was measured experimentally. Furthermore, we eliminated the equivalent residual magnetic field through a feedback system and compensated for the original gradient magnetic field in the system, which contributed to accurately revealing the frequency shift induced by the magnetic field gradient. The results indicate that the frequency ratio shift of the Xe isotope is proportional to the strength of the second-order linear transverse gradient magnetic field. This study provides a reference for the analysis and evaluation of the presence of the gradient magnetic field in the NMR angular velocity sensor.

Two-Dimensional Ultrathin Fe3Sn2 Kagome Metal with Defect-Dependent Magnetic Property.

Two-dimensional (2D) Fe3Sn2, which is a room-temperature ferromagnetic kagome metal, has potential applications in spintronic devices. However, the systematic synthesis and magnetic study of 2D Fe3Sn2 single crystals have rarely been reported. Here we have synthesized 2D hexagonal and triangular Fe3Sn2 nanosheets by controlling the amount of FeCl2 precursors in the chemical vapor deposition (CVD) method. It is found that the hexagonal Fe3Sn2 nanosheets exist with Fe vacancy defects and show no obvious coercivity. While the triangular Fe3Sn2 nanosheet has obvious hysteresis loops at room temperature, its coercivity first increases and then remains stable with an increase in temperature, which should result from the competition of the thermal activation mechanism and spin direction rotation mechanism. A first-principles calculation study shows that the Fe vacancy defects in Fe3Sn2 can increase the distances between Fe atoms and weaken the ferromagnetism of Fe3Sn2. The resulting 2D Fe3Sn2 nanosheets provide a new choice for spintronic devices.

First Principle Study on Structural, Electronic, Magnetic, and Optical Properties of Co-Doped Middle Size Silver Clusters.

The structural, electronic, magnetic, and optical properties of Co-doped 10-20-atom silver clusters are investigated by GGA/PBE via the density functional theory. The Ag-Co clusters form core-shell structures with a Co atom in the center. Co atom doping modulates electronic properties like energy gap, molecular softness, global hardness, electronegativity, and electrophilicity index. For the optical spectra of the Ag-Co clusters, the energy of their spectra overall exhibits little change with increasing numbers of atoms; the strongest peaks are roughly distributed at 3.5 eV, and the intensity of their spectra overall is strengthened. Raman and vibrational spectra reflect structural changes with Co atom addition. The addition of the Co atom alters magnetic moments of specific Ag-Co clusters, while others remain unchanged.

Spectroscopic Manifestations Of (Anti)Aromaticity In Oxidized And Reduced Porphyrin And Norcorrole.

Aromaticity and antiaromaticity are foundational principes in organic chemistry, regularly invoked to explain stability, structure, and magnetic and electronic properties. There are ongoing challenges in assigning molecules as aromatic or antiaromatic using optical spectroscopy. Here we report spectroelectrochemical and computational analyses of porphyrin (18π neutral, aromatic) and norcorrole (16π neutral, antiaromatic), and their oxidized (16π porphyrin dication) and reduced (norcorrole 18π dianion) forms. Our results show that while the visible spectra are characteristic of (anti)aromaticity consistent with Hückel's rules, the IR spectra are much less informative, owing to the relative rigidity of norcorrole. The results have implications for the assignment of (anti)aromaticity in both ground-state and time-resolved excited-state spectra.