Direct Magnetic Interaction Research Articles

A Route to Two-Dimensional Room-Temperature Organometallic Multiferroics: The Marriage of d-p Spin Coupling and Structural Inversion Symmetry Breaking.

Two-dimensional (2D) room-temperature multiferroic materials are highly desirable but still very limited. Herein, we propose a potential strategy to obtain such materials in 2D metal-organic frameworks (MOFs) by utilizing the d-p direct spin coupling in conjunction with center-symmetry-breaking six-membered heterocyclic rings. Based on this strategy, a screening of 128 2D MOFs results in the identification of three multiferroics, that is, Cr(1,2-oxazine)2, Cr(1,2,4-triazine)2, and Cr(1,2,3,4-trazine)2, simultaneously exhibiting room-temperature ferrimagnetism and ferroelectricity/antiferroelectricity. The room-temperature ferrimagnetic order (306-495 K) in these MOFs originates from the strong d-p direct magnetic exchange interaction between Cr cations and ligand anions. Specifically, Cr(1,2-oxazine)2 exhibits ferroelectric behavior with an out-of-plane polarization of 4.24 pC/m, whereas the other two manifest antiferroelectric characteristics. Notably, all three materials present suitable polarization switching barriers (0.18-0.31 eV). Furthermore, these MOFs are all bipolar magnetic semiconductors with moderate band gaps, in which the spin direction of carriers can be manipulated by electrical gating.

Quintuple Function Integration in Two-Dimensional Cr(II) Five-Membered Heterocyclic Metal Organic Frameworks via Tuning Ligand Spin and Lattice Symmetry.

Two-dimensional (2D) semiconductors (SCs) integrated with two or more functions are the cornerstone for constructing multifunctional nanodevices but remain largely limited. Here, by tuning the spin state of organic linkers and the symmetry/topology of crystal lattices, we predict a class of unprecedented multifunctional SCs in 2D Cr(II) five-membered heterocyclic metal organic frameworks that simultaneously possess auxetic effect, room-temperature ferrimagnetism, chiral ferroelectricity (FE), electrically reversible spin polarization, and topological nodal lines/points. Taking 2D Cr(TDZ)2 (TDZ = 1.2.5-thiadiazole) as an exemplification, the auxetic effect is produced by the antitetra-chiral lattice structure. The high temperature ferrimagnetism originates from the strong d-p direct magnetic exchange interaction between Cr cations and TDZ doublet radical anions. Meanwhile, the clockwise-counterclockwise alignment of TDZ's dipoles results in unique 2D chiral FE with atomic-scale vortex-antivortex states. 2D Cr(TDZ)2 is an intrinsic bipolar magnetic SC where half-metallic conduction with switchable spin-polarization direction can be induced by applying a gate voltage. In addition, the symmetry of the little group C4 of the lattice structure endows 2D Cr(TDZ)2 with topological nodal lines and a quadratic nodal point in the Brillouin zone near the Fermi level.

An intermetallic molecular nanomagnet with the lanthanide coordinated only by transition metals

Magnetic molecules known as molecular nanomagnets (MNMs) may be the key to ultra-high density data storage. Thus, novel strategies on how to design MNMs are desirable. Here, inspired by the hexagonal structure of the hardest intermetallic magnet SmCo5, we have synthesized a nanomagnetic molecule where the central lanthanide (Ln) ErIII is coordinated solely by three transition metal ions (TM) in a perfectly trigonal planar fashion. This intermetallic molecule [ErIII(ReICp2)3] (ErRe3) starts a family of molecular nanomagnets (MNM) with unsupported Ln-TM bonds and paves the way towards molecular intermetallics with strong direct magnetic exchange interactions—a promising route towards high-performance single-molecule magnets.

Enhanced flux pinning by magnetic CrB2 nanoparticle in MgB2 superconductor

Different from the non-magnetic pinning centers, the magnetic pinning centers have stronger flux pinning force due to the direct magnetic interaction between the magnetic pinning centers and the magnetic vortices, thus have been widely used to enhance the critical current density of various superconductors. In this article, nanoparticles of antiferromagnet CrB2 were introduced as magnetic pinning center to improve the flux pinning force density (Fp), irreversible field (Hirr), and critical current density (Jc) of MgB2. Compared to the pristine sample, the CrB2 doped MgB2 with low doping levels shows a significantly improved Jc and Fp, especially in the high field region. Hirr is also substantially enhanced. It is revealed that the magnetic flux pinning behavior of CrB2 doped samples obviously deviates from the surface pinning law followed by most pure MgB2. Through theoretical analysis and curve fitting, an extra pinning force superimposed on the surface pinning background is separated and identified, which follows the rule of point pinning. Such a pinning scenario is supported by the microstructure analyses which demonstrate that CrB2 nanoparticles are highly dispersed and embedded in MgB2 matrix, acting as effective pinning centers.

Two-dimensional bipolar magnetic semiconductors with high Curie-temperature and electrically controllable spin polarization realized in exfoliated Cr(pyrazine)2 monolayers

Exploring two-dimensional (2D) magnetic semiconductors with room temperature magnetic ordering and electrically controllable spin polarization is a highly desirable but challenging task for nanospintronics. Here, through first principles calculations, we propose to realize such a material by exfoliating the recently synthesized organometallic layered crystal Li$_{0.7}$[Cr(pyz)$_2$]Cl$_{0.7}$0.25$\cdot$(THF) (pyz = pyrazine, THF = tetrahydrofuran) [Science 370, 587 (2020)]. The feasibility of exfoliation is confirmed by the rather low exfoliation energy of 0.27 J/m$^2$, even smaller than that of graphite. In exfoliated Cr(pyz)$_2$ monolayer, each pyrazine ring grabs one electron from the Cr atom to become a radical anion, then a strong $d$-$p$ direct exchange magnetic interaction emerges between Cr cations and pyrazine radicals, resulting in room temperature ferrimagnetism with a Curie temperature of 342 K. Moreover, Cr(pyz)$_2$ monolayer is revealed to be an intrinsic bipolar magnetic semiconductor where electrical doping can induce half-metallic conduction with controllable spin-polarization direction.

Coherent radio emission from a population of RS Canum Venaticorum systems

Coherent radio emission from stars can be used to constrain fundamental coronal plasma parameters, such as plasma density and magnetic field strength. It is also a probe of chromospheric and magnetospheric acceleration mechanisms. Close stellar binaries, such as RS Canum Venaticorum (RS CVn) systems, are particularly interesting as their heightened level of chromospheric activity and possible direct magnetic interaction make them a unique laboratory to study coronal and magnetospheric acceleration mechanisms. RS CVn binaries are known to be radio-bright but coherent radio emission has only conclusively been detected previously in one system. Here, we present a population of 14 coherent radio emitting RS CVn systems. We identified the population in the ongoing LOFAR Two Metre Sky Survey as circularly polarised sources at 144 MHz that are astrometrically associated with known RS CVn binaries. We show that the observed emission is powered by the electron cyclotron maser instability. We use numerical calculations of the maser’s beaming geometry to argue that the commonly invoked ‘loss-cone’ maser cannot generate the necessary brightness temperature in some of our detections and that a more efficient instability, such as the shell or horseshoe maser, must be invoked. Such maser configurations are known to operate in planetary magnetospheres. We also outline two acceleration mechanisms that could produce coherent radio emission, one where the acceleration occurs in the chromosphere and one where the acceleration is due to an electrodynamic interaction between the stars. We propose radio and optical monitoring observations that can differentiate between these two mechanisms.

Study of the Structure, Magnetic, Thermal and Electrical Characterisation of ZnCr2Se4: Ta Single Crystals Obtained by Chemical Vapour Transport.

The new series of single-crystalline chromium selenides, Ta-doped ZnCr2Se4, was synthesised by a chemical vapour transport method to determine the impact of a dopant on the structural and thermodynamic properties of the parent compound. We present comprehensive investigations of structural, electrical transport, magnetic, and specific heat properties. It was expected that a partial replacement of Cr ions by a more significant Ta one would lead to a change in direct magnetic interactions between Cr magnetic moments and result in a change in the magnetic ground state and electric transport properties of the ZnCr2−xTaxSe4 (x = 0.05, 0.06, 0.07, 0.08, 0.1, 0.12) system. We found that all the elements of the cubic system had a cubic spinel structure; however, the doping gain linearly increased the ZnCr2−xTaxSe4 unit cell volume. Doping with tantalum did not significantly change the semiconductor and magnetic properties of ZnCr2Se4. For all studied samples (0 ≤ x ≤ 0.12), an antiferromagnetic order (AFM) below TN~22 K was observed. However, a small amount of Ta significantly reduced the second critical field (Hc2) from 65 kOe for x = 0.0 (ZnCr2Se4 matrix) up to 42.2 kOe for x = 0.12, above which the spin helical system changed to ferromagnetic (FM). The Hc2 reduction can lead to strong competition among AFM and FM interactions and spin frustration, as the specific heat under magnetic fields H < Hc2 shows a strong field decrease in TN.

Magnetic relaxation in dysprosium and terbium 1D-zigzag coordination chains having only 4,4′-bipyridine as connector

The coordination chain {[Dy(dbm)3bpy]·C7H8}n(1) having only 4,4′-bipyridine as connector has been prepared in high yield and its structural and magnetic properties have been investigated. It is isostructural with the terbium analogue {[Tb(dbm)3bpy]·C7H8}n(2) and features units repeating in a 1D-zigzag fashion, where the metal is octa-coordinated in a distorted square antiprism geometry. Despite the 1D structure, the absence of paramagnetic connectors prevents the direct magnetic intrachain interaction among the lanthanide ions. In zero magnetic field, only a small fraction of the magnetization of 1 displayed slow dynamics with no dependence on temperature. Upon application of a 1 kOe magnetic field, a relaxation process appears, compatible with a mixed Raman/Direct mechanisms. Magnetic dilution in the diamagnetic Y(III)-based analogue revealed that actually two distinct relaxation processes are active for 1, whose temperature dependence can be interpreted again with a mixed Raman/Direct relaxation model. Compound 2 displayed only in-field slow relaxation, compatible with the models employed for 1.

Electronic structure and magnetic properties of the Mg-rich intermetallic NdNiMg5 by hybrid density functional theory

Mg-rich intermetallic NdNiMg5 in orthorhombic phase with space group Cmcm (No. 63) has been studied theoretically using hybrid functional (HF–B3PW91) within the frame work of density functional theory (DFT). The calculated structural parameters and geometries are found in good agreement with the experiments. The electronic properties of the material reveal the metallic nature. Nd 4f-states splitting show that A2, y[t1] and z[t1] contributed in the valence band; x[t1], ksi[t2] and eta[t2] in conduction band; where zeta[t1] state completely lay at the Fermi level make the compound metallic. The electrical properties show that the material has significant conductivity above the room temperature. The stable magnetic phase of the compound is optimized which show that the material is stable in G-type antiferromagnetic (AFM) phase and Nd–Ni direct magnetic exchange interactions are involved. The calculated effective magnetic moments of Nd is 3.70 μB per unit cell. The post-DFT calculations also confirm the AFM phase of the compound with Neel temperature (TN) = 25 K and Curie-Weiss constant (θ) = −23 K. Based on the above physical properties it is expected that this intermetallic could be used in spin valve and magnetic memory devices.

Ferromagnetism triggered by nitrogen defects in graphitic carbon nitride

It remains a challenge to induce robust long-range ferromagnetism in graphene. Doping nitrogen in high concentration is considered as a potential approach. In this paper, three new graphitic carbon nitride structures with energetic stability in chemical formulae of C10N6, C9N7 and C7N9 are proposed and investigated by first-principles calculation. Both C10N6 and C9N7 are half-metals, and C7N9 is a spin-polarized metal. The itinerant p electrons occupy the spin-polarized narrow bands near the Fermi level, which induces Stoner ferromagnetism in the C10N6 and C9N7. The direct exchange between the delocalized magnetic moment of the itinerant π electrons is responsible for the ferromagnetism in the C7N9. The magnetic moment is determined by both spin-polarized electronic structures and long-range magnetic interaction. Intriguingly, besides the magnetic interactions between the itinerant π electrons, we also find direct magnetic interaction between localized in-plane unpaired electrons. Our results will assist in understanding ferromagnetism and motivate new experiments to produce robust magnetism in graphene-like materials following the proposed synthesis strategy.

Magnetic Heterostructures: Interface Control to Optimize Magnetic Property and Multifunctionality.

Generally, magnetic heterostructures are obtained by the growth of another component on the surface of seed nanoparticles. The direct electrical and magnetic interactions between the solid-state interfaces would endow the heterostructures with properties beyond the individual components. We have devoted the past few years to magnetic-optical, magnetic-catalytic, and exchange-coupled heterostructures, where the interface effects regulate and optimize the optical, catalytic, and magnetic properties, respectively. In this Spotlight on Applications, we describe our recent progress on magnetic heterostructures. Upon the understanding on the interface control, we then discuss our recent efforts to synthesize core-shell, dimer, and nanocomposite structures, while the regulation of their magnetic, optical, and catalytic properties is addressed in turn. Finally, we give the perspectives of magnetic heterostructures.

Jahn-Teller and geometric frustration effects on the structural and magnetic ground states of substituted spinels (Ni,A)Cr2O4 (A = Mn/Cu)

Comparative study of the effects of substitution (25%) of Jahn-Teller (JT) active Cu2+ and non JT active Mn2+ cations, at the Ni2+ site, on the geometric frustration (GF) and cooperative JT distortion (CJTD) in multiferroic NiCr2O4 has been carried out with the help of low-temperature magnetization, x-ray diffraction and time of flight (TOF) neutron powder diffraction (NPD) measurements. On Mn2+ substitution the CJTD, which causes elongation of the NiO4 tetrahedra in I41/amd phase of NiCr2O4, gets suppressed at room-temperature (RT) and stabilizes the Fd-3m phase in (Ni0.75Mn0.25)Cr2O4. On the contrary the Cu2+ substitution inverts the effect of CJTD and the tetrahedra get flattened at RT, which in turn oppositely distorts the I41/amd lattice in Ni0.75Cu0.25Cr2O4. The frustration index decreases on substitution. Intriguingly, the tetragonal to orthorhombic phase transition and the antiferromagnetic ordering, which are clearly evident in the pristine NiCr2O4 and the Cu2+ substituted sample respectively at 30 K and 70 K, have not been observed for the Mn2+ substituted sample. This has been attributed to the change in Cr3+- Cr3+ direct magnetic-interaction on structural transition. However, the long-range ferrimagnetic order remains intact for all the three compositions i.e. NiCr2O4, Ni0.75Mn0.25Cr2O4 and Ni0.75Cu0.25Cr2O4 occurring at 75 K, 70 K and 95 K, respectively. The Mn2+ substituted compound shows short-range magnetic correlation at low-temperatures, as evident from the diffuse and broad hump in the intensity-vs-d spacing plot of TOF NPD data. This short-range magnetic order has been attributed to the known spiral magnetic order.

Magnetic and Electronic Properties of π-d Interacting Molecular Magnetic Superconductor κ-(BETS)2FeX4 (X = Cl, Br) Studied by Angle-Resolved Heat Capacity Measurements

Thermodynamic picture induced by π-d interaction in a molecular magnetic superconductor κ-(BETS)2FeX4 (X = Cl, Br), where BETS is bis(ethylenedithio)tetraselenafulvalene, studied by single crystal calorimetry is reviewed. Although the S = 5/2 spins of Fe3+ in the anion layers form a three-dimensional long-range ordering with nearly full entropy of Rln6, a broad hump structure appears in the temperature dependence of the magnetic heat capacity only when the magnetic field is applied parallel to the a axis, which is considered as the magnetic easy axis. The scaling of the temperature dependence of the magnetic heat capacity of the two salts is possible using the parameter of |Jdd|/kB and therefore the origin of the hump structure is related to the direct magnetic interaction, Jdd, that is dominant in the system. Quite unusual crossover from a three-dimensional ordering to a one-dimensional magnet occurs when magnetic fields are applied parallel to the a axis. A notable anisotropic field-direction dependence against the in-plane magnetic field was also observed in the transition temperature of the bulk superconductivity by the angle-resolved heat capacity measurements. We discuss the origin of this in-plane anisotropy in terms of the 3d electron spin configuration change induced by magnetic fields.

The demagnetization factor for randomly packed spheroidal particles

We investigate if the demagnetization factor for a randomly packed powder of magnetic spheroidal particles depend on the shape of the spheroidal particles and what the internal variation in magnetization is within such a powder. A spheroid is an ellipsoid of revolution, i.e. an ellipsoid with two semi-major axis being equal. The demagnetization factor is calculated as function of particle aspect ratio using two independent numerical models for several different packings, and assuming a relative permeability of 2. The calculated demagnetization factor is shown to depend on particle aspect ratio, not because of direct magnetic interaction but because the particle packing depend on the aspect ratio of the particles. The relative standard deviation of the magnetization across the powder was 3\%-8\%, increasing as the particle shape deviates from spherical, while the relative standard deviation within each particle was relatively constant around 5\%.

Separation of two attractive ferromagnetic ellipsoidal particles by hydrodynamic interactions under alternating magnetic field.

In applications where magnetic particles are used to detect and dose targeted molecules, it is of major importance to prevent particle clustering and aggregation during the capture stage in order to maximize the capture rate. Elongated ferromagnetic particles can be more interesting than spherical ones due to their large magnetic moment, which facilitates their separation by magnets or the detection by optical measurement of their orientation relaxation time. Under alternating magnetic field, the rotational dynamics of elongated ferromagnetic particles results from the balance between magnetic torque that tends to align the particle axis with the field direction and viscous torque. As for their translational motion, it results from a competition between direct magnetic particle-particle interactions and solvent-flow-mediated hydrodynamic interactions. Due to particle anisotropy, this may lead to intricate translation-rotation couplings. Using numerical simulations and theoretical modeling of the system, we show that two ellipsoidal magnetic particles, initially in a head-to-tail attractive configuration resulting from their remnant magnetization, can repel each other due to hydrodynamic interactions when alternating field is operated. The separation takes place in a range of low frequencies f_{c1}<f<f_{c2}. The upper frequency limit f_{c2}τ_{r}≈0.04 (where τ_{r} is the rotation time scale) depends weakly on the ratio of magnetic field to particle magnetization strength, whereas f_{c1} tends to zero when this ratio increases.

Disappearance of a coronal hole induced by a filament activation

We present a rare observation of direct magnetic interaction between an activating filament and a coronal hole (CH). The filament was a quiescent one located at the northwest of the CH. It underwent a nonradial activation, during which filament material constantly fell and intruded into the CH. As a result, the CH was clearly destroyed by the intrusion. Brightenings appeared at the boundaries and in the interior of the CH, meanwhile, its west boundaries began to retreat and the area gradually shrank. It is noted that the CH went on shrinking after the end of the intrusion and finally disappeared entirely. Following the filament activation, three coronal dimmings (D1–D3) were formed, among which D1 and D2 persisted throughout the complete disappearance of the CH. The derived coronal magnetic configuration shows that the filament was located below an extended loop system, which obviously linked D1 to D2. By extrapolating this result, our observations imply that the interaction between the filament and the CH involved direct intrusion of the filament material to the CH and the disappearance of the CH might be due to interchange reconnection between the expanding loop system and the CH's open field.

The affinity of magnetic microspheres for Schistosoma eggs

Schistosomiasis is a chronic parasitic disease of humans, with two species primarily causing the intestinal infection: Schistosoma mansoni and Schistosoma japonicum. Traditionally, diagnosis of schistosomiasis is achieved through direct visualisation of eggs in faeces using techniques that lack the sensitivity required to detect all infections, especially in areas of low endemicity. A recently developed method termed Helmintex™ is a very sensitive technique for detection of Schistosoma eggs and exhibits 100% sensitivity at 1.3 eggs per gram of faeces, enough to detect even low-level infections. The Helminthex™ method is based on the interaction of magnetic microspheres and schistosome eggs. Further understanding the underlying egg-microsphere interactions would enable a targeted optimisation of egg-particle binding and may thus enable a significant improvement of the Helmintex™ method and diagnostic sensitivity in areas with low infection rates. We investigated the magnetic properties of S. mansoni and S. japonicum eggs and their interactions with microspheres with different magnetic properties and surface functionalization. Eggs of both species exhibited higher binding affinity to the magnetic microspheres than the non-magnetic microspheres. Binding efficiency was further enhanced if the particles were coated with streptavidin. Schistosoma japonicum eggs bound more microspheres compared with S. mansoni. However, distinct differences within eggs of each species were also observed when the distribution of the number of microspheres bound per egg was modelled with double Poisson distributions. Using this approach, both S. japonicum and S. mansoni eggs fell into two groups, one having greater affinity for magnetic microspheres than the other, indicating that not all eggs of a species exhibit the same binding affinity. Our observations suggest that interaction between the microspheres and eggs is more likely to be related to surface charge-based electrostatic interactions between eggs and magnetic iron oxide rather than through a direct magnetic interaction.

Synthesis of a new donor, MOET‐TTP, and the crystal structure, electrical, and magnetic properties of (MOET‐TTP)2MCl4 (M = Fe and Ga)

AbstractA new 2,5‐bis(1,3‐dithiol‐2‐ylidene)‐1,3,4,6‐tetrathiapentalene (BDT‐TTP) type donor, 2‐(4,5‐dimethoxy‐1,3‐dithiol‐2‐ylidene)‐5‐(4,5‐ethylenedithio‐1,3‐dithiol‐2‐ylidene)‐1,3,4,6‐tetrathiapentalene (MOET‐TTP) was synthesized and its magnetic and non‐magnetic anion salts (MOET‐TTP)2MCl4 (M = Fe and Ga), were prepared. These salts are isostructural and belong to the space group of P1. They show metal‐like behavior down to 200 K for the FeCl4 salt and 20 K for the GaCl4 salt. The band structures of these salts are two‐dimensional. The MCl4 anions are located between the donor columns and close to the ethylenedithio and methoxy groups of the donor molecules. The magnetic susceptibilities of the FeCl4 salts follow the Curie–Weiss law with Curie constant of 4.3 emu K mol−1 and Weiss temperature of θ = −1.8 K, revealing a weak antiferromagnetic interaction of 3d spins of the FeCl4 anions. The ${\rm Fe}\cdots {\rm Fe}$ (6.508(3) Å) and ${\rm Cl}\cdots {\rm Cl}$ (3.78–4.69 Å) distances in the crystal structure of the salt are significantly long. Therefore, the direct magnetic interaction between the 3d spins of the nearest neighboring Fe3+ ions does not seem readily accessible.

Increased deposition of polychlorinated biphenyls (PCBs) under an AC high-voltage power line

There is considerable public concern regarding the potential risks to health of electromagnetic fields in general and high-voltage power lines in particular. As epidemiological findings are not supported by a clearly defined mechanism of direct magnetic field interactions with the human body, potential indirect effects are of interest. It has been suggested that an increased exposure to chemical pollutants could occur near high-voltage power lines due to formation and deposition of charged aerosols. The current study reports empirical evidence that seems to support this hypothesis. The deposition of 18 congeners of polychlorinated biphenyls (PCBs) was studied by collecting samples of pine needles under a 400 kV AC power line and at reference sites in the vicinity. Compared to the reference sites, the average deposition of PCB congeners under the power line was almost double. This difference between the two groups of samples was statistically significant. While it is premature to draw any conclusions regarding the human exposure near high-voltage power lines, the issue deserves attention and further investigations.

Magnetic Interaction: A Transequatorial Jet and Interconnecting Loops

We present, to our knowledge for the first time, a rare observation of direct magnetic interaction between a transequatorial jet and interconnecting loops (IL) in the southern hemisphere. The jet originated from a flare and appeared to move outward along open field lines, but it passed so close to the IL that its edge met with one of the IL ends. As a result, the IL began to erupt, weak brightenings appeared at the meeting site, and a nearby dark feature was disturbed. After the eruption, in addition to a looplike dimming due to the disappearance of the IL, a dimming region was formed around its another end, which was very probably caused by the expansion or opening of its field lines and represented its evacuated feet. Two coronal mass ejections (CMEs) were observed within 2 hr in association with the event. One was related to the flare and the jet, while the other was due to the IL eruption. These observations suggest that a sole flare can not only trigger a CME but also simultaneously trigger an IL eruption by means of its interaction with a jet, so can lead to two interdependent CMEs, i. e., a sympathetic CME pair physically connected by the jet/IL interaction.