High-field magnetization and electronic spin resonance study in the twisted honeycomb latticeα-Mn2V2O7.

We report the single-crystal growth of Mn2V2O7and the results of magnetic susceptibility, high-field magnetization up to 55 T and high-frequency electric spin resonance (ESR) measurements for its low-temperatureαphase. Two antiferromagnetic (AFM) ordering at 17.5 K and 3 K and obvious magnetic anisotropy are observed inα-Mn2V2O7upon cooling. In pulsed high magnetic fields, the compound reaches the saturation magnetic moment of ∼10.5µBfor each molecular formula at around 45 T after two undergoing AFM phase transitions atHc1≈ 16 T,Hc2≈ 34.5 T forH//[11-0] andHsf1= 2.5 T,Hsf2= 7 T forH//[001]. In these two directions, two and seven resonance modes are detected by ESR spectroscopy, respectively. Theω1andω2modes ofH//[11-0] can be well described by two-sublattice AFM resonance mode with two zero-field gaps at 94.51 GHz and 169.28 GHz, indicating a hard-axis feature. The seven modes forH//[001] are partially separated by the critical fields ofHsf1andHsf2, displaying the two signs of spin-flop transition. The fittings ofωc1andωc2modes yield zero-field gaps at 69.50 GHz and 84.73 GHz forH//[001], confirming the axis-type anisotropy. The saturated moment and gyromagnetic ratio indicate the Mn2+ion inα-Mn2V2O7is in a high spin state with orbital moment completely quenched. A quasi-one-dimensional magnetism with a zig-zag-chain spin configuration is suggested inα-Mn2V2O7, due to the special neighbor interactions caused by a distorted network structure with honeycomb layer.

Angular dependence of spin-flop transition in triangular lattice antiferromagnet Cu2(OH)3Br.

We report angular dependence of spin-flop transition in triangular lattice antiferromagnet Cu2(OH)3Br by angle-dependent magnetization and ESR measurements. The results show that the antiferromagnetic easy magnetization axis is the diagonal direction (θ= 45°) of theac*plane, i.e., the orientation of Cu1 spins based on the magnetic structure (2020Phys. Rev. Lett.125037204), whereas the spin-flop axis is thebaxis. A phenomenological model is proposed to describe the angle-dependent spin-flop transitions. Based on this model, Cu1 spins are sensitive to external magnetic field, while Cu2 spins are robust against to the field, showing partial decoupling. The model is expected to be used in other uniaxial antiferromagnets with a more general easy axis and complex spin-flop transitions.

Field-induced magnetic transitions and strong anisotropy in α-CoV2O6 single crystal.

The Ising-like antiferromagnet α-CoV2O6 has received considerable interests because of stabilized 1/3 magnetization plateau around 5 K under magnetic field applied along magnetic easy c-axis. In this work, this magnetization plateau was studied by varying temperature or rotating magnetic field. As temperature decreased, this stabilized plateau collapsed, and additional magnetic transitions were observed. As a result, a rich magnetic phase diagram was constructed and extended to temperature lower than previously reported. When magnetic field moved from the c to b (or a) axis, the magnetization plateau developed with field directions and vanished finally when the field was restricted in the ab plane. An impressive observation is that this 1/3-plateau can be stabilized and remain robust even when magnetic field deviated from the c axis, accompanied by the evolutions of the magnetic moments and the critical transition fields. We suppose that the origins of these temperature and angular dependences of the 1/3 magnetization plateau are related to strong spin-orbital coupling. Indeed, electron spin resonance (ESR) measurement gives large Landé factor of 8.9, evidencing that there exists strong spin-orbital coupling.

Size reduction-induced chain breaking in Haldane-chain compounds SrNi2-x Mg x V2O8 (x = 0 and 0.1).

We report size reduction-induced chain breaking in the spin-1 Haldane-chain SrNi2-x Mg x V2O8 (x = 0 and 0.1) by magnetization and electron spin resonance measurements. For x = 0.0, the magnetic susceptibility of all samples can be well described by a temperature-independent term, a Curie-Weiss term and a Haldane-gap term. This implies that a reduced sample grain size breaks the long chain and creates a considerable number of S = 1/2 edge spins, resulting in the enhancement of magnetization and the decrease of Haldane gap in the samples. These edge spins as well as the other paramagnetic ions at grain boundary and surface might be weakly coupled with each other. For the Mg-doped sample with x = 0.1, there are more S = 1/2 spins creased in relative to x = 0.0 because of a combined effect of lattice defects, Mg-doping and reduced size. In addition, the antiferromagnetic resonance of x = 0.1 is also presented.

3D spin-flop transition in enhanced 2D layered structure single crystalline TlCo2Se2.

The enhanced 2D layered structure single crystalline TlCo2Se2 has been successfully fabricated, which exhibits field-induced 3D spin-flop phase transitions. In the case of the magnetic field parallel to the c-axis (B//c), the applied magnetic field induces the evolution of the noncollinear helical magnetic coupling into a ferromagnetic (FM) state with all the magnetization of the Co ion parallel to the c-axis. A striking variation of the field-induced strain within the ab-plane is noticed in the magnetic field region of 20-30 T. In the case of the magnetic field perpendicular to the c-axis (B ⊥ c), the inter-layer helical antiferromagnetic (AFM) coupling may transform to an initial canted AFM coupling, and then part of it transforms to an intermediate metamagnetic phase with the alignment of two-up-one-down Co magnetic moments and finally to an ultimate FM coupling in higher magnetic fields. The robust noncollinear AFM magnetic coupling is completely destroyed above 30 T. In combination with the measurements of magnetization, magnetoresistance and field-induced strain, a complete magnetic phase diagram of the TlCo2Se2 single crystal has been depicted, demonstrating complex magnetic structures even though the crystal geometry itself gives no indication of the magnetic frustration.

Slow magnetic relaxation in mononuclear seven-coordinate cobalt(II) complexes with easy plane anisotropy.

Two mononuclear seven-coordinate cobalt(II) complexes [Co(L)3(NO3)2] (L = 4-tert-butylpyridine, 1; L = isoquinoline, 2) were prepared and structurally analyzed by single-crystal X-ray crystallography. The coordination spheres of 1 and 2 exhibit distorted pentagonal bipyramid geometry. Analysis of their direct-current magnetic data reveals the existence of easy plane anisotropy (D > 0) with a small transverse anisotropy (E), which was further confirmed by high-field electron paramagnetic resonance (HFEPR) spectroscopy. Field-induced slow magnetic relaxations were observed under the applied dc field in complexes 1 and 2 by alternating-current magnetic susceptibility measurements. Importantly, these complexes are new instances of mononuclear high-coordinate cobalt(II)-based single-molecule magnets.

Disappearance of Ising nature in Ca3ZnMnO6 studied by high-field ESR.

High-field electron spin resonance measurements of an antiferromagnet Ca3ZnMnO6 isostructure, with the Ising-chain multiferroic Ca3CoMnO6, have been carried out. Two distinct resonance modes were observed below TN = 25 K, which is well explained by conventional antiferromagnetic resonance theory with easy-plane anisotropy. The zero-field spin gap is derived to be about 166 GHz, originating from the easy-plane anisotropy and exchange interaction. Our result suggests that the Dzyaloshinsky-Moriya interaction, which may induce spin canting, is absent. Disappearance of Ising anisotropy in Ca3ZnMnO6 suggests that the Co(4+) ion, as well as the Co-Mn superexchange, plays an important role for the Ising nature in Ca3CoMnO6.

Field-induced slow relaxation of magnetization in a tetrahedral Co(II) complex with easy plane anisotropy.

The mononuclear Co(II) complex CoBr (dmph = 2,9-dimethyl-1,10-phenanthroline) was obtained and X-ray structurally characterized as a distorted tetrahedron environment that is responsible for the moderately strong positive anisotropy of high spin Co(II). In combination with variable-field magnetic susceptibility data at low temperature, high-field electron paramagnetic resonance (HF-EPR) spectroscopy reveals the presence of easy-plane anisotropy (D > 0) in complex CoBr. Slow magnetic relaxation effects were observed for CoBr in the presence of a dc magnetic field. At very low temperatures, ac magnetic susceptibility data show the magnetic relaxation time, τ, to be temperature-independent, while above 2.4 K thermally activated Arrhenius behavior is dominated with Ueff = 22.8(8) cm(-1) and τ0 = 3.7(5) × 10(-10) s. Upon dilution of the complex within a matrix of the isomorphous compound ZnBr, ac susceptibility data reveal the individual molecular nature of the slow magnetic relaxation and indicate that the quantum tunneling pathway observed at low temperatures is likely mediated by intermolecular dipolar interactions.

Tuning transverse anisotropy in Co(III)-Co(II)-Co(III) mixed-valence complex toward slow magnetic relaxation.

Two cobalt mixed-valence complexes with different substituents have been prepared and structurally characterized by single-crystal X-ray diffraction to alter slow magnetic relaxation by tailoring the transverse anisotropy. The trinuclear complexes [(L(1))4Co3(H2O)2](NO3)4·CH3OH·5H2O (1-NO3) and [(L(2))4Co3(H2O)2](NO3)4·6H2O (2-NO3) feature a distorted octahedral Co(II) strongly hindered in a trinuclear Co(III)-Co(II)-Co(III) mixed-valence array. Detailed magnetic studies of 1-NO3 and 2-NO3 have been conducted using direct- and alternating-current magnetic susceptibility data. In accordance with variable-field magnetic susceptibility data at low temperatures, high-field electron paramagnetic resonance (HF-EPR) spectroscopy reveals the presence of an easy-plane anisotropy (D > 0) with a significant transverse component, E, in complexes 1-NO3 and 2-NO3. These findings indicate that the onset of the variation of distortion within complex 2-NO3 leads to a suppression of quantum tunneling of the magnetization within the easy plane, resulting in magnetic bistability and slow relaxation behavior. Consequently, the anisotropy energy scale associated with the relaxation barrier, 5.46 cm(-1) (τo = 1.03 × 10(-5) s), is determined by the transverse E term. The results demonstrate that slow magnetic relaxation can be switched through optimization of the transverse anisotropy associated with magnetic ions that possess easy-plane anisotropy.

X-ray magnetic circular dichroism of a valence fluctuating state in eu at high magnetic fields.

X-ray magnetic circular dichroism (XMCD) at the Eu L edge in two compounds exhibiting valence fluctuation, namely EuNi_{2}(Si_{0.18}Ge_{0.82})_{2} and EuNi_{2}P_{2}, has been investigated at high magnetic fields of up to 40 T. A distinct XMCD peak corresponding to the trivalent state (Eu(3+)), whose ground state is nonmagnetic (J = 0), was observed in addition to the main XMCD peak corresponding to the magnetic (J = 7/2) divalent state (Eu(2+)). This result indicates that the 5d electrons belonging to both valence states are magnetically polarized. It was also found that the ratio P_{5d}(3+)/P_{5d}(2+) between the polarization of 5d electrons (P_{5d}) in the Eu(3+) state and that of Eu(2+) depends on the material. The possible origin of the XMCD and an explanation of the material dependence of P_{5d}(3+)/P_{5d}(2+) are discussed in terms of hybridization between the conduction electrons and the f electrons.

Insulator-metal phase transition of Pr(0.6)Ca(0.4)MnO(3) studied by x-ray absorption spectroscopy in pulsed magnetic fields.

Evolution of the Mn K-edge x-ray absorption near edge structure (XANES) in Pr(0.6)Ca(0.4)MnO(3) at pulsed magnetic fields has been investigated. A small enhancement of XANES spectra is detected across the magnetic-field-induced transition from the charge- and orbital-ordered (COO) insulator to ferromagnetic metal at 20 K. It is found that the magnetic-field dependence of the enhancement shows clear hysteresis, as seen in the magnetization with metamagnetic transition, suggesting a significant correlation between the change in the XANES and the field-induced collapse of the COO state. The enhancement of the absorption can be explained by an increase of the 4p density of states due to a reduction of hybridization between the 4p state of the central Mn ion with the core hole and the neighboring Mn 3d state. Local structural change around Mn ions is expected to modify the strength of the hybridization.