Orbital ordering and magnetic field effect in MnV2O4

We studied the structural properties of an orbital-spin-coupled spinel oxide, MnV2O4, mainly by single-crystal x-ray diffraction measurement. It was found that a structural phase transition from cubic to tetragonal and ferrimagnetic ordering occur at the same temperature (Ts,TN=57 K). The structural phase transition was induced also by magnetic field above Ts. In addition, magnetic-field-induced alignment of tetragonal domains results in large magnetostriction below Ts. We also found that the structural phase transition is caused by the antiferro-type ordering of the V t2g orbitals.     

Non-stoichiometry in MgAl2O4 spinel

Stoichiometric magnesium aluminate spinel, MgAl₂O₄, contains equimolar proportions of Al₂O₃ and MgO. Spinel can, however, exhibit significant deviations from this stoichiometric composition. There is considerable disagreement concerning which species compensate for either excess Al₂O₃ or MgO non-stoichiometry. Here, we use empirical and quantum mechanical (density functional theory) atomistic simulation techniques to investigate the defect chemistry accommodating non-stoichiometry. The incorporation of excess Al₂O₃ was found to be a lower energy process than the solution of excess MgO. Elevated magnesium and aluminium cation vacancy defect concentrations are predicted in Al₂O₃ rich spinels, whilst MgO excess is facilitated by a combination of oxygen vacancy and magnesium interstitial defects.     

尖晶石结构自旋有序CaTi2O4单晶生长和磁化率特性研究

通过助溶剂熔融法并在氩气气氛炉中成功生长出高质量大尺寸的CaTi₂O₄的单晶.X射线衍射实验及能量损失谱EDS证实,制备的CaTi₂O₄单晶晶胞参数a=9.781?,b=9.966?,c=3.148?,所有样品均为单相,且符合化学计量比,样品高纯.通过直流磁化率的测量,首次给出了晶体的Van-Vleck顺磁因子为6.85×10^-5cm³/mol,Cure-Weiss温度为-0.44 K,呈弱反铁磁性.同时,通过单晶各向磁化率的测量,进一步确认了CaTi₂O₄晶体中一维有序Ti-Ti反铁磁dimer链的形成,并明确了其方向. 关键词： 2O₄')" href="#">CaTi₂O₄ 磁化率 各向异性 反铁磁二聚化     

Magnetic ordering in the spin-ice candidate Ho2Ru2O7

Neutron scattering measurements on the spin-ice candidate material Ho2Ru2O7 have revealed two magnetic transitions at T approximately 95 and approximately 1.4 K to long-range ordered states involving the Ru and Ho sublattices, respectively. Between these transitions, the Ho3+ moments form short-ranged ordered spin clusters. The internal field provided by the ordered S=1 Ru4+ moments disrupts the fragile spin-ice state and drives the Ho3+ moments to order. We have directly measured a slight shift in the Ho3+ crystal field levels at 95 K from the Ru ordering.     

Magnetic ordering in Nd2-xCexCuO4-y

The n-type cuprate superconductor and closely related samples of the general form Nd_2−x Ce _x CuO_4−y have been studied with the muon spin relaxation technique. Non-super-conducting samples display antiferromagnetism (AFM) withT _N below 150 K, the value being dependent upon both Ce concentration and oxygen depletion. The results are interpreted in terms of carrier concentration.     

Quasi-one-dimensional magnetism driven by unusual orbital ordering in CuSb2O6

Essentially all undoped cuprates exhibit a quasiplanar, fourfold Cu-O coordination responsible for the magnetically active antibonding 3d(x(2)-y(2)) like state. Here, we present an electronic structure study for CuSb(2)O(6) that reveals, in contrast, a half-filled 3d(3z(2)-r(2)) orbital. This hitherto unobserved ground state originates from a competition of in- and out-of-plaquette orbitals where the strong Coulomb repulsion drives the surprising and unique orbital ordering. This, in turn, gives rise to an unexpected quasi-one-dimensional magnetic behavior. Our results provide a consistent explanation of recent thermodynamical and neutron diffraction measurements.     

Magnetic properties of the mixed spinel NiAlxCrxFe2-2xO4

The crystal structure and magnetic properties of the Al and Cr cosubstituted disordered spinel series NiAl_xCr_xFe_2-2xO₄ are investigated by means of Xray diffraction, magnetization, a.c. susceptibility and Mössbauer effect measurements. The lattice constants are determined and the applicability of Vegard's law has been tested. The variation of the saturation magnetic moment per formula unit measured at 77 K and 300 K with Al–Cr content is satisfactorily explained on the basis of Neel's collinear spin ordering model for =0.1–0.5. The Mössbauer spectra at 300 K have been fitted with two sextets in the ferrimagnetic state corresponding to Fe³⁺ at tetrahedral (A) and octahedral (B) sites for 0.5. Mössbauer results confirm a collinear ferrimagnetic structure for =0.1–0.5. The Curie temperature obtained from a.c. susceptibility decreases nearly linear with increase of Al–Cr concentration from =0.1 to 0.5.     

Spin-glass-like ordering in the spinel ZnFe2O4 ferrite

In the present study, spin-glass-like ordering has been observed in the spinel ZnFe₂O₄ ferrite. Field cooled (FC) and zero-field cooled (ZFC) DC magnetizations display divergence at low temperature, which indicates a frozen state with the freezing temperature of T_f=21 K. Frequency dependence of AC susceptibility measurement was performed on the sample. It shows a peak at around T_f, with the peak position shifting as a function of driving frequency, indicating a spin-glass-like transition of the sample. The sample shows a typical spin-glass behavior with a manifestation of non-equilibrium dynamics of the spin glass, such as aging, rejuvenation and memory effects. These experimental findings indicate that Zn-ferrite exhibits a spin-glass-like phase at low temperature and it is not canted antiferromagnetic.     

Magnetic,transport, thermal properties and orbital state for spinel MnTi2O4

We systematically investigated the various properties of MnTi₂O₄. The compounds are found to be conducted by small polarons with different activation energies across the temperature T₁ and deviate from the Curie–Weiss law for the magnetic susceptibility at T₁. Also at T₁ do the specific heat undergo a crossover. As indicated by the X-ray diffraction peaks, the series of phenomena near the characteristic temperature T₁ are attributed to the happening of the micro-structural distortion, and the distortion implies the short-range orbital ordering state below T₁. This short-range oribtal ordering state is supported by the little upturn of the thermal conductance at T₁. As the temperature decreases, the systems enter a long-ranged collinear ferrimagnetic state at a lower temperature T_N. Moreover, the compounds decreases in thermal-electric power with the decrease of temperature and undergoes a p-type to n-type transition at the temperature T_pn. Through the quantitative theoretical analysis, both the decrease of the thermal power and the p-type to n-type transition are cooperatively induced by spin–orbit (SO) coupling and the Jahn–Teller (JT) effect.     

Magnetic properties of ultra-fine particles of Mn0.5Fe0.5Fe2O4 spinel system

A systematic study of the magnetic properties of ultra-fine particles of Mn_0.5Fe_0.5Fe₂O₄ spinel system has been undertaken. The effect of temperature on the magnetic properties of particles and the ferrofluid has been studied. Analysis of the data yields information on the anisotropy constant, particle size distribution and superparamagnetic behaviour. The results are explained on the basis of existing theories.     

Magnetic properties and antiferromagnetic Cu ordering in Pr2CuO4

Bulk-magnetisation measurements and neutron-scattering experiments were performed both on a polycrystalline sample and on a single-crystal of Pr₂CuO₄ in the temperature range from 1.5 to 300 K. Pr₂CuO₄ crystallizes with theT (Nd₂CuO₄)-type structure. We observed antiferromagnetic ordering of the Cu moments belowT _N =(190±2) K in a single crystal and belowT _N =(250±10)K in powder material. The magnetic unit cell dimensions area _m =2a _o ,c _m =c _o ;the Cu moments are oriented in the basal plane with a magnetic saturation moment of _Cu=(0.45±0.12) _B . Pr³⁺ does not order magnetically above 1.5K due to its crystal-field induced singlet ground state as verified by inelastic neutron scattering.     

A first-principles study on phase transition induced by charge ordering of Mn3+/Mn4+ in spinel LiMn2O4

A first-order transition at 290 K in LiMn₂O₄ with a cubic spinel-type structure is known to degrade the electrochemical performance of the positive electrode of rechargeable lithium-ion batteries. Using first-principles density functional theory (DFT), we confirm that the phase transition is induced by charge-ordering of Mn³⁺/Mn⁴⁺ accompanied by orbital-ordering due to Jahn–Teller distortion, which is in agreement with the previous experimental results of Rodríguez-Carvajal et al. [J. Rodríguez-Carvajal, G. Rousse, C. Masquelier, M. Hervieu, Phys. Rev. Lett. 81 (1998) 4660]. The optimized structure of the low-temperature (LT) phase has orthorhombic symmetry with five distinct crystallographic sites for Mn. The spin integration at each Mn site shows that Mn³⁺ resides at three Mn sites and the remaining two sites are occupied by Mn⁴⁺ ions. Total energy calculations indicate that the LT phase is about 0.23 eV/ LiMn₂O₄ more stable than cubic LiMn₂O₄ (high-temperature phase). The electrochemical Li extraction reaction from the LT phase is also investigated using DFT calculations. The results indicate that the reaction is initially divided into two voltage regions. Electrostatic interactions in the LT phase are calculated using a point charge model, accounting for the features of the electronic configurations and electrochemical reactions.     

Configurational entropy-induced phase transition in spinel LiMn2O4

The spinel-type LiMn$_{2}$O$_{4}$ is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety. Experimentally, it is observed that in this compound there occur the structural phase transitions from cubic ($Fd\bar{3}m)$ to tetragonal ($I4_{1}/{amd}$) phase at slightly below room temperature. To understand the phase transition mechanism, we compare the Gibbs free energy between cubic phase and tetragonal phase by including the configurational entropy. Our results show that the configurational entropy contributes substantially to the stability of the cubic phase at room temperature due to the disordered Mn$^{3+}$/Mn$^{4+}$ distribution as well as the orientation of the Jahn-Teller elongation of the Mn$^{3+}$O$_{6}$ octahedron in the the spinel phase. Meanwhile, the phase transition temperature is predicted to be 267.8 K, which is comparable to the experimentally observed temperature. These results serve as a good complement to the experimental study, and are beneficial to the improving of the electrochemical performance of LiMn$_{2}$O$_{4}$ cathode.     

Successive orbital ordering transitions in NaVO2

Physical property measurements on samples of triangular-lattice NaVO2 reveal two successive orbital ordering transitions. At 300 K, the structure is rhombohedral. At 98 K, the system undergoes a second-order transition to a monoclinic phase in which the in-plane V-V distances separate into four short and two long bonds, corresponding to orbital ordering of one electron per V3+. Below 93 K, there is a first-order transition to a second monoclinic phase with four long and two short V-V bonds, consistent with orbital ordering of two electrons per V3+. Long range magnetic ordering of 0.98(2)mu_(B) per V3+ (3d(2)) sets in at the 93 K structural transition. The orbital ordering relieves the geometric frustration and leads to a magnetically ordered ground state.     

Magnetic-field switching of crystal structure in an orbital-spin-coupled system: MnV2O4

We studied the magnetic and structural properties of spinel MnV2O4, which has S=5/2 spin with no orbital degrees of freedom on the Mn2+ site and S=1 spin and three orbital degrees of freedom on the V3+ site. We found that the ferrimagnetic ordering at TN=56.5K and the structural phase transition at Ts=53.5K are closely correlated in this compound and found a switching of crystal structure between cubic and tetragonal phases by the magnetic field. This phenomenon can be explained by the coupling between orbital and spin degrees of freedom in the t2g states of the V site.