Spin autocorrelation of Ni in K2Mn0.975Ni0.025F4 studied by nuclear spin-lattice relaxation

From the nuclear spin-lattice relaxation of the out-of-layer ¹⁹F nuclei in magnetic fields perpendicular to the c-axis the low-frequency component of the autocorrelation function 〈S^z(t)S^z(O)〉 of Ni in ordered K₂Mn_0.975Ni_0.025F₄ is found to be substantially reduced relative to the Mn host. The experimental rates vs temperature are in accord with those for relaxation involving two spin excitations calculated with local Green's functions.     

Fe2+ localized excitations in the random antiferromagnet with competing spin anisotropies, Fe(1−x)CoxBr2

The Fe²⁺ localized magnetic excitations observed in the Co-rich antiferromagnetic phase of the randomly mixed system with competing Ising and XY spin anisotropies, Fe(_1?x)Co_xBr₂ have been analyzed quantitatively. The calculated frequency-field diagram reproduces well the experiments. The expectation values of the Fe²⁺ spin components in the ground state are calculated. It is shown that even in the Co-rich antiferromagnetic phase Fe²⁺ spins make an angle with the c-plane of the crystal in which Co²⁺ spins are confined.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Structural, thermal and magnetic properties of Ni1−xMnxFe2O4 nanoferrites

In this paper, the structural, thermal and magnetic properties of Ni_1−xMn_xFe₂O₄ are presented. It is observed that high concentration of Mn²⁺ ions into NiFe₂O₄ tends to reduce the particle size. Calcination at 500 °C has resulted in the growth of Ni_1−xMn_xFe₂O₄ nanoparticles, but the calcination at 900 °C has led to the evaporation of the majorities of the polyvinyl alcohol. After calcination at 900 °C, crystallographically oriented NiMnFe₂O₄ nanoparticles are formed. These Ni_1−xMn_xFe₂O₄ nanoparticles show hysteresis behaviour upon magnetization. On the other hand, saturation magnetization (Ms) values decreases with increasing Mn content in ferrite due to the influence of Mn²⁺ ion in the sub lattice.     

Neutron scattering study of two-dimensional Ising nature of K2CoF4

By neutron elastic and quasi-elastic scattering from K₂CoF₄, sublattice magnetization and spin correlations are examined quantitatively. The obtained critical exponents β, ν, γ, and η coincide precisely with those from Onsager's exact solution for the two-dimensional Ising model.     

Magnetic study 2D-antiferromagnets Ba2NiF6 and Ba2FeF6 by neutron diffraction and mossbauer spectroscopy

The 2D-antiferromagnetism of tetragonal Ba₂NiF₆ and Ba₂FeF6 — whose structure derives from that of K₂NiF₄ — has been studied by magnetization measurements and by powder neutron diffraction. The magnetic cell is 2a, 2$\text{a}$,$\text{c}$ and the magnetic moments (μ_Ni²⁺ = 1.9μB and μ_Fe²⁺ = 3.46μB) lie along c. This has been confirmed by Mossbauer spectroscopy for Ba₂FeF₆.     

Magnetic properties of the compounds N(CH3)4MnIIMIII(CN)6 ·8 H2O(MIII = Mn,Fe)

In the isostructural cyanobridged chain compounds N(CH₃)₄Mn^IIM^III(CN)₆ · 8H₂O high spin Mn(II) ions couple antiferromagnetically to low spin Mn(III) of Fe(III) ions. The Mn^II–Mn^III compound orders ferrimagnetically below T_N = 28.5 ± 1 K. The tetragonal a and b axes are easy ones for the magnetic moments. In the Mn^II–Fe^III compound antiferromagnetic order occurs below T_N = 9.3 K, with spins aligned along the tetragonal c axis. The compound undergoes a meta-magnetic transition from the antiferromagnetic to a ferrimagnetic phase. This occurs at 2 K for a field H_crit ≈ 1.2 T. The temperature dependence of H_crit, which vanishes at T_N, is followed. The tricritical temperature T¹ is ～ 5 K.     

Spectroscopic properties of Fe ions at tetragonal sites—Crystal field effects and microscopic modeling of spin Hamiltonian parameters for Fe (S=2) ions in K2FeF4 and K2ZnF4

Magnetic and spectroscopic properties of the planar antiferromagnet K₂FeF₄ are determined by the Fe²⁺ ions at tetragonal sites. The two-dimensional easy-plane anisotropy exhibited by K₂FeF₄ is due to the zero field splitting (ZFS) terms arising from the orbital singlet ground state of Fe²⁺ ions with the spin S=2. To provide insight into the single-ion magnetic anisotropy of K₂FeF₄, the crystal field theory and the microscopic spin Hamiltonian (MSH) approach based on the tensor method is adopted. Survey of available experimental data on the crystal field energy levels and free-ion parameters for Fe²⁺ ions in K₂FeF₄ and related compounds is carried out to provide input for microscopic modeling of the ZFS parameters and the Zeeman electronic ones. The ZFS parameters are expressed in the extended Stevens notation and include contributions up to the fourth-order using as perturbation the spin-orbit and electronic spin-spin couplings within the tetragonal crystal field states of the ground ⁵D multiplet. Modeling of the ZFS parameters and the Zeeman electronic ones is carried out. Variation of these parameters is studied taking into account reasonable ranges of the microscopic ones, i.e. the spin-orbit and spin-spin coupling constants, and the energy level splittings, suitable for Fe²⁺ ions in K₂FeF₄ and Fe²⁺:K₂ZnF₄. Conversions between the ZFS parameters in the extended Stevens notation and the conventional ones are considered to enable comparison with the data of others. Comparative analysis of the MSH formulas derived earlier and our more complete ones indicates the importance of terms omitted earlier as well as the fourth-order ZFS parameters and the spin-spin coupling related contributions. The results may be useful also for Fe²⁺ ions at axial symmetry sites in related systems, i.e. Fe:K₂MnF₄, Rb₂Co_1−xFe_xF₄, Fe²⁺:Rb₂CrCl₄, and Fe²⁺:Rb₂ZnCl₄.     

Structure and magnetic properties of a new single-molecule magnet [Mn11Fe1O12 (CH3COO)16(H2O)4].2CH3COOH.4H2O

A new single-molecule magnet [Mn₁₁Fe₁O₁₂ (CH₃COO)₁₆(H₂O)₄]?2CH₃COOH?4H₂O (Mn₁₁Fe₁) has been synthesized.The structure has been studied by the single crystal x-ray diffraction. The difference of Jahn--Teller distortion between Fe³⁺ and Mn³⁺ ion reveals that Fe³⁺ ion substitutes for Mn³⁺ ion on the Mn(3) sites in the Mn₁₂ skeleton. The temperature dependence of the magnetization gives a blocking temperature T_B=1.9K for Mn₁₁Fe₁. Based on the magnetization process analysis of the crystal at T=2K, we suggest that Mn₁₁Fe₁ has the ground state with a total spin S= 11/2.     

Magnon modes and impurity spin resonance in FeBr2 doped with 1% Mn2+

We report results of far infrared magneto-absorption experiments in FeBr₂ doped with 1% MnBr₂. Using radiations from several carcinotrons covering the frequency range 77–600 GHz, we observe both the spectra corresponding to the localized Mn²⁺ impurity modes and the uniform magnon modes of the host crystal. The excitation energy gap of the A.F. magnons at zero field is E_o = 500 ± 2 GHz.     

Characterization of the 2D antiferromagnets Rb2MnCl4 and Rb3Mn2Cl7 : Optical,Raman and magnetic circular dichroism studies

Below T_N, the site symmetry at the Mn²⁺ ion is centrosymmetric (Rb₂MnCl₄) and non-centrosymmetric (Rb₃Mn₂Cl₇) respectively. As a result, one expects the appearance of magnetic dipole or electric dipole exciton origins in the optical spectra. These were clearly seen via polarized absorption and magnetic circular dichroism measurements through the 4T₂(D) band. The zone edge magnon frequencies are found to be 80 cm^?1 (Rb₂MnCl₄) and 90 cm^?1 (Rb₃MnCl₂in7). The two compounds are also easily distinguished through their room temperature axial absorption (⁴T₂ (G) band) and Raman spectra. Low temperature data indicate that the tetragonal field plays an important role.     

EPR investigation on exchange coupled Mn2+ pairs in (CH3)4NCdCl3

EPR experiments were performed at Q-band and 300 K on Mn²⁺ doped (CH₃)₄NCdCl₃. Beside the single ion resonance many weak lines could be observed which can be attributed to nearest neighbour pairs of Mn²⁺ lying along the crystallographic c-axis. The spectra can be described using a Hamiltonian for strongly exchange coupled pairs. The obtained data show that the ionic separation varies in the different spin states. So an additional interaction occurs on the Mn²⁺ dimer, which can be interpreted as an exchange striction effect.     

Magnetic excitations in the two dimensional planar antiferromagnets K2FeF4 and Rb2FeF4

The magnetic excitation spectrum of K₂FeF₄ and Rb₂FeF₄, two K₂NiF₄-structure planar antiferromagnets with rather large anisotropy and spins perpendicular to the c-axis, has been measured by Raman and FIR-spectroscopy. One of the two predicted one-magnon transitions and the two-magnon mode have been observed in K₂FeF₄ (Rb₂FeF₄) at 48.5 cm^-1 (37.6 cm^-1) and 182.0 cm^-1 (160.5 cm^-1) respectively. The magnetic field and temperature dependence of the spectra are reported too. The data are discussed on the basis of an easy plane spin model Hamiltonian. In K₂FeF₄: Mn²⁺ a low lying magnetic impurity mode is observed at 40.5 cm^-1.     

Synthesis and magnetic properties of InM2+CrS4(M2+ = Mn,Fe,Co, Ni)

The crystallographic and magnetic properties of the compounds InM²⁺CrS₄(M = Mn, Fe, Co, Ni) were studied. Three of these compounds except MnInCrS₄ were antiferromagnetic. The Néel termperature and paramagnetic Curie temperature were determined to be 20 and 82K for InFeCrS₄, 36 and 115K for InCoCrS₄ and 22 and 26K for InNiCrS₄, respectively.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Magnetization studies of TbFeO3

The spontaneous magnetization and principal magnetic susceptibilities of TbFeO₃ were measured from 4.2 to 300 K. The weak ferromagnetic moment is along the c crystallographic axis in the entire temperature range. The field dependence of the magnetization at 4.2 K was also studied. The magnetic behavior is interpreted in terms of an interaction between the ordered Fe³⁺ spin system and the electrons occupying the lowest lying “accidental” doublet of the Tb³⁺ ions. The FeTb interaction and the Tb³⁺ Van Vl eck susceptibility along the c axis play significant roles in determining the magnetic configuration of the Fe³⁺ spin system. No indication was found that the TbTb interaction plays a significant role in the magnetic behavior of TbFeO₃ at temperature above 4.2 K.     

Electron hopping and optic phonons in Eu3S4

Raman scattering on single crystals of Eu₃S₄ does not show the allowed q=o phonon modes in the cubic phase and exhibits no new modes in the distorted low temperature phase (T<186 K). Above the Curie temperature T_c=3.8 K the scattering is dominated by a spin-disorder induced one-phonon density of states allowing for the observation of the zone boundary phonon breathing mode of the S^2?ions. This mode does not show any anomaly near the charge order -disorder phase transition T_t=186 K. Temperature tunable spin fluctuations associated with the temperature activated Eu²⁺→Eu³⁺ electron hopping are detected in the scattering intensity, superimposed on the usual thermal spin disorder.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Effects of Mn substitution of Co and Fe in spinel CoFe2O4 thin films

Effects of Mn substitution for Co and Fe on the structural and magnetic properties of inverse-spinel CoFe₂O₄ have been investigated. Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ thin films were prepared by a sol–gel method. The observed increase of the lattice constant of Mn_xCo_1−xFe₂O₄ indicates that Mn²⁺ ions substitute the octahedral Co²⁺ sites. Conversion electron Mössbauer spectroscopy data indicate that a fraction of octahedral Co²⁺ ions exchange sites with tetrahedral Fe³⁺ ions through Mn doping. Vibrating-sample magnetometry data exhibit a large increase of saturation magnetization for both Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ films compared to that of the CoFe₂O₄ film. Such enhancement of magnetization can be explained in terms of a breaking of ferrimagnetic order induced by the Co²⁺ migration.     

Mössbauer study of Fe2+ ions in trigonal sites of spinels: GeFe2O4, GeCo2O4, GeNi2O4

We discuss here the results and the interpretation in the crystalline-field approach of some Mössbauer experiments on Fe²⁺ ions in the spinels GeFe₂O₄, GeCo₂O₄ and GeNi₂O₄. Once the sign of the quadrupolar interaction e²qQ has been deduced from a magnetic spectrum, the thermal variation of e²qQ may be used for determining the electronic level scheme of the Fe²⁺ ion (including the energies and wavefunctions of the levels). Then we may predict the form and magnitude of the spin hamiltonian, of the magnetic anisotropy and of the hypefine field tensor. Below T_N the experimental results are expressed in terms of a molecular-field, the eventual variations of which have been studied in magnitude and in orientation; by using the same calculation for the three compounds, we obtained a reasonable agreement between the experimental and calculated values of the hyperfine field at 0°K.