The effect of misalignment on the spin-flop transition in K2FeF5

Spin-flop transitions in K₂FeF₅ subject to an applied field (i) parallel to the easy axis, and (ii) directed at 33° to the easy axis are found to be (i) abrupt and (ii) smooth, in accordance with theoretical predictions.     

Mössbauer study of ultrafine FeF2 particles

Ultrafine antiferromagnetic FeF₂ particles (<10 nm) were prepared by a new technique, viz, the SF₆-sensitized infrared photodecomposition of Fe(CO)₅ induced by a transversely excited atmospheric (TEA) CO₂ laser. The magnetic properties have been examined by⁵⁷Fe Mössbauer spectroscopy. At low temperatures the magnetic hyperfine field decreases faster with increasing temperature than the hyperfine field of the bulk; this behavior appears to be consistent with collective magnetic excitations. The transition between the paramagnetic and antiferromagnetic states takes place at a higher temperature and over a broader range as compared to the bulk. FeF₂ ultrafine particles are relatively sensitive to oxidation; cubic-type iron oxide is formed.     

Impurity thermodynamics of a Heisenberg antiferromagnet - Mn:FeF2

The temperature dependence of the ⁵⁵Mn and ¹⁹F NMR in antiferromagnetic FeF₂ with 1% Mn impurities was used to determine the magnetizations σ_i, σ_nn and σ_nnn vs. T for the impurity and neighboring Fe ions. σ_i vs. T was found to be well described by an effective field theory in agreement with the thermodynamic Greens' function prediction for an impurity mode below the host-magnon band. The magnitude of the FeMn nnn exchange interaction J′₂ in Fe:MnF₂ and Mn:FeF₂ differ slightly from each other but the nn interaction J′₁ changes sign.     

Free electron laser-far infrared study of FeF2:Mn

The first use of a free electron laser (FEL) for condensed matter research was made on FeF₂:Mn with the far infrared radiation from the UCSB FEL. The versatility of the FEL for linear and nonequilibrium spectroscopy is demonstrated in studies of the host and impurity modes.     

Giant enhancement of the Raman scattering by local magnon modes in FeF2:Mn2+

A study of the local magnon mode in FeF₂ crystals with Mn²⁺ impurities by inelastic Raman light scattering is presented. Though the interaction between the radiation and the Mn spins is negligible the scattering by the s₀ local mode is very strong. The data of the frequency and the scattering intensity are analyzed in terms of a magnetization coupled mode approach.     

Theory of Raman scattering and infrared absorption by interacting phonon-magnon states in FeF2

It is shown theoretically that, in the presence of a strong magnetic field, effects due to the interaction betweenB _1g ,E _g,TA phonons and magnons should be important in the Raman and infrared absorption spectrum of FeF₂. As a result the two magnon line should split. A microscopic Hamiltonian for the interactions has been derived. The calculated values of theE _g phonon-one magnon interaction, 9.9 cm^–1, and of theB _1g phonon-two magnon coupling, 6.3 cm^–1, are comparable to those in FeCl₂2H₂O metamagnet, in which C phonon-magnon hybrydization has been observed [1]. It is shown that hybridization between two magnon andB _1g orTA phonon can occur in FeF₂ if the magnon energy approaches the phonon energy due to increasing magnetic field or increasing temperature.On the leave from Technical University, Pozna, Institute of Physics, Pozna 61–138 Piotrowo 3, Poland     

The pressure dependence of the néel temperature in FeF2

A Mössbauer measurement of the pressure dependence of the Néel temperature in FeF₂ is reported. Up to the maximum pressure of 50 kbar T_N increases at the rate of 0.27 ± 0.03°K/kbar. When this pressure dependence is converted to volume dependence, the result, d In T_N/d In V = 3.2 ± 0.3, is found to obey the $\text{“10}\text{3}$ rule” established by Bloch for a wide variety of antiferromagnetic insulators.     

Compression mechanism of GaF3 and FeF3: a high-pressure X-ray diffraction study

The VF₃-type compounds MF₃ with M = Fe and Ga have been studied by high-pressure energy-dispersive X-ray diffraction. The compression mechanism was found to be highly anisotropic for both compounds, with the c-axis showing little pressure dependence. The volume reduction is mainly achieved through coupled rotations of the MF₆ octahedra around the c-axis, which reduces the length of the a-axis. The compression mechanism of both compounds is reasonably well described in terms of deformation of an 8/3/c2 sphere-packing model up to the pressures where the fluorine atoms become hexagonally close-packed. It is proposed that both compounds enter a phase with the fluorine atom arranged in a “super-dense” sphere packing at higher pressures. The zero pressure bulk modulus of FeF₃ and GaF₃ was determined as 12(2) and 37(3) GPa, respectively, and a scaling relation between the zero pressure bulk modulus and unit cell volumes was found for TiF₃, CrF₃, FeF₃ and GaF₃.     

One-dimensional magnetism in N2H6FeF5,

A new Fe(III) fluoride N₂H₆FeF₅ has been investigated by magnetic susceptibility measurements and Mössbauer resonance. It has a one-dimensional magnetic behaviour. The intrachain exchange integral ($\text{J}\text{k}\text{= -10.2}\text{K}$) has been determined by fitting the χ^-1 = f(T) curve and the ratio between the inter- and intrachain exchange integrals evaluated with Oguchi's formula. Below T_N = 9 K, N₂H₆FeF₅ shows a long range three-dimensional anti-ferromagnetic ordering.     

Etude de la structure magnetique et de la transition de typr “spin-flop” de Rb2FeF5

The nature of the magnetic interactions in the chain compound Rb₂FeF₅ has been investigated using neutron diffraction and magnetic measurements under high applied fields. Rb₂FeF₅ orders antiferromagnetically at T_N = 8.0 ± 0.5 K; the magnetic structure is of the A_Z + G_X mode and the moment of the Fe³⁺ ion extrapoled to 0K is 3.5 ± 0.2 μ_B, this low value being due to zero-point spin reduction. Within a chain the Fe³⁺ ions are antiferromagnetically coupled with an exchange constant of J/k = ?8.8 K. A spin-flop behavior has been observed and interpreted on the basis of the molecular field theory. The critical field was found to be H_C = 65 kOe at 1.7 K.     

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.     

Calculation of the interface exchange coupling constants between Fe and FeF2-like fluorides

The interface exchange coupling between ferromagnetic (F) and antiferromagnetic (AF) materials is interesting in itself and has also attracted recent attention in relation to the exchange bias phenomenon. A major difficulty in developing a reliable exchange bias theory lies in the fact that both the F and AF interface characteristics (geometry and physical parameters) are hard to determine experimentally and complicated to estimate theoretically. We adopt in this paper two alternative interface configurations to obtain upper and lower bounds for the computed values of the exchange coupling across the interface between metallic Fe and insulating FeF₂, derived on the basis of ab initio calculations implemented for a periodic supercell. Electronic structures and total energies were computed within density functional theory using the generalized gradient approximation for the exchange correlation potential. We expect the results obtained to be useful in model simulations with larger unit cells and non-collinear spins.     

Measurement of Debye-Waller factors by Raman scattering from inter-term excitons and exciton-multiphonon states in FeF2

We have observed inter-term Raman scattering from ⁵T_2g→⁵E_g Frenkel excitons in antiferromagnetic FeF₂. It differs qualitatively from previously observed intra-term scattering in a sharply reduced zero-phonon cross section and the appearance of relatively strong exciton-phonon scattering. Since the Raman process is fully allowed, it is possible to measure excited state Debye-Waller factors, D, and we find $\text{D(Λ}{}_3{}^{\mathrm{+}}\text{+ Λ}{}_4{}^{\mathrm{+}}\text{,}{}^5\text{E}{}_{\mathrm{g}}\text{) = 0.04}$ and $\text{D(Λ}{}_1{}^{\mathrm{+}}\text{,}{}^5\text{E}{}_{\mathrm{g}}\text{) = 0.03}$.     

Mössbauer study of isothermal crystallization kinetics of the amorphous iron III fluoride FeF3, 0.4HF

The amorphous fluoride FeF₃,xHF (0.4?×?1) synthetized by a soft chemistry reaction, crystallizes to R-FeF₃. Crystallization was followed as a function of time at several constant temperatures by Mössbauer spectroscopy. The evolution of R-FeF₃ rate is in good agreement with a Johnson-Mehl-Avrami transformation equation: The crystallization proceeds like a first-order reaction with an activation energy of ≈2 eV.     

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.     

High field Mössbauer spectroscopy on a disordered paramagnet: FeF3, 0.4HF

High Field Mössbauer Spectroscopy has been carried out on an amorphous ferric fluoride: FeF₃, 0.4HF. Below the spin-freezing temperature, the external field cannot align the magnetic moments which are drawing a speromagnetic structure. At higher temperatures, the magnetic moments are colinearly aligned parallel to the external field direction. A progressive canting of the moments is observed in the intermediate temperature range resulting from a competition between molecular field distribution and applied field.     

Kritisches Temperaturverhalten des Magnetfeldes am Kernort von57Fe in wasserfreiem Eisenhalogenid FeF3

Using the Mössbauer-Spectroscopy the temperature dependence of the magnetic fieldH(T) at the site of the⁵⁷Fe-nuclei in FeF₃ has been measured fromT=78 K toT=400 K. From the experimental data the Néel-Temperature was determined to beT _N =362,5(1) K. Measurements in the vicinity of the Néel-point (0,87≦T/T _N ≦ 0.999) yield a critical exponentβ=0.354(6) and a value for the coefficient D=1.23(3).     

Fourth-order spin Hamiltonian terms for Fe2+ in rutile structure antiferromagnet FeF2

The paper deals with the spectroscopic and magnetic properties of Fe²⁺ ions in FeF₂. The microscopic spin Hamiltonian theory for Fe²⁺ in crystalline environments with second-kind orthorhombic symmetry is considered. Explicit formulas for the parameters B₀⁽²⁾(D),B₂⁽²⁾(E), g_x, g_y, g_z and, for the first time in the literature, the fourth-order parameters B₀⁽⁴⁾, B₂⁽⁴⁾ and B₄⁽⁴⁾, are derived. Using semi-empirical data for the ⁵D-term energy levels of Fe²⁺ ion in FeF₂, the pressure dependence of the parameters B_q^(k) in the region from 0 to 133 kbar is discussed. The relative role of the fourth-order parameters with respect to the second-order ones is found to increase strongly with pressure (e.g. in the region studied, D increases only by a factor of 3, whereas B₀⁽⁴⁾ increases by a factor of nearly 20). The magnetocrystalline anisotropy of FeF₂; is considered in the strong anisotropy model taking into account the fourth-order spin Hamiltonian terms. The uniaxial anisotropy constants K₁ and K₂ are derived theoretically and their pressure dependence is discussed quantitatively. The theory and numerical results of this paper are useful with regard to Fe²⁺ in other isomorphic fluorides, namely: MgF₂, ZnF₂, VF₂ and MnF₂. It is found that the fourth-order spin Hamiltonian parameters are accessible to experimental detection from spectroscopic studies on Fe²⁺ in non-magnetic fluorides and magnetic studies on Fe²⁺ : MnF₂ and FeF₂, preferably under high pressure.     

Pulsed laser deposited iron fluoride thin films for lithium-ion batteries

Iron fluoride thin films were successfully grown by Pulsed Laser Deposition (PLD), and their physico-chemical properties and electrochemical behaviours were examined by adjusting the deposition conditions, such as the target nature (FeF₂ or FeF₃), the substrate temperature (T_s ≤ 600 °C), the gas pressure (under vacuum or in oxygen atmosphere) and the repetition rates (2 and 10 Hz). Irrespective of the FeF₂ or FeF₃ target nature, iron fluoride thin films, deposited at 600 °C under vacuum, showed X-ray diffraction (XRD) patterns corresponding to the FeF₂ phase. On the other hand, iron fluoride thin films deposited at room temperature (RT) from FeF₂ target were amorphous, whereas the thin films deposited from FeF₃ target consisted of a two-phase mixture of FeF₃ and FeF₂ showing sharp and broad diffraction peaks by XRD, respectively. Their electrochemical behaviour in rechargeable lithium cells was investigated in the 0.05-3.60 V voltage window. Despite a large irreversible capacity on the first discharge, good cycling life was observed up to 30 cycles. Finally, their electrochemical properties were compared to the ones of iron oxide thin films.