Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Magnetism and the magnetocaloric effect in PrMn1.6Fe0.4Ge2

The magnetic and magnetocaloric properties of PrMn_1.6Fe_0.4Ge₂around the ferromagnetic transitions T _C ^inter ~ 230 K and T _C ^Pr ~ 30 K have been investigated by magnetisation, ⁵⁷Fe Mössbauer spectroscopy and electron paramagnetic resonance (EPR) measurements over the temperature range 5–300 K. The broad peaks in magnetic entropy around T_C ^inter (intralayer antiferromagnetism of the Mn sublattice to canted ferromagnetism) and T_C ^Pr (onset of ferromagnetic order of Pr sublattice in addition to ferromagnetically ordered Mn sublattice) are typical of second order transitions with maximum entropy values of -ΔS _M ~ 2.0 J/kg K and -ΔS _M ~ 2.2 J/kg K respectively for ΔB = 0–6 T. The EPR signal around T = 48 K of g value g ~ 0.8 is consistent with paramagnetic free ion Pr^3?+?. Below T_C ^Pr ~ 30 K the g value increases steadily to g ~ 2.5 at 8 K as saturation of the Pr^3?+? ion is approached. The EPR measurements indicate additional effects in this system below T ~ 20 K with the appearance of EPR signals of low g value g ~ 0.6.     

Localization of conduction electrons and the magnetic properties of the molecular metals β″-(BEDT-TTF)4NH4[M(C2O4)3] · DMF (M = Cr3+, Fe3+)

Quasi-two-dimensional organic metals β″-(BEDT-TTF)₄NH₄[M(C₂O₄)₃] · DMF containing the oxalate complexes of Cr³⁺ or Fe³⁺ ions between the conducting organic layers of the BEDT-TTF molecules are studied by EPR spectroscopy, and the contributions of these metallic complexes, conduction electrons, and non-equilibrium lattice defects to the magnetic susceptibility are determined. An analysis of the temperature dependence of the magnetic susceptibility and the EPR line shape has revealed partial localization of conduction electrons at T < 20 K in the crystals with Cr³⁺ ions. The size of the localization region is close to the size of an individual BEDT-TTF molecule. The localization effect weakens as nonequilibrium defects disappear during long-term storage at room temperature. The localization of conduction electrons is found to be accompanied by the appearance of weak antiferromagnetic interaction between the Cr³⁺ ions at T < 20 K, which disappears when Fe³⁺ ions substitute for Cr³⁺ ions.     

A Low Temperature (10 K) High-Frequency (208 GHz) EPR Study of the Non-Kramers Ion Mn3+ in a MnMo6Se8 Single Crystal

A high-frequency (208 GHz) electron paramagnetic resonance (EPR) study on Mn³⁺ (3d⁴, S = 2) ions embedded in a MnMo₆Se₈ single crystal has been performed at 10 K. The experimental spectra reveal the presence of only one set of EPR lines from Mn³⁺ ions, whose magnetic axes are oriented along the crystal axes. The spin-Hamiltonian parameters are evaluated by the method of least-squares, fitting all the observed line positions simultaneously, for the three orthogonal orientations of the external magnetic field. The symmetry of the spin Hamiltonian at the site of the Mn³⁺ ions has been deduced from the EPR spectra.     

Spin-spin interaction of Dy3+ ions in KY(WO4)2

The spin-spin interaction of Dy³⁺ ions in a KY(WO₄)₂ single crystal is investigated by electron paramagnetic resonance (EPR) spectroscopy at a temperature of 4.2 K and a frequency of 9.2 GHz. The EPR spectra of ion pairs located in different coordination shells are analyzed. It is revealed that the considerable contribution to the spin-spin interaction of the nearest neighbor ion pair nn is made not only by the magnetic dipole-dipole interaction but also by the isotropic exchange interaction with the parameter I _nn = (+601 ± 17) × 10^?4cm^?1. The exchange interaction in pairs of more widely spaced ions is substantially weaker: I _5n = (?38 ± 3) × 10^?4cm^?1 and I _9n = (+18 ± 4) × 10^?4cm^?1. For the other ion pairs, the magnetic dipole-dipole interaction dominates. It is found that the EPR spectra of single ions and ion pairs exhibit a superhyperfine structure associated with tungsten nuclei.     

EPR spectra of a GdMnO3 thin film on a SrTiO3 substrate

Electron paramagnetic resonance (EPR) spectra of a GdMnO₃/SrTiO₃ thin film in the X band have been measured in the temperature interval from 200 to 450 K. Signals from two types of paramagnetic centers have been observed in the spectra. The first paramagnetic center is a subsystem of Gd³⁺ ions, in the EPR spectrum of which the fine structure lines are resolved below 350 K. The second paramagnetic center is a system of manganese and gadolinium ions, in the EPR spectrum of which an exchange-narrowed line is observed with the width ΔH several times less than the width ΔH of an exchange-narrowed line observed in the GdMnO₃ single crystal. Unusual magnetic properties are due to the mismatch of the lattice parameters of the GdMnO₃ thin film and the SrTiO₃ substrate.     

EPR study of the low temperature charge density wave state of o-TaS3

We report an EPR study of the chain conductor o-TaS₃ in the low temperature charge density wave (CDW) state. The EPR spectrum is attributed to Fe³⁺ (S=5/2) impurities. A power law for the temperature dependence of the EPR intensity, (T^−α with an exponent α∼0.8) found below ∼30 K is very close to that previously found in magnetic susceptibility measurements. The possible role of these impurities in the susceptibility data are discussed.     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Fe2+ spin transition in [Fe(trz)(Htrz)2](BF4) as evidenced by a variable temperature EPR study

The EPR of Fe³⁺ ions has been used for the first time to evidence a low-spin (S=0) to high-spin (S=2) transition of Fe²⁺ ions in an octahedral ferrous complex [Fe(trz)(Htrz)₂](BF₄). The temperature dependence of the intensity of the Fe³⁺ EPR line atg=4.3 reveals a spin transition which occurs for the Fe²⁺ ions, with hysteresis. The transition temperatures areT _c↑=374 K in the warming mode andT _c↓=345 K in the cooling mode. The analysis of the EPR spectral data indicates the presence of a structural phase transition accompanying the spin transition.     

An Electron Paramagnetic Resonance Study of the Orbital Ordering Compound MgTi<Subscript>2</Subscript>O<Subscript>4</Subscript>

We report the electron paramagnetic resonance (EPR) studies of MgTi₂O₄ in the 300–140 K range. Above the transition temperature T _t (~258 K), the EPR results indicate that MgTi₂O₄ is paramagnetic. The parameters of the EPR spectra show an anomalous change at T _t. The clear EPR lines can be observed in temperature between T _t and 220 K. Besides that the EPR intensity, g value, and EPR linewidth increase with decreasing temperature; in temperature range below 220 K, no clear EPR line can be detected. The EPR spectra results demonstrate that magnetic spin-singlet state and the orbital density wave of MgTi₂O₄ system are formed gradually with decreasing temperature at low temperature range.     

EPR and optical absorption studies on VO ions in KZnClSO4·3H2O single crystals—an observation of superhyperfine structure

EPR spectra of VO²⁺ ions doped in KZnClSO₄·3H₂O single crystals have been studied at different temperatures. The EPR spectrum shows a well-resolved hyperfine and superhyperfine structure patterns. The angular variation of EPR spectra reveals the presence of more than three magnetic complexes, which correspond to distinct sites of VO²⁺ ion. From the angular variation EPR data, the spin-Hamiltonian parameters are evaluated and discussed. The optical absorption spectrum studied at room temperature shows bands corresponding to C_4v symmetry. From the EPR and optical data, the molecular-orbital bonding coefficient ε² and β² are evaluated and discussed. The observed five-line superhyperfine structure has been attributed to four protons (with I=1/2) from the surrounding water molecules of one of the vanadyl sites.     

EPR of cadmium ferric voltaite above the ferrimagnetic transition

A single isotropic EPR line of Fe³⁺ in synthetic cadmium ferric voltaite, (NH₄)₂Cd₅Fe₃Al(SO₄)₁₂ · 18H₂O, was observed in a wide temperature range from 295 to 1.57°K. The ferrimagnetic transition temperature of CdFe voltaite was determined to be ～ 0.7°K using the temperature dependence of the g-factor and the line width. The cubic crystal field parameter, a, for Fe³⁺ in CdFe voltaite is extracted from the EPR line width measurement using the exchange-narrowed line width model of Anderson and Weiss. The parameter a for Fe³⁺ in CdFe voltaite at 4.2°K is 157 × 10^-4cm^-1 which is consistent with the corresponding values for Fe³⁺ in other cubic structures.     

Temperature and pressure dependences of EPR spectra of Gd ion doped in the EuAl3(BO3)4 monocrystal

The ground state of Gd³⁺ ions substituting for trivalent europium in the EuAl₃(BO₃)₄ single crystal was studied by electron paramagnetic resonance (EPR) over the temperature range of 300-4.2 K and at pressures up to 9 kbar. The EPR spectra were analysed using the spin Hamiltonian of axial symmetry. The following parameters are reported: g=1.981±0.002, b₂⁰=280.18±0.12, b₄⁰=−12.95±0.08 and b₆⁰=0.61±0.12 (at Т=298 K). The distortions of the nearest environment of Gd³⁺ ion were analysed within the framework of the superposition model of crystal field.     

Raman scattering in magnetic US3

A Raman scattering investigation of magnetic US₃ has been made from 7 to 300 K. Comparison of room temperature spectra with those of the non magnetic isostructural sulfide HfS₃ allowed the assignment of most of the lines to $\textcolor{red}{}\text{=}\text{0}$ optical phonons. Drastic changes take place in the 10?150 cm^?1 range when lowering the temperature down to 7 K : four equally spaced lines appear at 54, 72.5, 91 and 109.5 cm^?1. Three of them broaden significantly with increasing temperature and disappear near 50 K, at which previous measurements indicate a maximum in the magnetic susceptibility and suggest a magnetic phase transition. The stronger fourth line is still observed at 100 K and merges into a phonon line at higher temperature. These four lines are attributed to electronic transitions within the 5f² configuration of U⁴⁺. Their temperature dependences appear to involve a spin-dependent scattering mechanism and are consistent with antiferromagnetic ordering.     

A 236 GHz Fe3+ EPR Study of Nanoparticles of the Ferromagnetic Room-Temperature Semiconductor Sn1−x Fe x O2 (x = 0.005)

High-frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe³⁺ ions at 255 K are reported in a Sn_1?x Fe _x O₂ powder with x = 0.005, which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as the overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe³⁺ ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1) + I(HS2) + I(HS3) + I(HS4)) × exp(?0.00001B), where B is the magnetic field intensity in Gauss, I represents the intensity of an EPR line (HS1, HS2, HS3, HS4), and BL stands for the baseline (the exponential factor, as found by fitting to the experimental spectrum, is related to the Boltzmann population distribution of energy levels at 255 K, which is the temperature of the sample in the spectrometer). These high-frequency EPR results are significantly different from those at X-band. The large values of the zero-field splitting parameter (D) observed here for the four centers at the high frequency of 236 GHz are beyond the capability of X-band, which can only record spectra of ions with much smaller D values than those reported here.     

EPR studies of Gd3+-doped Ce2(SO4)3.8H2O and La2(SO4)3.9H2O single crystals

EPR spectra of Gd³⁺-doped Ce₂(SO₄)₃.8H₂O and La₂(SO₄)₃.9H₂O single crystals have been measured with an X-band spectrometer at room and low temperatures. The absolute signs of spin Hamiltonian parameters have been determined for the La₂(SO₄)₃.9H₂O host from intensities of lines at liquid helium temperature; for the Ce₂(SO₄).8H₂O host the lines broaden considerably below 60 K, not permitting the determination of absolute signs of spin Hamiltonian parameters. The data are analysed using a rigourous least-squares procedure, fitting simultaneously all lines obtained for several orientations of the external magnetic field. The zero-field splittings have been computed for both the hosts. The characteristics of EPR spectra of Gd³⁺ in these hosts are compared with those obtained in other rare-earth trisulphate octahydrate hosts.     

V4+ in SrTiO3: A Jahn-Teller impurity

EPR results of V⁴⁺, with $\text{S =}\text{1}\text{2}$, in SrTiO₃ are reported. The tetragonal local symmetry of the impurity ion is related to strong T_2g × ?_g coupling as evidenced by intensity variations in the presence of stress. At 4.2 K the V⁴⁺ EPR behaviour is related to the intrinsic local strain in SrTiO₃.     

Single-crystal EPR studies of transition-metal ions in inorganic crystals at very high frequency

Electron paramagnetic resonance (EPR) single-crystal rotation studies at very high frequency (249.9 GHz) of transition metal ions with electron spins greater than one-half are reported. At 249.9 GHz, the spectra are in the high-field limit despite large zero-field splittings. This leads to a considerable simplification of the spectra, and aids in their interpretation. Single-crystal 249.9 GHz EPR spectra of Ni²⁺ in Ni₂CdCl₆· 12H₂O, Mn²⁺ (0.2%) in ZnV₂O₇, and Fe³⁺ (2%) in CaYA10₄ were recorded at 253 K in an external magnetic field of up to 9.2 T, along with those at X-band and Q-band frequencies at 295 K and lower temperatures. The goniometer used at 249.9 GHz for single-crystal rotation is based on a quasi-optical design and is an integral part of a special Fabry-Pérot resonator. The values of the spin-Hamiltonian parameters were estimated from a simultaneous fitting of all of the observed line positions at several microwave frequencies recorded at various orientations of each crystal with respect to the external magnetic field with least-squares fitting in conjunction with matrix diagonalization. Estimates of zero-field splitting parameterD at room temperature are: for Ni²⁺, about ?31 GHz (site I) and about ?7 GHz (site II); for Mn²⁺, about 6 GHz; and for Fe³⁺, about 29 GHz.     

Domain structure and phase transitions of LiKSO4:EPR of SO−4 centers

Analysis of the EPR of SO⁻₄ centers in LiKSO₄ crystals indicates that the SO⁻₄ centers are associated with local positive-ion vacancies. Twin-domains of the 〉110〈 types are observed to be temperature-dependent. The anomaly at 215 K on cooling is associated with a sudden growth of the twins and the anomaly at 190 K is associated with a p6₃ to p6₃P6,mc structural phase transition.