Electron spin resonance in nickel near Tc

The temperature dependence of the FMR and EPR linewidth of bulk nickel single crystals was measured from 260 to 410°C at 9.85 GHz. A linewidth falling off rapidly with increasing temperature was found in a region above T_c: 365<T<385°C. An interpretation by the critical behaviour of the spin system is discussed.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.     

Linebroadening in DF-ODMR spectra of triplet excitons in the anthracene-1, 2, 4, 5-tetracyanobenzene single crystal near its structural phase transition

The temperature evolution of the DF-ODMR spectra of triplet excitons in the A-TCNB crystal has been studied in the vicinity of its order-disorder phase transition at T_c=204 K. Linewidth measurements were carried out for two selected orientations of the magnetic field in which the two crystal sites of the ordered phase appear as magnetically inequivalent and equivalent, respectively. In the former case the linebroadening observed near T_c was attributed to changes in the long-range order parameter and to the short-range clustering formation along the slacks. In the second case the sharp increase in the linewidth near T_c was interpreted and briefly discussed in terms of the critical slowing down of the fluctuations in the order parameter associated with the phase transition.     

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.     

Electron spin resonance analysis of magnetic structures in La2/3Ca1/3MnO3

Measurements of electron spin resonance (ESR) of La_2/3Ca_1/3MnO₃ (LCMO) in the ferromagnetic and paramagnetic phases were carried out. Phase transition and temperature dependence of the peak-to-peak ESR linewidth were determined. The transition temperature between ferromagnetic and paramagnetic phases was observed at 265 K. A prominent increase of the peak-to-peak linewidth with decreasing temperature below T_c was observed. Using the dynamic scale theory and block spin transformation in critical phenomenon, the quantitative calculation of peak-to-peak linewidth at near T_c was made, which was in good agreement with the experimental data. It was believed that the long interactions between the ferromagnetic microregions for LCMO played a key role in determining the ESR linewidth.     

Variable temperature EPR study of Fe2+ spin transition in Cu2+ doped [Fe(trz)(Htrz)2](BF4)

The temperature dependence of the EPR spectrum of Cu²⁺ in the range 293–393 K exhibits a low-spin (S=0) to high-spin (S=2) transition of the Fe²⁺ ions, with hysteresis (T _c↑=363 K,T _c↓=343 K). At 103 K, the principal values of theg and hyperfine tensors of Cu²⁺ ions are revealed by hyperfine structure.     

EPR and Optical Absorption Study of VO2+ Ions Doped Potassium Hexaaquazinc (II) Sulfate Single Crystals

X-band single-crystal electron paramagnetic resonance (EPR) studies are done on VO²⁺ ions doped in potassium hexaaquazinc (II) sulfate, K₂[Zn (H₂O)₆] (SO₄)₂ (PHZS) at room temperature. The spin Hamiltonian parameters, i.e., g and A tensors and their direction cosines, are evaluated by the standard diagonalization procedure using angular variation of the EPR spectra in three planes (ab, bc* and c*a), with the help of a computer program. The EPR spectrum is simulated using the EasySpin program to verify the calculations. The detailed EPR analysis indicates the presence of two magnetically inequivalent VO²⁺ sites. Both the vanadyl complexes are found to take up the substitutional position in the host lattice. The optical absorption spectrum of VO²⁺ ions doped in PHZS single crystal at room temperature is also recorded and four main d–d transfer bands in the visible region are assigned. The theoretical band positions are obtained using energy expressions and a good agreement is found with the experimental values. With the help of assigned bands the crystal-field parameters (Dq, Ds and Dt) are evaluated. Finally, with the optical and EPR data, the nature of bonding in the complex is discussed.     

Electron spin resonance and longitudinal relaxation around phase transition in La0.9Ca0.1 MnO3

With original modulation technique, the longitudinal electron spin-relaxation timeT ₁ has been measured in the La_1-xCa_xMnO₃ manganite (x = 0.1) both in the paramagnetic state and around the temperature (T _c) of the ferromagnetic ordering. The data are compared with the evolution of the transverse relaxation time T₂ as determined from the electron spin resonance (ESR) linewidth. Well above T_c, theT ₁ =T ₂ equality was confirmed, whereas a steep slowing down ofT ₂ was observed asT _c was approached (theT ₁/T₂ ratio increased by two orders of magnitude). The temperature dependence ofT ₁ within the whole temperature range was found to be consistent with that ofT · χ(T), where χ(T) is the electron-spin susceptibility obtained from the ESR absorption area. The interpretation suggests that both the longitudinal and transverse electron-spin relaxation rates are governed by strong exchange interaction between the Mn ions, the ESR linewidth being inhomogeneously broadened in the vicinity of the phase transition.     

Magnetic and EPR studies of the EuFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystal

Magnetic and electron paramagnetic resonance (EPR) properties of EuFe₃(BO₃)₄ single crystals have been studied over the temperature range of 300–4.2 K and in a magnetic field up to 5 T. The temperature, field and orientation dependences of susceptibility, magnetization and EPR spectra are presented. An antiferromagnetic ordering of the Fe subsystem occurs at about 37 K. The easy direction of magnetization perpendicular to the c axis is determined by magnetic measurements. Below 10 K, we observe an increase of susceptibility connected with the polarization of the Eu sublattice by an effective exchange field of the ordered Fe magnetic subsystem. In a magnetic field perpendicular to the c axis, we have observed an increase of magnetization at T < 10 K in the applied magnetic field, which can be attributed to the appearance of the magnetic moment induced by the magnetic field applied in the basal plane. According to EPR measurements, the distance between the maximum and minimum of derivative of absorption line of the Lorentz type is equal to 319 Gs. The anisotropy of g-factor and linewidth is due to the influence of crystalline field of trigonal symmetry. The peculiarities of temperature dependence of both intensity and linewidth are caused by the influence of excited states of europium ion (Eu³⁺). It is supposed that the difference between the g-factors from EPR and the magnetic measurements is caused by exchange interaction between rare earth and Fe subsystems via anomalous Zeeman effect.     

EPR studies of linewidth anomalies at phase transitions in [N(C2H5)4]2MnCl4

We have studied [N(C₂H₅)₄]₂MnCl₄ crystal by X-band CW EPR spectra in the temperature range 170-300 K. The angular dependences of linewidth ΔH were measured and described in the light of a double-layer system (2D) with exchange interactions. Two temperature anomalies of linewidth ΔH were found at T₁=225 K and T₂=192 K on cooling. Different behaviors of ΔH anomalies recorded for an external magnetic field parallel and perpendicular to the ab crystallographic plane indicate ordering/disordering of MnCl₄ groups in this plane and their displacement along the c-axis which occurs in the temperature of about 225 K.     

Magnetic resonance of spin clusters and triplet excitations in a spin-Peierls magnet with impurities

The magnetic resonance spectrum of spin clusters formed in spin-Peierls magnets in the vicinity of impurity ions is investigated. The observed temperature dependences of the effective g-factor and the linewidth of the electron paramagnetic resonance (EPR) in crystals of Cu_1?x Ni_xGeO₃ are described in the model of the exchange narrowing of the two-component spectrum with one component ascribed to spin clusters and exhibiting an anomalous value of the g-factor and the other related to triplet excitations. An estimation of the size of the suppressed dimerization region around the impurity ion is obtained (this region includes about 30 copper ions). The dependence of the effective g-factor and the EPR linewidth on the impurity concentration at low temperatures indicates the interaction of clusters.     

EPR Study of the Vanadium Ions in Mg2SiO4 Crystal

Vanadium-doped forsterite crystal has been studied with X-band electron paramagnetic resonance (EPR) spectroscopy. The sample was grown by the Czochralski technique in an argon atmosphere with 2 vol% of hydrogen. The EPR spectrum of the sample at T = 15 K is predominantly represented by the V⁴⁺ ion signals that possess a characteristic eight-line hyperfine structure and are observed close to g = 2. The observation of the two magnetically nonequivalent centers in the angular dependence in the (ab) crystal plane and one center in the (ac) and (bc) planes, combined with the published optical spectroscopy data, unambiguously show that the V⁴⁺ ions are located at the silicon lattice site. Principal values of the hyperfine A and g-tensor and magnetic axes orientations of the V⁴⁺ centers have been determined. The orientation disorder of the V⁴⁺ centers has been found around the crystalline c axis but not in the (ab) crystal plane. The angular variation of the hyperfine component linewidth is described best with a disorder range of ±3.0°.     

EPR linewidths in an unusual copper chloride chain system

The EPR linewidths in [(CH₃)₂CHNH₃]₂CuCl₄ have been measured at 78 K. The salt contains two types of structurally and magnetically inequivalent chains. Each chain can be visuallized as a narrow ribbon cut from the two dimensional (RNH₃)₂CuCl₄ structures. The EPR g values are consistent with the structural characteristics of each chain. The linewidths are influenced by anisotropic and antisymmetric exchange, and also exhibit low dimensional spin diffusion behavior. The symmetry axis of the diffusional behavior is normal to the plane of the ribbon, implying that the spin correlations in the ribbons are two dimensional in nature.     

Angle-selective measurements of spin soliton in ladder polydiacetylene by pulsed 94 GHz EPR

Angle-selection experiments of a spin soliton in randomly oriented ladder polydiacetylene were carried out by pulsed electron paramagnetic resonance (EPR) at W-band. EPR measurement using 94 GHz microwaves increased the difference in the resonance field due tog anisotropy of the spin soliton to allow the orientation dependence of transient nutation, electron nuclear double resonance (ENDOR) and spin relaxations to be investigated. The shape of theg anisotropy-resolved nutation spectrum was discussed on the basis of the EPR transition moments and the differences between spin relaxation times. Reliable assignments of hyperfine couplings to the β protons (H_β) of the alkyl side chains were achieved with the support of W-band ENDOR measurements. No significant orientational dependence in theT ₁ andT ₂ processes was found in terms of isotropy of the H_β-hyperfine interaction.     

Elastic properties of CsCN

The temperature dependence of the elastic constants of CsCN exhibiting the CsCl structure was measured with ultrasonic and neutron techniques. The room temperature values were found to bec ₁₁=18.8,c ₁₂=10.7 andc ₄₄=2.95 10¹⁰ dyn/cm². The sound waves inT _2g andE _g symmetries exhibit anomalous temperature effects which are similar but definitively weaker than those in the NaCl type cyanides. In addition we measured the acoustic phonon dispersion along [100] and [110]. These results are compared with recent molecular dynamics calculations.     

Paramagnetic centers in nonmetallic amorphous polyphthalocyanines

Electron paramagnetic resonance (EPR) spectra of nonmetallic amorphous polyphthalocyanines are investigated in the temperature range 295–500 K. The EPR spectrum of nonmetallic amorphous polyphth-alocyanine samples at room temperature prior to heating is a narrow singlet of approximately Lorentzian shape with a linewidth ΔH_pp ≈ 1.7 Oe, a splitting factor g=2.00, and an intensity I_EPR ≈ 10¹⁷ spins/g. It is found that the intensity and linewidth of the EPR spectrum increase with increasing temperature. Beginning with a characteristic temperature T₁, both parameters, ΔH_pp and I_EPR, become dependent on time (under isothermal conditions). Computer calculations of the spectra demonstrate that the EPR spectrum can be represented as a superposition of two lines with substantially differing parameters whose dependences on the temperature and micro-wave power also differ significantly. The possible reasons for the existence of electron paramagnetic resonance centers of two types with different degrees of delocalization of a charge carrier with a magnetic moment in nonmetallic amorphous polyphthalocyanines are discussed.     

Proton dynamics in antiferroelectric CsH3(SeO3)2 single crystal investigated by 1H NMR measurements

¹H nuclear magnetic resonance (NMR) measurements have been performed to study the proton dynamics associated with the antiferroelectric transition of a hydrogen-bonded single crystal of CsH₃(SeO₃)₂. Herein, ¹H NMR spectrum, shift, linewidth, and spin-lattice relaxation rate 1/T₁ are measured in the temperature range of 80–296 K with the c-axis parallel to a magnetic field of ~4.85 T. The spectrum exhibits a composite structure with two narrow peaks at 296 K; at a low temperature, this structure evolves into a single broad shape with three humps. This complex shape and evolution are deconvoluted into five or six components based on the number of inequivalent and disordered hydrogen sites. By estimating the chemical shift and linewidth for each proton site, we identify all peaks. The spin-lattice relaxation recovery exhibits a double-exponential behavior with two relaxation times, short T_1S and extremely large T_1L. Both T_1S and T_1L follow Arrhenius behavior. From the respective 1/T₁(T), the activation energies for proton motion are measured to be small: 1.16 ± 0.1 and 0.83 ± 0.06 kJ/mol for T_1S and T_1L, respectively. While the static NMR data, chemical shift and linewidth, show no evidence for the transition, the dynamic data 1/T_1L highlights a clear increase across T_N = 145 K, which is possibly a signature of the 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 of Fe ions in sodium borophosphate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectral investigations have been carried out on Fe³⁺ ions doped sodium borophosphate glasses (NaH₂PO₄-B₂O₃-Fe₂O₃). The EPR spectra exhibit resonance signals with effective g values at g=2.02, g=4.2 and g=6.4. The resonance signal at g=4.2 is due to isolated Fe³⁺ ions in site with rhombic symmetry whereas the g=2.02 resonance is due to Fe³⁺ ions coupled by exchange interaction in a distorted octahedral environment. The EPR spectra at different temperatures (123-295 K) have also been studied. The intensity of the resonance signals decreases with increase in temperature whereas linewidth is found to be independent of temperature. The paramagnetic susceptibility (χ) was calculated from the EPR data at various temperatures and the Curie constant (C) and paramagnetic Curie temperature (θ_p) have been evaluated from the 1/χ versus T graph. The optical absorption spectrum exhibits bands characteristic of Fe³⁺ ions in octahedral symmetry. The crystal field parameter (Dq) and the Racah interelectronic repulsion parameters (B and C) have also been evaluated and discussed.     

EPR of Cu2+-doped tris-sarcosine calcium chloride

The EPR study of the Cu²⁺-doped tris-sarcosine calcium chloride (TSCC) at room temperature is reported. Two magnetically inequivalent sites for Cu²⁺ were observed. The rhombic spin Hamiltonian parameters are determined by fitting the EPR spectra for two centres: Cu²⁺(I) g₁ = 2.0276, g₂ = 2.0517, g₃ = 2.4019, A₁ = 82, A₂ = 128, A₃ = 152 [G] and Cu²⁺(II) g₁ = 2.0231, g₂ = 2.0368, g₃ = 2.5294, A₁ = 76, A₂ = 92, A₃ = 156 [G]. The ground state wave function is also determined. The g-anisotropy is evaluated and compared with the experimental value. Further, the optical study of the crystal at room temperature is carried out and the nature of bonding in the complex is discussed.