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.     

Spin crossover in the magnetic phase transition in YBa2(Cu1−x Fex)3O7±δ superconductors

All iron ions in the Cu1 and Cu2 local lattice sites of the YBa₂(Cu_0.9 ⁵⁷Fe_0.1)₃O_7.01 superconductor with T _c=31 K experienced magnetic ordering below T _m=22 K. Therefore, at T < T _m, magnetic ordering coexisted with superconductivity. According to the Mössbauer spectroscopy data, iron ions in Cu2 (Fe2) sites were in the low-spin state at T < T _m(S= 3/2 or 1/2), whereas an equal number of iron ions in Cu1 (Fe1) sites were in the high-spin Fe³⁺ state (S=5/2). The magnetic transition near T _m changed iron ion spin states-low-spin ions turned into high-spin ions, and vice versa. This preserved the spin balance between iron ions in the Cu1 and Cu2 layers. Control measurements on other samples of the YBa₂(Cu_{1? x} Fe_x)₃O_7±δ series substantiated these conclusions.     

Heterometallic fullerides of Fe and Cu groups with the composition K2MC60 (M=Fe+2, Fe+3, Co+2, Ni+2, Cu+1, Cu+2, Ag+1)

Heterometallic fullerides with composition K₂MC₆₀, synthesized by exchange chemical reaction of K₅C₆₀ or K₄C₆₀ with chlorides of metals Fe and Cu groups have been investigated by X-ray diffraction, magnetic resonance, Raman and Mössbauer spectroscopy. Magnetization and susceptibility measurements have also been carried out. Metal chlorides from Fe and Cu groups enable to cover the whole range of electronic configuration of metal from d⁵ to d¹⁰. Heterometallic fullerides with M=Cu⁺², Fe⁺², Fe⁺³ and Ni⁺² appeared to be superconductors with T_c=13.9–16.5 K. Ferromagnetism and superconductivity coexist in investigated fulleride K₂Fe⁺³C₆₀.     

Magnetism and superconductivity in R1.5Ce0.5MSr2Cu2O10‐δ (M=Ru and Fe) compounds

It is shown here, that the superconducting (SC) R_1.5Ce_0.5RuSr₂Cu₂O_10-δ (RCeRuSCO, R= Eu and Gd) materials (T_c ～ 32 and 42 K) are also antiferromagnetically (AFM) ordered at T _N(Ru) ～ 122 and 180 K, respectively, thus, T_N ? T_c, a trend which is contrary to that obtained in “magnetic‐SC” intermetallic systems. Mössbauer spectroscopy (MS) on 0.5% ⁵⁷Fe doped samples shows that all Fe ions reside in the Ru site which is magnetically ordered, whereas SC is confined to the CuO₂ planes. On the other hand, for Y_1.5Ce_0.5FeSr₂Cu₂O₉ (YCeFSCO) no SC is found and the Cu–O planes order AFM at T _N(Cu)=31 K. MS studies reveal two in equivalent Fe sites, and that Fe resides predominantly (60%) in the Cu(1) site. In both sites, the Fe does not order magnetically, and the low T _N(Cu) obtained is due to frustration of the Cu moments by the presence of Fe. T _N is sensitive to oxygen concentration and shifts toward 260 K when oxygen is depleted.     

Revealing the Spin-Hamiltonian and Characteristic Parameters of Paramagnetic Centers in Cu2+-Doped Potassium Metabisulfite (K2S2O5) Single Crystal by Electron Paramagnetic Resonance Technique

The present study is mainly related to finding out spin-Hamiltonian parameters of Cu²⁺-doped potassium metabisulfite [K₂S₂O₅] single crystals using electron paramagnetic resonance (EPR) technique which has been applied in the temperature range from 297 to 113 K for single and powder crystals of the title compound. The existence of two complexes and two Cu²⁺ sites for each complex was concluded from the angular variation of the EPR spectra. Having constructed the g and the hyperfine tensors, the spin-Hamiltonian parameters have been obtained for these two complexes. Using these parameters, the covalency parameter (α ²), mixing coefficients (α and β) and Fermi contact term (K) have been calculated.     

Mössbauer effect study of SrEu2Fe2O7

The antiferromagnetic ferrite SrEu₂Fe₂O₇ was studied by Mössbauer effect of⁵⁷Fe in the range 77–650 K. Analysis of the data gives a Neel temperature of 544 K±2 K and an extrapolated effective magnetic fieldH(OK) of 545 kG. Good fit to the spectrum at 290 K is obtained withH _eff=475 kG, δ=0.37 mm/s, 1/2e ² qQ(1+η ²/3)=0.70mm/s, θ and ?=90°. The Brillouin function forS=5/2 poorly fits the experimental data of hyperfine magnetic fields. In the critical rangeH _eff can be described byH(T)=H(0)D(1?T/T _N )^β, where β nearly 0.29. The quadrupole interaction parameter is quite temperature independent, of the order of 0.69 mm/s in the paramagnetic state. Agreement with the value obtained by a point charge calculation is good. The largest axis of the EFG tensor,V _zz , lies in the plane (110), making an angle of 22.6° with thec axis. The direction of magnetization is nearly perpendicular toV _zz in [110] direction.     

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.     

EPR studies on aqueous sucrose solutions using (Cu(H2O)6)2+ spin probe

EPR investigations using Cu²⁺ ion as a probe have been performed on supersaturated sucrose solution with percent concentration c = 66 as a function of temperature T, and at room temperature as a function of c. The motionally averaged spectrum of [Cu(H₂O)₆]²⁺ was used to monitor the changes in intermolecular interactions that occur as a function of [c, T]. A drastic increase in the line width, symptomatic of increase in the rotational correlation time of [Cu(H₂O)₆]²⁺, is observed between 293 and 288 K. The motionally averaged spectrum disappears below 281 K. The motionally averaged spectrum is also absent in the room temperature spectra of the solution with c= 85. Even in the [c, T] range where [Cu(H₂O)₆]² is found to be nearly static, these molecules appear to have an orientational fluctuation manifesting in the m ₁ dependence of the line width of the parallel component.     

EPR study of Fe3+ and Mn2+ in CeO2 and ThO2

Attempts were made to grow CeO₂ and ThO₂ single crystals doped with transition metal ions. Only Fe³⁺ and Mn²⁺ could be detected by the EPR technique. The EPR spectrum of Fe³⁺ in CeO₂ exhibits the well-known fine structure in cubic fields. The parameters areg=2.0044(1) anda=15.6(1)·10^?4 cm^?1. The hyperfine constantA for⁵⁷Fe in hexahedral coordination was found to be 8.9(1)·10^?4 cm^?1. The EPR spectrum of Mn²⁺ in CeO₂ reveals two cubic Mn²⁺ centers. The parameters for center 1 areg=1.9999(1) andA=86.9(1)·10^?4 cm^?1 and for center 2g=1.9984(1) andA=87.0(1)·10^?4 cm^?1. Heating the Mn doped CeO₂ samples in hydrogen, the Mn²⁺ centers transform from cubic into trigonal centers with approximate values ofg=1.9988(2),A=84.5(6)·10^?4 cm^?1 andD=203(1)·10^?4 cm^?1. The two observed Mn²⁺ centers in ThO₂ exhibita priori axial symmetry with approximate values ofg=2.0006(2),A=88.9(4)·10^?4 cm^?1 andD=33(3)·10^?4 cm^?1.     

Local structure of bivalent copper centers in SrF2 crystals: An ENDOR spectroscopic study

Structural distortions of the SrF₂ crystal lattice near the bivalent copper impurity Jahn-Teller center are investigated by the ENDOR method (v=9.3 GHz, T=4.2 K). The approximate directions and the magnitudes of displacements of a Cu²⁺ impurity ion and its surrounding F^? ions are determined with respect to one of the anionic networks in the crystal matrix. The tensor components for the ligand hyperfine interaction (LHFI) with fluorine ions separated from the impurity by a distance R≤6.2 Å are obtained from the angular dependences of the location of the ENDOR resonance lines. It is found that the parameters of magnetic interactions between the impurity and these ligands contain the contributions determined by the covalence of bonds in the impurity complex and the polarization of electron shells of the ligands.     

Spin gap, phase separation and d-wave pairing as revealed by electron spin-lattice relaxation in 123 and 124 YBaCuO systems doped with Gd3+

With an original modulation technique, the Gd³⁺ electron spin-lattice relaxation has been investigated in normal and superconducting states of YBa₂Cu₃O_6+x (123) and YBa₂Cu₄O₈ (124) compounds doped with 1% Gd. In the 123 sample withx = 0.9T _c = 90 K), theT ₁ behavior within 50 <T< 200 K reveals the [1 ? tanh²(Δ/2kT)]/T dependence typical of a spin gap opening with Δ ≈ 240 K. Below 50 K, the exponential slowing down ofT ₁ is limited by the Korringa-like behaviorT ₁ T = const); the same Korringa-like law is found in the 123 sample withx = 0.59 (T _c = 56 K) within the total 4.2–200 K temperature range. This is interpreted in terms of microscopic separation of the normal and superconducting phases allowing for the electron spin cross-relaxation between them. In the 124 sample (T _c = 82 K), the Gd³⁺ relaxation rate below 60 K is found to obey a power lawT _n with an exponentn ≈ 3. Such a behavior (previously reported for nuclear spin relaxation) is indicative of the d-wave superconducting pairing. Additional paramagnetic centers characterized by relatively slow spin-lattice relaxation are found in both 123 and 124 systems. A well-pronounced change in theT ₁ temperature dependence atTT* ≈ 180–200 K is observed for these slowly relaxing centers as well as for the conventional, fast-relaxing Gd³⁺ ions, suggesting microscopic phase separation and a change in the relaxation mechanism due to electronic crossover related with the opening of the spin gap. This hypothesis is supported by some “180 K anomalies” previously reported by other authors.     

Distribution of hyperfine fields of57Fe2+ in amorphous LiNbO3: Mössbauer study at low temperatures in high magnetic fields

Mössbauer spectra of amorphous LiNbO₃ doped with⁵⁷Fe²⁺ ions were measured atT≥4.2 K in external magnetic fields up toH=5.5 T. It was found that the oxygen octahedra around the high-spin Fe²⁺ ions are randomly distorted obeying no symmetry at all. The correlation of isomer shift and quadrupole splitting is probably due to T_2g distortions.     

Heavy ion irradiation effects inc-axis oriented thin films of YBa2(Cu0.97 57Fe0.03)3O7 studied by CEMS

Fullyc-axis oriented thin films of YBa₂ (Cu_0.97 ⁵⁷Fe_0.03)₃O₇ on <100> SrTiO₃ substrate were irradiated with different fluences ? of 500 MeV¹²⁷I parallel to thec-axis. The samples were investigated by means of x-ray diffraction, resistiveT _c measurements and conversion electron Mößbauer spectroscopy (CEMS). Irradiation results in the appearance of a fourth quadrupole doubletE in the CEMS-spectra (E _Q=1.1 mm/s, IS=0.26 mm/s), whose intensity increases with increasing ?. The Debye Waller factor of the new Fe-speciesE is only about 60% of that of the speciesA, B, andC proving that irradiation with high energy heavy ions results in latent tracks of lower density. from the hyperfine parameters of speciesE we conclude that the latent tracks are mainly formed by the “green phase” Y₂BaCuO₅. We derived the radius of the latent tracks to be about 26 Å.     

Intermediate electronic relaxation betweenS=3/2 andS=1/2 states in Fe(J-mph)NO with a jäger-type ligand J-mph

The incomplete spin transition between the low-spin (LS) (S=1/2) and the intermediate-spin (IS) (S=3/2) states in the iron (III) complex Fe(J-mph)NO (mph=4-methyl-o-phenylene), centered atT _c≈212 K, has been studied with⁵⁷Fe Mössbauer spectroscopy and magnetic susceptibility measurements between 80 K and 320 K. The lineshape of the Mössbauer spectra is well reproduced by a two state stochastic relaxation model resulting in values of about 2·10⁶ s^?1 to 7·10⁶ s^?1 for the IS→LS transition rate constantk _IL. The kinetics of this spin transition can be described by an Arrhenius equation yielding activation energiesE _IL=1.1 (2) kJ/mol andE _LI=6.1 (2) kJ/mol for the IS→LS and LS→IS conversion, respectively.     

NMR and spin-lattice relaxation rate of89Y,63Cu in radiation disordered YBa2Cu3O6.9

NMR line shifts and spin-lattice relaxation rates of⁸⁹Y and⁶³Cu in YBa₂Cu₃O_6.9 were measured in disordered samples irradiated by fast neutrons with a fluence of: ?=5·10¹⁸ cm^?2 (T _c ^ons =70 K), ?=1.2·10¹⁹ cm^?2 (T _c ^ons =20 K), in order to investigate the evolution of spin susceptibility χ_S under irradiation. According to the data obtained, χ_S decreases markedly as structural disorder accumulates in the samples. The variation of χ_S is related closely to that observed in oxygen-depleted YBa₂Cu₃O_7?δ compounds with nearly the sameT _c value. The data for yttrium display some features that are absent in oxygen-depleted samples. The different temperature dependence of the⁸⁹Y and⁶³Cu Knight shifts and the increase of the⁸⁹Y spin-lattice relaxation rate in irradiated samples are discussed in terms of the electron localization effects arising in the CuO₂ planes due to the radiation-induced structural disorder.     

Mössbauer studies of magnetic behavior of 3d-doped REBa2Cu3−x Fe x O7+δ (RE=Y,Er, Dy,Gd)

A Mössbauer study has been made on⁵⁷Fe ions substituted into the Cu(1) site of REBa₂Cu_3?x Fe _x O_7+δ (RE=Y, Er, Dy, Gd;x=0.15, 0.30). At low temperature, the iron atoms antiferromagnetically order with a transition temperature which is dependent on the Fe concentration. The temperature dependence of the magnetic subspectra representing Fe ions with various local oxygen environments in YBa₂Cu_3?x Fe _x O_7+δ and ErBa₂Cu_3?x Fe _x O_7+δ fit a 2D-Ising model with a ratio of the anisotropic exchange between the two directions on the order of 0.5–1.0(10^?3) for the Y-compounds and on the order of 1 for the Er-compounds. The magnitude of the local dopant magnetization is related to a short-range chemical order which determines the magnetic chain size and defines the correlation lengths. For the Y-compound, the order is quasi-1D with strong intrachain but very weak interchain coupling. For the Er-compounds, the magnetic coupling is Ising 2D. The strong fluctuation behavior expected in low dimensional systems above and belowT _N is observed via characteristic relaxation in the Mössbauer linewidth nearT _N. For both the Dy- and Gd-compounds, the magnetic order is 3D. The magnitude of the rare-earth magnetic moments appears to affect the character of the magnetic interaction in the Cu(1)-site. However, a Mössbauer effect measurement at¹⁵⁵Gd nuclei in GdBa₂Cu_2.85Fe_0.15O_7+δ (T _N(Fe)～14 K) shows paramagnetic behavior at 4.9 K.     

Critical current density and flux pinning in La2−xPrxCa2x Ba2Cu4+2xOz (x=0.1-0.5) superconductors

Polycrystalline La_2−xPr_xCa_2xBa₂Cu_4+2xO_z (LPCaBCO) compounds with x=0.1-0.5 were synthesized by solid-state reaction method and studied by room temperature X-ray diffraction, dc resistivity, dc magnetization and iodometry. The superconducting transition temperatures in these tetragonal triple perovskite compounds increases from 32 to 62 K (T_c^onset values) with increasing dopant concentration. The mixing of rare earth La³⁺ and Pr^3+/4+ ions at rare earth site (La³⁺) along with substitution of divalent Ca²⁺ results in the shrinkage of unit cell volume. The contraction of unit cell volume due to larger ion being substituted by smaller ions, gives rise to creation of pinning centres in the unit cell leading to increase in critical current density and flux pinning.     

Possible oxygen hopping in the YBa2Cu3O7 system observed by Mössbauer spectroscopy

In situ high temperature⁵⁷Fe Mössbauer measurements have been performed on samples of YBa₂ (Cu_1?xFe_x)₃O_7?δ withx=0.005 andx=0.010, in pure oxygen or in air, in the range 295 K≤T≤640 K. TheT-dependence of Fe species, of the Debye-Waller factorf(T) as well as of the hyperfine parameters is analysed.     

Mössbauer studies of hyperfine fields in disordered Fe2CrAl

Heusler-like alloy Fe₂CrAl was prepared and studied. Structure determination was done by X-ray. The structure was found to conform to the B₂ type. Magnetic hyperfine fields in this sample were studied by the Mössbauer effect. The Mössbauer spectra were recorded over a range of temperature from 40 to 296 K. The Mössbauer spectra showed the co-existence of a paramagnetic part with a magnetic hyperfine portion at all recorded temperatures. Even with the distribution in the magnetic hyperfine field, the average hyperfine field follows the (T/T _c)^3/2 law. The paramagnetic part of the hyperfine field is explained in terms of the clustering of Cr atoms.