Magnetic properties and Eu Mössbauer effects of mixed valence europium copper sulfide, Eu2CuS3

Ternary europium copper sulfide Eu₂CuS₃ have been investigated by X-ray diffraction, ¹⁵¹Eu Mössbauer spectroscopy, magnetic susceptibility, magnetization, and specific heat measurements. In this compound, Eu²⁺ and Eu³⁺ ions occupy two crystallographically independent sites. The ¹⁵¹Eu Mössbauer spectra indicate that the Eu²⁺ and Eu³⁺ ions exist in the molar ratio of 1:1, and the Debye temperatures of Eu²⁺ and Eu³⁺ are 180 and 220 K, respectively. In its magnetic susceptibility, the divergence between the zero-field cooled and field cooled susceptibilities appears below 3.4 K. The specific heat has a λ-type anomaly at the same temperature. From the field dependence of magnetization at 1.8 K, the Eu²⁺ ion was found to be in the ferromagnetic state with the saturation magnetization M_S=6.7 μ_B.     

Antiferromagnetism of perovskite EuZrO3

Polycrystalline EuZrO₃ has been synthesized by the solid-state reaction between EuO and ZrO₂, and its structural and magnetic properties have been investigated. Rietveld analysis of the X-ray diffraction pattern indicates that EuZrO₃ crystallizes in an orthorhombic perovskite structure. ¹⁵¹Eu Mössbauer effect measurement reveals that almost all the europium ions are present as the divalent state and occupy distorted sites with non-axial electric field gradients, in agreement with the orthorhombic structure. In contrast to previous reports, an antiferromagnetic transition was observed around 4.1 K. The magnetic structure below the Néel temperature has been discussed.     

The binary gallide Eu5Ga9 - crystal structure, chemical bonding and physical properties

The title compound was prepared from the elements by reaction in a sealed tantalum tube at 1320 K followed by slow cooling to 970 K or, alternatively, in glassy carbon crucibles with HF melting. The crystal structure of Eu₅Ga₉ was refined from single-crystal data: Cmcm, a=4.613(1) Å, b=10.902(3) Å, c=26.097(6) Å, Z=4, R_F=0.036, 811 structure factors and 46 variables. The structure is described as a three-dimensional network formed by gallium atoms with europium atoms embedded in the cavities. The bonding analysis (LMTO, ELF) confirmed this representation of the structure. Magnetic susceptibility measurements show Curie-Weiss behavior above 60 K with a magnetic moment per Eu atom of 8.12(1) μ_B, indicating divalent europium. Eu₅Ga₉ orders antiferromagnetically at 19.0(5) K with re-ordering at 6.0(5) K. The electrical resistivity shows a metallic temperature dependence and magnetic scattering. ¹⁵¹Eu Mössbauer spectroscopic experiments are compatible with divalent europium and show complex magnetic hyperfine field splitting below the ordering temperature.     

Studies on the compounds in the BaFeS system. I. Linear chain antiferromagnetism of Ba2FeS3 and related compounds Ba2CoS3 and Ba2MnS3

Magnetic susceptibilities of Ba₂FeS₃, Ba₂CoS₃, and Ba₂MnS₃ show rounded maxima at 130, 125, and 100 K, respectively, which are due to quasi-one-dimensional antiferromagnetic short-range ordering. Intrachain interactions, $\text{J}\text{k}$, are estimated to be ?20, ?15, and ?12 K, respectively. ⁵⁷Fe Mössbauer spectra of Ba₂FeS₃ and ⁵⁷Fe-doped Ba₂CoS₃ and Ba₂MnS₃ at 4.2 K show long-range antiferromagnetic ordering, due to the interchain interaction. The profile of Mössbauer spectra at 4.2 K is analyzed based on the coexistence of magnetic hyperfine and quadrupole interactions, and magnetic hyperfine fields at 4.2 K are estimated to be 36, 29, and 59 kOe, respectively.     

A study of magnetic interactions in M2EuRuO6 (M = Ca,Sr, Ba) by 151Eu Mössbauer spectroscopy

The series of compounds M₂EuRuO₆ (M = Ca, Sr, Ba) has been studied by ¹⁵¹Eu Mössbauer spectroscopy. X-Ray data show them to be structurally derived from the ABO₃ perovskite lattice, but only the Ba compound gives positive evidence to suggest ordering of the $\text{Eu}{}^{\mathrm{3+}}\text{Ru}{}^{\mathrm{5+}}$ cations. The ¹⁵¹Eu resonance shows magnetic hyperfine splitting at 4.2 K. The Ru⁵⁺OEu³⁺ORu⁵⁺ exchange takes place by admixture of low-lying excited states into the diamagnetic J = 0 ground-state of the Eu³⁺. The Curie temperatures are approximately 18, 31, and 42 K for the Ca, Sr, and Ba compounds. Detailed analysis shows that substantial disorder of cations occurs, being quite large for Ca, <8% for Sr, and <5% for Ba. However, it appears that considerable canting of the Ru⁵⁺ spins takes place in the Ba compound immediately below the Curie temperature as a result of the disorder and low anisotropy at the Ru sites. This effect is much reduced in the more distorted Sr compound.     

New Compounds of the ThCr2Si2-Type and the Electronic Structure of CaM2Ge2 (M: Mn-Zn)

Two new compounds were synthesized by heating mixtures of the elements at 975-1025 K and characterized by single-crystal X-ray methods. CaZn₂Si₂ (a=4.173(2) Å, c=10.576(5) Å) and EuZn₂Ge₂ (a=4.348(2) Å, c=10.589(9) Å) crystallize in the ThCr₂Si₂-type structure (space group I4/mmm; Z=2). Magnetic susceptibility measurements of EuZn₂Ge₂ show Curie-Weiss behavior with a magnetic moment of 7.85(5)μ_B/Eu and a paramagnetic Curie temperature of 10(1) K. EuZn₂Ge₂ orders antiferromagnetically at T_N=10.0(5) K and undergoes a metamagnetic transition at a low critical field of about 0.3(2) T. The saturation magnetization at 2 K and 5.5 T is 6.60(5) μ_B/Eu. ¹⁵¹Eu Mössbauer spectroscopic experiments show one signal at 78 K at an isomer shift of −11.4(1) mm/s and a line width of 2.7(1) mm/s compatible with divalent europium. At 4.2 K full magnetic hyperfine field splitting with a field of 26.4(4) T is detected. The already known compounds CaM₂Ge₂ (M: Mn-Zn) also crystallize in the ThCr₂Si₂-type structure. Their MGe₄ tetrahedra are strongly distorted with M=Ni and nearly undistorted with M=Mn or Zn. According to LMTO electronic band structure calculations, the distortion is driven by a charge transfer from M-Ge antibonding to bonding levels.     

A study of the solid solutions (EuO)1−x(LnN)x (where Ln = Nd,Eu, Gd) by europium-151 Mössbauer spectroscopy

The magnitude of the magnetic hyperfine field at Eu^II in the cubic solid solutions (EuO)_1?x(LnN)_x (where Ln = Nd, Eu, Gd) has been determined at 4.2°K by ¹⁵¹Eu Mössbauer spectroscopy. The resultant effective hyperfine field is found to be almost independent of composition because of a number of compensating effects.     

Multiple magnetic phase transitions,dilute Fe hyperfine fields and europium valence instabilities in RMn2Si2-xGex,R=rare earth

Mössbauer studies of dilute⁵⁷Fe and¹⁵¹Eu in RMn₂Si_2-xGe_x (R=La, Sm, Eu and Gd) at temperatures 4.2 K to 480 K have been performed. The diamagnetic iron and europium reveal the magnetic order of the Mn and rare earth sublattices through transferred hyperfine interactions. The⁵⁷Fe studies show that in LaMn₂Si₂, LaMn₂Ge₂, and SmMn₂Ge₂ the Mn is magnetically ordered above the known Curie temperatures, and the compounds are antiferromagnets up to T_N=470 K, 415 K and 385 K respectively. Studies of¹⁵¹Eu in R_1-xEu_xMn₂Si₂, (R=La, Gd) display Eu subspectra corresponding to Eu²⁺, Eu³⁺ and intermediate valant Eu. All display large magnetic hyperfine fields.     

Synthesis, structure and properties of SrAu3In3 and EuAu3In3—New indides with gold zig-zag chains

New indides SrAu₃In₃ and EuAu₃In₃ were synthesized by induction melting of the elements in sealed tantalum tubes. Both indides were characterized by X-ray diffraction on powders and single crystals. They crystallize with a new orthorhombic structure type: Pmmn, Z=2, a=455.26(9), b=775.9(2), c=904.9(2) pm, wR2=0.0425, 485 F² values for SrAu₃In₃ and a=454.2(2), b=768.1(6), c=907.3(6) pm, wR2=0.0495, 551 F² values for EuAu₃In₃ with 26 variables for each refinement. The gold and indium atoms build up three-dimensional [Au₃In₃] polyanionic networks, which leave distorted hexagonal channels for the strontium and europium atoms. Within the networks one observes Au2 atoms without Au-Au contacts and gold zig-zag chains (279 pm Au1-Au1 in EuAu₃In₃). The Au-In and In-In distances in EuAu₃In₃ range from 270 to 290 and from 305 to 355 pm. The europium atoms within the distorted hexagonal channels have coordination number 14 (8 Au+6 In). EuAu₃In₃ shows Curie-Weiss behavior above 50 K with an experimental magnetic moment of 8.1(1) μB/Eu atom. ¹⁵¹Eu Mössbauer spectra show a single signal at δ=−11.31(1) mm/s, compatible with divalent europium. No magnetic ordering was detected down to 3 K.     

Analysis of hyperfine interactions of Fe IN FeF2, MnF2 and ZnF2

Analysis of magnetic hyperfine interactions of Fe²⁺ in FeF₂, Fe²⁺:MnF₂ and Fe²⁺:ZnF₂ yields a core polarization hyperfine field H_c = −514 ± 30 kOe and a value of 〈r⁻³〉_eff = 3.9 ± 0.04 au.     

Magnetic properties of EuLn2O4 (Ln=rare earths)

Ternary rare earth oxides EuLn₂O₄ (Ln=Gd, Dy-Lu) were prepared. They crystallized in an orthorhombic CaFe₂O₄-type structure with space group Pnma. ¹⁵¹Eu Mössbauer spectroscopic measurements show that the Eu ions are in the divalent state. All these compounds show an antiferromagnetic transition at 4.2-6.3 K. From the positive Weiss constant and the saturation of magnetization for EuLu₂O₄, it is considered that ferromagnetic chains of Eu²⁺ are aligned along the b-axis of the orthorhombic unit cell, with neighboring Eu²⁺ chains antiparallel. When Ln=Gd-Tm, ferromagnetically aligned Eu²⁺ ions interact with the Ln³⁺ ions, which would overcome the magnetic frustration of triangularly aligned Ln³⁺ ions and the EuLn₂O₄ compounds show a simple antiferromagnetic behavior.     

Mössbauer 237Np and crystallographic studies of MIINpF6·3H2O (MII = Mn,Fe, Co) compounds

The compounds M^IINpF₆3H₂O with M^II = Mn, Fe, Co were prepared as single crystals by hydrothermal synthesis (T = 400°C, P = 2000 bars). CoNpF₆3H₂O crystallises in a monoclinic system with C2 space group. Cell parameters are a = 12.143(9) ā; b = 6.922(5) ā; c = 7.942(5) ā; β = 92.84°.The Mössbauer measurements were performed in a conventional He Cryostat. The Mössbauer source used in the experiments was a 500 mCi ²⁴¹Am metal with a conventional sine mode drive system.A microbalance magnetometer attached to a varying temperature Cryostat was used for the susceptibility measurements. The maximum applied magnetic field was 14KG.The Mössbauer spectroscopy of ²³⁷Np shows a magnetically split hyperfine spectrum at 4.2K for all those compounds.The spectra can be fitted with a magnetic hyperfine field associated to a quadrupole splitting using the linear correlation between B_eff and e²qQ. From isomer shift measurements, we confirm the IV charge state of Np in these 3 compounds.The magnetic susceptibility shows antiferromagnetic type transition. 1/ξ = f(T) follows a Curie-Weiss law above T_N.     

Ab initio MO LCAO UHF calculations of magnetic hyperfine interactions in NO3 and NO2−3. Hyperfine and quadrupole couplings from endor data for NO2−3

Ab initio methods, the unrestricted Hartree—Fock approximation, have been used to determine equilibrium geometries and magnetic hyperfine couplings of NO₃ and NO^2?₃. The electric quadrupole coupling constants of NO^2?₃ are evaluated both theoretically by UHF and experimentally using a new method for analyzing ENDOR data. The geometries and coupling constants for NO² and CO^?₂ have been recalculated.     

EPR study of the NO2+3 radical in irradiated K(UO2)(NO3)3 and K2(UO2)(NO3)4 single crystals

A new radical observed at low temperature in γ-irradiated K₂(UO₂)(NO₃)₄ single crystals has been tentatively assigned to a hitherto unknown oxyanion radical, NO²⁺₃. The assignment and the lack of ¹⁴N hyperfine structure, together with the g factors which are lower than the free-spin value, are discussed in terms of an orbital level scheme.     

Magnetic ordering of divalent europium in double perovskites Eu2LnTaO6 (Ln=rare earths): Magnetic interactions of Eu ions determined by magnetic susceptibility, specific heat, and Eu Mössbauer spectrum measurements

Structures and magnetic properties of double perovskite-type oxides Eu₂LnTaO₆ (Ln=Eu, Dy-Lu) were investigated. These compounds adopt a distorted double perovskite structure with space group P2₁/n. Magnetic susceptibility, specific heat, and ¹⁵¹Eu Mössbauer spectrum measurements show that the Eu²⁺ ions at the 12-coordinate sites of the perovskite structure are antiferromagnetically ordered at ∼4 K, and that Ln³⁺ ions at the 6-coordinate site are in the paramagnetic state down to 1.8 K.     

Magnetic and calorimetric studies on rare-earth iron borates LnFe3(BO3)4 (Ln=Y, La-Nd, Sm-Ho)

A series of rare-earth iron borates having general formula LnFe₃(BO₃)₄ (Ln=Y, La-Nd, Sm-Ho) were prepared and their magnetic properties have been investigated by the magnetic susceptibility, specific heat, and ⁵⁷Fe Mössbauer spectrum measurements. These borates show antiferromagnetic transitions at low temperatures and their magnetic transition temperatures increase with decreasing Ln³⁺ ionic radius from 22 K for LaFe₃(BO₃)₄ to 40 K for TbFe₃(BO₃)₄. In addition, X-ray diffraction, specific heat, and differential thermal analysis (DTA) measurements indicate that the phase transition occurs for the LnFe₃(BO₃)₄ compounds with Ln=Eu-Ho, Y, and its transition temperature increases remarkably with decreasing Ln³⁺ ionic radius from 88 K for Ln=Eu to 445 K for Ln=Y.     

A Fe Mössbauer study of charge ordering and phase separation in the rare-earth manganates, Nd0.5Ca0.5MnO3 and Nd0.5Sr0.5MnO3

Mössbauer studies of 2% ⁵⁷Fe-doped Nd_0.5Ca_0.5MnO₃ and Nd_0.5Sr_0.5MnO₃ have been carried out over the 4.2-300 K range after ensuring that such doping does not change their basic properties. The charge-ordering transition in these manganates is marked by abrupt changes in the quadrupole splitting. In the case of Nd_0.5Ca_0.5MnO₃, two phases manifest themselves on cooling below the charge-ordering transition temperature. The evolution of the spectra as a function of temperature shows that long-range magnetic order does not occur sharply. The observed evolution with temperature is different in the two materials studied. In Nd_0.5Ca_0.5Mn_0.98⁵⁷Fe_0.02O₃, it resembles that of a disordered magnetic material, whereas the temperature dependence of line shape of Nd_0.5Sr_0.5Mn_0.98⁵⁷Fe_0.02O₃ is typical of a superparamagnetically relaxed magnetic system. Although both the manganates show well-resolved magnetic hyperfine spectra at 4.2 K, the lines are slightly broad indicating possible coexistence of phases at low temperatures. A weak paramagnetic signal is also seen in the spectra of both the manganates at 4.2 K.     

Magnetic and Electrical Properties, Eu Mössbauer Spectroscopy, and Chemical Bonding of REAgMg (RE=La, Ce, Eu, Yb) and EuAuMg

Single-phase samples of REAgMg (RE=La, Ce, Eu, Yb) and EuAuMg were prepared by reacting the elements in sealed tantalum tubes in a high-frequency furnace. LaAgMg and CeAgMg adopt the hexagonal ZrNiAl-type structure, while EuAgMg, YbAgMg, and EuAuMg crystallize with the orthorhombic TiNiSi type. Chemical bonding was exemplarily investigatedfor EuAgMg and EuAuMg on the basis of TB-LMTO-ASAcalculations. Magnetic susceptibility measurements indicatePauli paramagnetism for LaAgMg and YbAgMg with room-temperature susceptibilities of 2.4(1)×10⁻⁹ and 1.5(1)×10⁻⁹ m³/mol, respectively. CeAgMg remains paramagnetic down to 2 K. The experimental magnetic moment of 2.52(2) μ_B/Ce above 50 K is compatible with trivalent cerium. EuAgMg and EuAuMg are paramagnetic above 50 K with experimentalmagnetic moments of 7.99(5) μ_B/Eu for the silver and 7.80(5) μ_B/Eu for the gold compound, indicating divalent europium. Ferromagnetic ordering is detected at T_C=22.0(3) K (EuAgMg) and T_C=36.5(5) K (EuAuMg). At 4.2 K and 5 T the saturation magnetizations are 7.1(1) and 7.3(1) μ_B/Eu for EuAgMg and EuAuMg, respectively. According to the very small hysteresis, EuAgMg and EuAuMg may be classified as soft ferromagnets. All compounds are metallic conductors. For EuAgMg and EuAuMg freezing of spin-disorder scattering is observed below T_C. At 78 K ¹⁵¹Eu Mössbauer spectra show isomer shifts of −9.00(4) and −8.72(8) mm/s for EuAgMg and EuAuMg, respectively. Full magnetic hyperfine field splitting is detected at 4.2 K with hyperfine fields of 17.4(1) and 18.3(2) T at the europium nuclei of EuAgMg and EuAuMg.     

Photon echoes in the 3P0 ← 3H4 transition of Pr3+/LaF3

Photon-echo quantum beats observed in the two-pulse and three-pulse photon echo of the ³P₀ ← ³H₄ transition in Pr³⁺/LaF₃ were used to determine the excited-state spin-hamiltonian. In addition we report on the anomalous stimulated photon echo observed in the same transition which in a magnetic field may acquire a lifetime of about 30 minutes.     

Hyperfine interactions in MgF2:Fe2+ and ZnF2:Fe2+ by Mössbauer spectroscopy

Measurement of the magnetic hyperfine interaction in paramagnetic Fe²⁺ in ZnF₂ and MgF₂ by Mössbauer spectroscopy is reported. The results, ?275 ± 3 kOe and ?270 ± 3 kOe for ZnF₂:Fe²⁺ and MgF₂:Fe²⁺ respectively are compared with a previous analysis of hyperfine interactions in the rutile fluorides.