Single crystal and powder EPR study of trivalent gadolinium in Cs2NaBiCl6 in the 30-300 K interval

A crystalline electric field cubic symmetry site has been reported for Gd³⁺ in Cs₂NaBiCl₆ at room temperature. This host exhibits an apparent structural transformation below 100 K that is completely reversible. However, an EPR examination for a powdered sample of Cs₂NaBiCl₆:Gd³⁺ clearly demonstrates that there are no new large crystalline electric field symmetry sites arising between the transition temperature (100 K) and 30 K, suggesting, therefore, that the site symmetry remains predominantly cubic even at temperatures close to 30 K. In order to substantiate this statement, a computer EPR powder simulation was performed using the single-crystal-spin-Hamiltonian parameters obtained from the three different sites that emerge from the original site while observed at 30 K. A remarkable agreement is observed while comparing the computer-simulated data with that of powdered experimental data. It is important to mention here that several attempts were done trying to fit the observed new spectra to lower crystalline field symmetries, however, our best analytical adjustment was obtained with the cubic spin-Hamiltonian.Below 30 K, new structural transitions are present and the lattice loses its original cubic nature. However, at 10 K the EPR spectrum of the crystal again shows only seven lines that are very broad. This new spectrum cannot be fitted with previously used cubic spin-Hamiltonian parameters.     

Estimation of T1 for Co2+ ions from the temperature variation of the ESR linewidths for VO2+ in Cs2Co(SeO4)2·6H2O single crystals

The electron spin resonance of VO²⁺ is studied in single crystals of Cs₂M″ (SeO₄)₂·6H₂O (M″ = Zn, Co) from 290 to 77 K at ～ 9.45 GHz. The line broadening of VO²⁺ spectra on cooling the Cs₂Co(SeO₄)₂·6H₂O crystal is explained on the basis of host spin-lattice relaxation narrowing. T₁ for Co²⁺ is estimated to be ≈ 1.7 × 10^?12 sec. at 290 K.     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

Soft mode and structural phase transition in the cubic elpasolite Cs2NaNdCl6

Inelastic neutron scattering measurements have been performed on the elpasolite Cs₂NaNdCl₆ in the cubic phase. It is found that the cubic-to-tetragonal phase transition at 137 K is driven by a zone-center soft phonon mode. The mode is of symmetry Λ^′₁₅ and corresponds to a rotation of the Cl₆ octahedra. The characteristics of the phase transition are similar to those observed in some compounds of the perovskite and antifluorite structures.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Scintillation and anomalous emission in elpasolite Cs2LiLuCl6:Ce

The luminescence and scintillation properties of Cs₂LiLuCl₆:0.5%Ce³⁺ are presented. Special attention is devoted to a 9.4 ns fast emission at 275 nm that can only be excited via the highest cubic field 5d_e state of Ce. Contrary to Cs₃LuCl₆ and Cs₂LiYCl₆, where the same type of fast emission was observed, the emission in Cs₂LiLuCl₆ is still observed at room temperature. Assuming that the 5d_e state is located inside the host conduction band (CB), we propose that the emission originates from a mixed state at or just below the bottom of the CB and ends at the 4f ground state of Ce³⁺. To proof this model we studied the thermal quenching of the anomalous luminescence and performed X-ray photoelectron spectroscopy. A model for a temperature-activated energy transfer from the anomalous state to the lowest 5d_t excited state of Ce³⁺ explains most of the results. Besides the 275 nm emission, the material shows 5d_t-4f Ce³⁺ emission at 370 and 406 nm and 2 ns fast core-valence luminescence when excited with 16-22 eV photons. The scintillation properties of Cs₂LiLuCl₆:Ce are briefly discussed.     

Unusual luminescence of octahedrally coordinated divalent europium ion in Cs2MP2O7 (M=Ca, Sr)

The excitation and emission spectra of octahedrally coordinated europium ion (Eu²⁺) ions in Cs₂M²⁺P₂O₇ (M²⁺=Ca, Sr) are reported and discussed. The remarkable features of the Eu²⁺ luminescence in these phosphate materials include (a) very large Stokes shift of emission (∼1 eV), (b) high luminescence quenching temperature, and (c) unusually low energy of the emitted photons for Eu²⁺ luminescence in phosphate-based materials. The broad emission bands of Eu²⁺ in Cs₂CaP₂O₇ and Cs₂SrP₂O₇ peak at 607 and 563 nm, respectively. The Stokes shift, crystal field splitting, centroid shift and the red shift of the Eu²⁺ 4f⁶5d¹ electronic configuration have been estimated from the relevant optical data. The radiative lifetime of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is ∼1.2 μs. The nature of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is discussed and arguments are presented to associate the luminescence with an extreme case of normal 4f⁶5d¹→4f⁷[⁸S_7/2] emission.     

4fN-15d energy levels of lanthanides: aquasi-angular-momentum approach and its application to Cs2NaYF6:Er3+

<正>The spin-orbit interaction of the 5d electron needs to be taken into account to give the proper energy structure for the 4f^N-15d configuration of heavy lanthanide ions occupying a site with ligands forming an octahedron.This paper derives theoretical results for the energy structure by treating the t₂ orbitals as quasi p orbitals and then using angular-momentum coupling techniques.An analytic expression for the electric dipole absorption line strengths between 4f^N multiplets and 4f^N-15d states is given in terms of various angular-momentum quantum numbers and re-coupling coefficients.The result is then applied to interpret the excitation spectrum of Cs₂NaYF₆:Er³⁺.The high-spin and low-spin states of Cs₂NaYF₆:Er³⁺ are discussed in terms of the wavefunctions obtained by using the developed theoretical model.     

Optical spectroscopy of Yb in the Cs2NaYF6 single crystal

Results of the optical spectroscopy investigation of the cubic paramagnetic center Yb³⁺ ion in the Cs₂NaYF₆ single crystal are presented. The Stark level energies of the Yb³⁺ multiplets are established from absorption, luminescence and excitation luminescence spectra and the crystal field parameters are calculated. Information about the phonon spectra of Cs₂NaYF₆ crystals is obtained from the electron-vibrational structure of the optical absorption and luminescence spectra.     

Novel RCo5Ga7 intermetallic compound

The novel RCo₅Ga₇ (R=Y, Tb, Dy, Ho and Er) intermetallic compounds have been synthesized, and their crystallographic and magnetic properties have been studied using X-ray diffraction and magnetic measurement. RCo₅Ga₇ crystallizes in an orthorhombic structure with ScFe₆Ga₆ type. The space group is Immm, and Z=2. According to the structural refinement result, the 2a, 4e, 4f, 4g, 4h, and 8k crystal positions are occupied by 2R, 4Ga^I, 4(Ga^II, Co^I), 4Ga^III, 4(Ga^IV,Co^II), and 8(Co^III,Ga^V), respectively. The RCo₅Ga₇ intermetallic compound can be stabilized in the range of the radius ratio of R_Re/R_(Co,Ga)<1.36. The RCo₅Ga₇ compound exhibits a paramagnetic behavior. The magnetization at 5 K ranges from 28.93 to 40.62 emu/g.     

Structural first-order transformation in La2/3Ba1/3MnO3: ESR study

We have studied by the electron-spin resonance (ESR) and static magnetic field techniques, the La_2/3Ba_1/3MnO₃ perovskite, which was previously shown to exhibit a martensitic phase transformation in the vicinity of T_s∼200 K [Physical Review B 68, 054109 (2003)], leading to its structural phase-segregated state. Resonant absorptions reveal that in the temperature interval from 100 K to 340 K the compound represents a mixture of two ferromagnetic phases possessing different magnetizations, in varying proportions depending on the temperature, and a small amount of a paramagnetic phase. The results agree well with the previous neutron diffraction study. Applied in the ESR experiments, magnetic fields (2–6 kOe) strongly affect the magnetization curves: even magnetic field as high as 700 Oe modifies the anomaly in the phase transformation region and removes the difference between the zero-field cooled and field-cooled magnetization curves, which implies that the difference in the magnetic susceptibility of the coexisting phases is small and the magnetic domain configuration can be easily changed.     

The effect of sulfide substitution in the mixed conductor Cu7PSe6

Cu₇PSe₆ is a mixed conductor exhibiting structural phase transitions above and below room temperature that are accompanied by step-like changes in electrical conductivity. The substitution of S²⁻ for Se²⁻ in Cu₇PSe₆ significantly enhances electrical conductivity at room temperature compared to that observed for the pure compound. In the case of Cu₇P(Se_0.80S_0.20)₆, a nearly temperature-independent electrical conductivity exceeds 1 S/cm with no evidence of any phase transitions throughout the temperature interval 200-400 K. However, the ionic contribution accounts for just 2% of the total electrical conductivity in this solid solution at room temperature.     

Electron spin resonance investigation of the structural phase transitions in Alurea6(ClO4)3 and Ga urea6(ClO4)3

Second order structural phase transitions in Alur₆(ClO₄)₃ and Gaur₆(ClO₄)₃ with T_c ～ 300 K are studied by means of ESR on single crystals doped with the analogous Cr(III) compound. The transitions are antiferrodistortive and of the displacive type, the displacements resulting from the condensation of a X₂ mode $\text{(k = (0}\text{1}\text{2}\text{1}\text{2}\text{))}$ of the ClO₄ ions. The ESR parameters have the same temperature dependence as the order parameters and can be described by D and E～φ～. The space group describing the structure changes from S₆² to S₂¹, and the number of domains is multiplied by three. Above 300 K the crystals already consist of two domains, resulting from a ferrodistortive phase transition D_3d⁶ → S₆². The actual transition temperature of the latter phase transition lies at some temperature above the decomposition temperature of the crystals.     

Scattering properties of the ultracold 133Cs2 triplet state

The elastic scattering properties of ultracold 133Cs2 triplet state are investigated in detail.We construct a potential curve of the 133Cs2 triplet state,based on the latest ab initio molecular potential data and show how the scattering parameters are obtained by using three methods:the Numerov method,the semiclassical method and the variable phase method,where the scattering lengths of the 133Cs2 triplet state,i.e.301.79a0,300.67a0 and 310.81a0 are obtained respectively,with a0 being the Bohr radius.We also calculate the effective range and the number of bound states for the 133Cs2 triplet state.Our results are in agreement with the recent experimental data and the theoretical calculations.This confirms that the results of the scattering properties of the ultracold 133Cs2 triplet state,calculated by using these three methods,are reliable.     

Luminescence of CsPbBr3-like quantum dots in CsBr single crystals

Luminescence and decay kinetics of the Pb²⁺ aggregates in CsBr host crystals were measured in the 4–300 K temperature interval and in 10⁻¹⁰–10⁻³ time scale. Their emission properties are similar to those of CsPbBr₃ bulk crystal showing a subnanosecond free exciton emission in the 520–540 nm spectral region and slower trapped exciton emission in the 530–580 nm spectral region. An efficient energy exchange between the free and trapped exciton states is shown by the temperature dependencies of emission spectra. The quantum size effect is demonstrated in the high energy shift and broadening of the absorption and emission spectra and an estimate of the size of the CsPbBr₃-like aggregates is provided. Independent evidence of the presence of the CsPbBr₃ and Cs₄PbBr₆ aggregated phases in the CsBr host was obtained by X-ray structural studies.     

Polarized reflectance spectrum of β-(BEDT-TTF)2PF6

The polarized reflectance spectrum of β-(BEDT-TTF)₂PF₆ was measured over the spectral range from 720 cm^?1 to 25, 000 cm^?1 at 293 K (semiconductive phase) and at 318 K (metallic phase). The infrared band found in the conductivity spectrum, which was obtained by the Kramers-Kronig transformation of the reflectance data, is interpreted as the one associated with inter-band transition.     

金属间化合物PrMn6Sn6的结构、磁性与119Sn穆斯堡尔谱研究

采用电弧熔炼法制备了金属间化合物PrMn₆Sn₆.X射线衍射表明该化合物具有HoFe₆Sn₆型(空间群为Immm)晶体结构.磁测量表明该化合物为铁磁性，居里温度为325　K.在15—360　K范围内测量了¹¹⁹Sn穆斯堡尔谱，得到了8个Sn原子晶位的转移超精细场随温度的变化，并且讨论了Mn亚晶格与Pr亚晶格的磁有序方向. 关键词： 6Sn₆')" href="#">PrMn₆Sn₆ 穆斯堡尔谱 磁结构     

Structure,thermal behavior,and dielectric properties of new cesium hydrogen sulfate arsenate: Cs<Subscript>2</Subscript>(HSO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs₂(HSO₄)(H₂AsO₄). The title compound crystallizes in the monoclinic system with the P2₁/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm^?1and 1200–50 cm^?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs₂(HSO₄)(H₂AsO₄) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10^?4 Ω^?1 cm^?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”_max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.     

Raman scattering study of the phase sequence in A2BX4 halides

Raman spectra of Cs₂ZnI₄ single crystal have been measured in different scattering orientations covering the successive phase transitions down to 68 K. Two second order anomalies at around ice temperature (270 K) and at ～ 92 K are observed. The anomaly around ice temperature exhibits the features of a normal-incommensurate transition evidenced by softening of a low-lying lattice phonon whose frequency decreases as the transition temperature is approached from below whereas the latter one appears to arise from usual structural distortions.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.