High-pressure behaviour and elastic properties of heavy rare-earth Gd monopnictides

Pressure-induced structural phase transition of gadolinium monopnictides GdX (X=As and Sb) has been studied theoretically using an inter-ionic potential theory. This method has been found quite satisfactory in case of the pnictides of rare-earth and describes the crystal properties in the framework of rigid-ion model. We have modified the ionic charge so that it may include the Coulomb-screening effect by the delocalization of f electron of the rare-earth ion. The anomalous structural properties of these compounds with many f electrons have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Gd ion with the p orbital of neighbouring pnictogen ion. Both the compounds are found to undergo from their initial NaCl (B₁) structure to body centered tetragonal (BCT) structure at high pressure and agree well with the experimental results. The BCT structure is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82–0.85. The nature of bonds between the ions is predicted by simulating the ion–ion (Gd–Gd and Gd–X) distance at high pressure. Elastic properties of these compounds have also been studied with their second-order elastic constants.     

Magnetoelastic contribution to the thermal expansion of the rare-earth phosphates TbPO4 and TmPO4

The thermal expansion of the rare-earth phosphates TbPO₄ and TmPO₄ having zircon structure has been investigated experimentally and theoretically. Significant magnetoelastic anomalies of the thermal expansion have been identified and the magnetoelastic contributions have been isolated allowing for corrections to the variation of the phonon contribution along the rare-earth ion series. It is shown that the magnetoelastic contribution to the thermal expansion of terbium and thulium phosphate is well described by the temperature dependence of the quadrupole moments of the rare-earth ions. The fully symmetric magnetoelastic coefficients for Tb³⁺ and Tm³⁺ are determined and a comparison is made of the magnetoelastic anomalies of the thermal expansion and the magnetoelastic coefficients of rare-earth phosphates and vanadates allowing for the differences in the crystal fields of the two isomorphic groups of zircons. Fiz. Tverd. Tela (St. Petersburg) 39, 106–111 (January 1997)     

Thermal vibrations and the structure of quasi-two-dimensional R 2CuO4 crystals (R=La, Pr, Nd, Sm, Eu, and Gd)

Thermal vibrations of ions in R ₂CuO₄ crystals (R=La, Pr, Nd, Sm, Eu, Gd) were studied by x-ray diffractometry. A comparative analysis of thermal displacements of the copper and rare-earth ions permitted a conclusion as to the main interactions responsible for the structural state of the CuO₂ sheets and of a crystal as a whole. The structural properties were found to correlate with the magnitude of the ionic radius and with the ground state of the rare-earth ions.     

Wide-band EPR spectroscopy of YAlO3: Tm3+ single crystals

The YAlO₃: Tm³⁺ single crystal has been studied on a wide-band EPR spectrometer. The EPR spectra of Tm³⁺ ions in the frequency range of 90–160 GHz have been detected for the first time. It has been confirmed that thulium ions substitute the position of Y³⁺ in the crystal lattice. The detected spectra have been described with the use of a spin Hamiltonian with the effective spin S = 1/2. A comparative analysis of the orientation of the magnetic axes of the Tm³⁺ paramagnetic center with earlier data on other rare-earth ions has been performed.     

Specific heat of Ce x La1 − x B6 in the low cerium concentration limit (x ≤ 0.03)

The specific heat of high-quality Ce _x La_{1 ? x} B₆ (x = 0, 0.01, 0.03) single crystals is studied in the temperature range 0.4–300 K. LaB₆ samples with various boron isotope compositions (¹⁰B, ¹¹B, ^nat B) are analyzed to estimate the effect of boron vacancies. The experimental data are used to take into account the electron component correctly under the renormalization of the density of states at T < 8 K, the contribution of the quasi-local vibrational mode of a rare-earth ion with the Einstein temperature Θ_E ≈ 152 K, the Debye contribution from the rigid cage of boron atoms with the Debye temperature Θ_D ≈ 1160 K, and the low-temperature Schottky contribution related to the presence of 1.5?2.3% boron vacancies in the rare-earth hexaborides. The detected low-temperature anomalies in the specific heat are shown to be interpreted in terms of the formation of two-level systems with an energy ΔE = 92–98 K caused by the displacement of rare-earth ions from their centrosymmetric positions. A scenario of heavy fermion formation that is alternative to the Kondo mechanism is proposed for the systems with a magnetic impurity.     

Analysis of oxygen shell splitting in hydrothermally grown single crystal ThO2(200)

Single crystals of ThO₂ have been synthesized using hydrothermal growth and studied using the X‐ray absorption fine structure (XAFS) technique. The extended X‐ray absorption fine structure (EXAFS) has been extracted from the XAFS and analyzed using a novel, computational Latin hypercube sampling method. The methodology not only confirms the expected space group and crystal structure, it also identifies the origin of a previously reported split O shell. Since EXAFS is a local order analysis technique, the O shell splitting is identified as an O atom occupying an interstitial site. This result is significant for examining O^2– transport in a ThO₂ matrix and corroborating research indicating partial Th 5f occupancy that is similar to hyper‐stoichiometric UO_2+x compounds. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

A study of the EXAFS associated with the K absorption discontinuity of copper in CuGa and CuGe alloys

The extended X-ray absorption fine structure (EXAFS) associated with the K absorption discontinuity of copper has been studied in the pure metal and in some copper-gallium and copper-germanium alloys, using a bent crystal X-ray spectrograph. The results obtained are discussed in the light of the recent theory of EXAFS proposed by Lytle, Sayers and Stern. It has been shown for the first time that there exists in alloys a correlation between the EXAFS parameter α₁ and e/a ratio. This correlation has been used to obtain the value of the lattice parameter “a” for Cu-27 at.% Ge alloy, which is not available in literature.     

Temperature evolution of the crystal structure of Bi1 − x Pr x FeO3 solid solutions

The crystal structure of solid solutions in the Bi_{1 ? x} Pr _x FeO₃ system near the structural transition between the rhombohedral and orthorhombic phases (0.125 ≤ x ≤ 0.15) has been studied. The structural phase transitions induced by changes in the concentration of praseodymium ions and in the temperature have been investigated using X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. It has been established that the sequence of phase transformations in the crystal structure of Bi_{1 ? x} Pr _x FeO₃ solid solutions with variations in the temperature differs significantly from the evolution of the crystal structure of the BiFeO₃ compounds with the substitution of other rare-earth elements for bismuth ions. The regions of the existence of the single-phase structural state and regions of the coexistence of the structural phases have been determined in the investigation of the crystal structure of the Bi_{1 ? x} Pr _x FeO₃ solid solutions. A three-phase structural state has been revealed for the solid solution with x = 0.125 at temperatures near 400°C. The specific features of the structural phase transitions of the compounds in the vicinity of the morphotropic phase boundary have been determined by analyzing the obtained results. It has been found that the solid solutions based on bismuth ferrite demonstrate a significant improvement in their physical properties.     

Crystal field effects in rare-earth ferroborates RFe3(BO3)4 with R = Nd, Tb, Dy, or Er

Crystal field effects in rare-earth ferroborates RFe₃(BO₃)₄ with various rare-earth elements are studied theoretically. The rare-earth magnetoelastic interaction Hamiltonian is written in a multipole approximation. The field and temperature dependences of the multipole moments and strain susceptibilities of rare-earth ions in the ferroborate structure are calculated. A comparative analysis of anomalies in the thermal expansion and elastic constants of rare-earth ferroborates with Tb and Dy ions having identical magnetic structure but differing in the degree of anisotropy of the rare-earth ion is performed.     

Intensity of the <Emphasis Type="Italic">f-f</Emphasis> transitions of Nd<Superscript>3+</Superscript>, Er<Superscript>3+</Superscript>, and Tm<Superscript>3+</Superscript> rare-earth ions in calcium niobium gallium garnet crystals

This paper reports on the results of the investigation into the intensities of the f-f transitions of Nd³⁺, Er³⁺, and Tm³⁺ ions in calcium niobium gallium garnet (CNGG) crystals. The values of the oscillator strengths and line strengths obtained for hypersensitive transitions and the intensity parameters Ω _t of the rare-earth ions in the CNGG crystals are compared with the corresponding quantities for crystals of other garnets and some oxide and fluoride crystals. The assumption is made that an increase in the oscillator strengths and line strengths for the hypersensitive transitions and the intensity parameters Ω₂ of the Nd, Er, and Tm ions in the CNGG crystals as compared to those for crystals of other garnets is associated with the specific features revealed in the crystal structure of the calcium niobium gallium garnet, in particular, with the lowering of the symmetry of the positions occupied by rare-earth ions in the crystal structure.     

EPR Spectroscopy of Impurity Thulium Ions in Yttrium Orthosilicate Single Crystals

The frequency-field and orientation dependences of the electron paramagnetic resonance (EPR) spectra are measured for impurity Tm³⁺ ions in yttrium orthosilicate (Y₂SiO₅) single crystals by stationary EPR spectroscopy in the frequency range of 50–100 GHz at 4.2 K. The position of the impurity ion in the crystal lattice and its magnetic characteristics are determined. The temperature dependences of the spin–lattice and phase relaxation times are measured by pulse EPR methods in the temperature range of 5–15 K and the high efficiency of the direct single-phonon mechanism of spin–lattice relaxation is established. This greatly shortens the spin–lattice relaxation time at low temperatures and makes impurity Tm³⁺ ions in Y₂SiO₅ a promising basis for the implementation of high-speed quantum memory based on rare-earth ions in dielectric crystals.     

Additive colouring of CaF2:Yb crystals: determination of Yb2+ concentration in CaF2:Yb crystals and ceramics

When growing CaF₂ crystal doped with rare-earth ions, most of these ions are present in a trivalent state. However, due to contact with graphite crucible, a small proportion of a number of ions (Eu, Sm, Yb and Tm) are reduced to a bivalent state. A similar situation takes place during fabrication of CaF₂ ceramics doped with rare-earth metals. This fact is of particular importance for laser CaF₂:Yb crystals (ceramics), a promising material for short-pulse, high-power, high-energy diode-pumped solid state lasers since the presence of bivalent Yb ions can be a source of thermal losses. To date, there has been no technique to determine Yb²⁺ concentration in as-grown crystals. The proposed technique is based on a total reduction of Yb³⁺ ions via the heating of as-grown CaF₂ crystals with known concentration of Yb in the reducing atmosphere of metal vapour and determining the cross section of absorption bands of Yb²⁺ ions. The knowledge of these parameters allows estimation of the Yb²⁺ content in CaF₂:Yb crystals or ceramics by analysing their absorption spectra. Examples of using this technique are given. The technology of CdF₂ crystals reduction (an “additive colouring”) and features of colouring of crystals doped with rare-earth ions are considered.     

Local surrounding of Mn in LaMn1−xCoxO3 compounds by means of EXAFS on Mn–K

A systematic study of LaMn_1?xCo_xO₃ perovskite series by means of X-ray absorption spectroscopy in the extended X-ray absorption fine structure (EXAFS) range of the K-absorption edge of Mn is reported. The Mn–K edge absorption measurements in the EXAFS region were performed to study the local surrounding of Mn ions. Polycrystalline powder samples of LaMn_1?xCo_xO₃ (x=0, 0.02; 0.2; 0.4; 0.5; 0.6; 0.8) prepared by solid-state reaction were used. The EXAFS spectra were analyzed with the FEFF8 computer program. The Mn–O distances of Mn to the nearest oxygen surroundings were evaluated for the samples in the series and compared with the Co–O distances obtained by EXAFS in V. Procházka et al., JMMM 310 (2007) 197 and with results of X-ray powder diffraction in C. Autret, J. Phys. Condens. Matter 17 (2005) 1601.     

Electron paramagnetic resonance of Gd3+ ions in powders of LaF3:Gd3+ nanocrystals

The observation of electron paramagnetic resonance of Gd³⁺ ions in nanosized powders of rare-earth fluorides LaF₃:Gd³⁺ has been reported. The measurements have been performed on a single crystal and micro- and nanosized powders at room temperature. Electron paramagnetic resonance spectra and spin-Hamiltonian parameters of Gd³⁺ ions have been obtained. A qualitative difference of spectra in nano- and micropowders due to the increase in the spread of the crystal field parameters with the decrease in the particle size has been found. The relationship between the single-crystal domain size and the hydrothermal treatment time has been established.     

Photomagnetic effect in molecular magnets based on nitrosyl complexes of ruthenium and rare-earth ions

The magnetic properties of new bifunctional molecular magnets based on nitrosyl complexes of ruthenium and thiacalix[4]arenes of rare-earth ions (Gd³⁺, Dy³⁺) have been investigated. A photoinduced decrease in the magnetization of the molecular magnet with rare-earth ions Gd³⁺ and the absence of a photomagnetic effect in crystals with rare-earth ions Dy³⁺ have been revealed at a temperature of 2 K. It has been found that, in the sample containing Dy³⁺ ions, the magnetization deviates by 6% from the calculated value for noninteracting ions. A comparison of the results obtained for two groups of isostructural samples, which differ only in the type of rare-earth ions, has demonstrated that the observed deviation of the magnetization is caused by the interaction of the orbital moment of the Dy³⁺ ions with the crystal field.     

Exafs study of structural phase transitions in RbVF4

Successive structural transitions of RbVF₄ have been studied with extended X-ray absorption fine structure (EXAFS) of Rb ions. It is found that there are some modulations in the pre-edge and post-edge regions of the X-ray absorption spectrum in the vicinity of the structural phase transitions above room temperature. By analyzing the EXAFS, it is also found that local spatial distortions around the Rb ions are induced at the structural transitions.     

Pressure effects on EXAFS Debye-Waller factor and melting curve of solid krypton

The pressure effects on atomic mean-square displacement, extended X-ray absorption fine structure (EXAFS) Debye-Waller factor and melting temperature of solid krypton have been investigated in within the statistical moment method scheme in quantum statistical mechanics. By assuming the interaction between atoms can be described by Buckingham potential, we performed the numerical calculations for krypton up to pressure 120?GPa. Our calculations show that the atomic mean-square displacement and EXAFS Debye-Waller factor of krypton crystal depend strongly on pressure. They make the robust reduction of the EXAFS peak height. Our results are in good and reasonable agreements with available experimental data. This approach gives us a relatively simple method for qualitatively calculating high-pressure thermo-physical properties of materials. Moreover, it can be used to verify future high-pressure experimental and theoretical works.     

硬脂酸稀土对PVC热稳定性的作用机理研究

采用FTIR及XRD对硬脂酸稀土稳定剂进行结构表征 ,可知硬脂酸稀土中硬脂酸酸根与稀土离子间的作用主要是离子键性质的 ,且硬脂酸稀土具有层状晶体结构 ,晶层中稀土离子倾斜于基面。刚果红法测定结果表明 ,随着硬脂酸稀土用量增加 ,PVC的热稳定时间呈现增加的趋势 ,4种不同稀土硬脂酸盐稳定能力大小顺序为Last>Ndst>Yst>Dyst。通过FTIR对PVC稀土稳定体系稳定机理进行预测 ,结果表明Last和Ndst两种稀土稳定剂能取代不稳定的Cl原子 ,阻止PVC分子链上脱HCl反应 ,改变构象使其达到稳定的效果。Yst和Dyst在改变构象方面贡献较不明显。     

Understanding the influence of nanoenvironment on luminescence of rare-earth ions

This paper presents an overview of the recent results on upconversion and photoluminescence of rare-earth ions in nanoenvironments. The role of the rare-earth ion concentration, crystal size and crystal phase on the up and downconversion emission of rare-earth ions in oxide nanocrystals and their underlying mechanisms are discussed. It is also found that the luminescence lifetime of the excited state rare-earth ions is sensitive to the particle crystalline phase and size. The analysis suggests that the modifications of radiative and nonradiative relaxation mechanisms are due to local symmetry structure of the host lattice and crystal size respectively     

Rutherford backscattering spectroscopy and surface morphology of amorphous As2Se3 films modified with complex compounds Ln(THD)3 (Ln=Eu,Tb, Er,Yb)

In this work we report the results on study of amorphous As₂Se₃ films modified with rare-earth dipivaloylmethanates Ln(THD)₃ (Ln=Eu, Tb, Er, Yb) using different diagnostic techniques. The rare-earth, oxygen and carbon concentrations have been determined by Rutherford backscattering spectroscopy and nuclear reaction analysis. The films have smooth surfaces with typical roughness the sizes of which have been changed with chemical modification. According to the results on nuclear microanalysis and IR spectroscopy the assumptions about the local environment of the rare-earth ions in amorphous matrix can be suggested.