Theoretical and comparative investigations of Yb ion in MWO4 and M′MoO4 scheelites crystals (M=Sr, Pb, Ca, Ba) and (M′=Sr, Pb, Ca, Cd)

The crystal-field model is applied to a series of scheelites crystals (CaWO₄, SrWO₄, PbWO₄, BaWO₄, CdMoO₄, CaMoO₄, SrMoO₄ and PbMoO₄) doped with the Yb³⁺ ion. The calculated crystal-field parameters present a general trend of variation with M²⁺ ionic radius of the host cation. The maximum splitting ΔE of the ²F_7/2 manifold of the Yb³⁺ ion is then obtained as a function of N_V crystal-field strength parameters. The agreement between experimental results and theoretical predictions for all investigated systems is very satisfactory. The crystal-field effects are very important for the prediction of emission energies of the Yb³⁺ ion in different scheelites.     

The lowest triplet state of luminescent scheelites: a study of the MoO24- ion by electron paramagnetic resonance with optical detection

The fine-structure and g tensors of the luminescent triplet state of the molybdate anion in single-crystals of CaWO₄:MoO₄, CdMoO₄ and PbMoO₄, all with the scheelite structure, are reported. In all three hosts the MoO24- ion is distorted on excitation. The directions of the principal axes of the fine-structure and g tensors support the idea that the effect results from the combined action of a Jahn-Teller instability and the crystal field. The hyperfine coupling of the ⁹⁵Mo and ⁹⁷Mo nuclei points towards excitation to an orbital with a large contribution of Mo 4d_3z2-2r.     

Bandgap-width correction for luminophores CaMoO<Subscript>4</Subscript> and CaWO<Subscript>4</Subscript>

Submicron-powder luminophores CaMoO₄ and CaWO₄ obtained via solid-phase reactions have been studied using diffuse-reflection (DR) spectroscopy and photoluminescence (PL) spectroscopy. It is found that the diffuse-reflection spectrum in the range of a fundamental absorption edge of <300 nm is distorted by PL overlapping, so that subsequent calculations of optical band gap E _g of luminophores CaMoO₄ and CaWO₄ result in an overestimation of this value. An algorithm for the correct processing of diffuse-reflection spectra is described. It is based on a subtraction of the photoluminescence spectrum in the range of fundamental absorption. The correct E _g values and energy values for the defect levels in the bandgap of CaWO₄ and CaMoO₄ are determined to amount to 4.78, 4.83, and 4.86 ± 0.01 eV and 3.97, 4.07, 4.16 ± 0.01 eV, respectively.     

Temperature dependence of the ground state splitting of Mn2+ in some scheelite type crystals

The EPR spectrum of Mn²⁺ in CaMoO₄, CdMoO₄, CaWO₄ and SrWO₄ has been investigated in the temperature range from 4.2–380 K. Results are given for the Spin-Hamiltonian parametersb ₂ ⁰ andb ₄ ⁰ . They are completed by data forb ₂ ⁰ of Mn²⁺ in SrMoO₄ [1] and discussed with respect to resonant vibrations.     

Fascinating morphologies of lead tungstate nanostructures by chimie douce approach

Lead tungstate occurs in nature as tetragonal stolzite of scheelite (CaWO₄) type and monoclinic raspite. In this work, we report, the typical growth of snowflake-like tetragonal stolzite and bamboo-leaf-like monoclinic raspite nanocrystals of PbWO₄ via a simple aqueous precipitation method and a polyol (polyethylene glycol-200) mediated precipitation method at room temperature (27 °C). The synthesised PbWO₄ nanocrystals were characterised by XRD, SEM, EDAX and TGA–DTA. The UV-Vis absorption and photoluminescence studies of PbWO₄ nanocrystals in the two morphologies were performed. The nuclei of PbWO₄ nanocrystals in aqueous medium self-assemble in a tetragonal manner to form the snowflake-like crystals. In polyol medium, PbWO₄ nuclei preferentially grow by oriented attachment process to form the bamboo-leaf-like morphology. The specific morphology of the regularly assembled PbWO₄ nanocrystals in the two phases finds applications in nanoelectronics and photonics. Compared to other well-known scintillators, PbWO₄ is most attractive for high-energy physics applications, because of its high density, short decay time and high irradiation damage resistance.     

Possibility of adjusting photoluminescence spectra of Ca scheelites (CaMoO<Subscript>4</Subscript>: Eu<Superscript>3+</Superscript> and CaWO<Subscript>4</Subscript>: Eu<Superscript>3+</Superscript>) to the emission spectrum of incandescent lamps

The peculiarities of the photoluminescence of compounds CaMoO₄: Eu³⁺ and CaWO₄: Eu³⁺ with the scheelite structure associated with a change in the short- and long-range orders of the crystal lattice upon a change in the activator (Eu³⁺) of the photoluminescence range in the interval 1–4 mol %, in which the photoluminescence of the matrix is preserved in the range 484–557 nm, are investigated using X-ray phase analysis as well as photoluminescence, Raman, and diffuse reflection spectroscopies. The introduction of Eu³⁺ ions leads to the reconstruction of the lattice so that up to 10% of these ions stimulate the formation of centrosymmetric localization upon the substitution of Ca²⁺ ions in the noncentrosymmetric positions. It is found that the spectral radiant emittance of the more effective luminophore CaMoO₄: Eu³⁺ can be adjusted to this parameter for an incandescent lamp for the Eu³⁺ concentration of 1–2 mol %.     

Isomer shift in BaSnO3 under a pressure up to 15 GPa

The dependence of the unit cell volume of BaSnO₃ on the pressure up to 15 GPa has been investigated and the constants of the Murnaghan equation of state B ₀ = 178.39 ± 4.09 GPa and B′₀ = 4.68 ± 0.56 have been obtained using the X-ray diffraction method. The change of the isomer shift (IS) in BaSnO₃ with a variation in the pressure P has been examined using the gamma resonance method. This quantity is ?IS(P)/?P = ?(0.00474 ± 0.0002) mm s^?1 GPa^?1 or, taking into account the measurements of the unit cell parameter under pressure, ?IS/?L = 1.42 mm s^?1Å^?1, where L is the tin-oxygen distance.     

High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

Polarization selection rules for the allowed optical transitions in europium-terbium double activated calcium tungstate phosphor

The paper is devoted to the problem of the optical anisotropy of the rare-earth ions occupying low-symmetry positions in crystals. The crystal field multiplets arising from LSJ terms of Eu³⁺ and Tb³⁺ ions in the crystal field of calcium tungstate scheelite (CaWO₄) are analyzed (S₄ point symmetry). The selection rules, in particular, polarization rules for the allowed electric dipole optical transitions in the electronic shells of the Eu³⁺ and Tb³⁺ in CaWO₄ host lattice are discussed. Special attention is paid to the study of the angular (polarization) dependence of the two-photon absorption that seems to be an effective tool for the understanding of the complicated optical pattern. The peculiarities of the anisotropy of the two-photon absorption prove to be specific for each allowed dipole transition in S₄ symmetry center.     

EPR of radiation induced MoO 4 3- -centres in lead tungstate

Paramagnetic MoO ₄ ^3- impurity centres are created in undoped PbWO₄ single crystals by X-ray excitation at liquid nitrogen temperature. The Spin-Hamiltonian data of the axial electron-centre are discussed in a covalent model which takes into account contributions of cation states. Characteristic differences in EPR- and thermoluminescent features of PbWO₄ with respect to other scheelite type tungstates can be explained in terms of the lead ion 6s ²-configuration.Part of thesis, Giessen 1977 (D26)     

Analysis of lead molybdate and lead tungstate synthesized by a sonochemical method

Lead molybdate and lead tungstate nanoparticles were successfully synthesized by a sonochemical method for 1 h. XRD patterns showed the body-centered tetragonal structures of PbMoO₄ and PbWO₄, and were in accordance with those of the simulation and JCPDS software. Calculated lattice parameters are a = b = 5.4233 Å and c = 12.1253 Å for PbMoO₄, and 5.4570 Å and 12.0995 Å for PbWO₄. They are in accordance with those of the corresponding JCPDS software. TEM images show that the particles were 29.09 ± 5.22 nm and 21.05 ± 2.68 nm for PbMoO₄ and PbWO₄, respectively. Raman and FTIR vibrations were investigated to identify a definite existence of the structures.     

Structural property of CsCl-type sodium chloride under pressure

The structure and equation of state of CsCl-type sodium chloride have been determined using high-pressure powder X-ray diffraction from 32 to 134 GPa. The CsCl-type phase remains stable over this entire pressure range. Pressure-volume data can be fitted with a Vinet equation of state with K_30 GPa=135.1 GPa, K′_30 GPa=3.9, and V_30 GPa=27.70 Å³. The nearest-neighbour distance between sodium and chlorine atoms decreased as pressure increased. Significant discrepancies of nearest-neighbour distance between previous theoretical predictions and this study were observed at pressures higher than 70 GPa.     

Variable-Temperature and High-Pressure Micro-Raman Spectra of Inorganic Artists' Pigments: Crystalline Wulfenite,Lead(II) Molybdate(VI), PbMoO4

Variable-temperature (?150°C to 600°C) and high-pressure (up to ～5 GPa) micro-Raman spectra have been obtained for the mineral wulfenite [lead(II) molybdate(VI), PbMoO₄], a main constituent of the artists' pigment, orange molybdate. The spectra were quite similar in both the temperature and the pressure studies, except for broadening and shifting of some peaks. No phase changes were detected, although there is possibly some amorphization beginning at ～600°C. The photoacoustic IR spectrum in the 1950–450 cm^?1 region is reported for characterization purposes. The long-term stability of PbMoO₄ with respect to extreme changes in both temperature and pressure illustrates the importance of orange molybdate in artwork and protective coatings.     

Luminescence decay of lead tungstate and lead molybdate

The temperature dependence of the luminescence decay of PbWO₄ and PbMoO₄ has been investigated as part of an attempt to identify the nature of the unknown emitting centres. This dependence is found to be anomalous.     

Pulsed laser induced synthesis of scheelite-type colloidal nanoparticles in liquid and the size distribution by nanoparticle tracking analysis

Pulsed laser ablation (PLA) of ceramic target in liquid phase was successfully employed to prepare calcium tungstate (CaWO₄) and calcium molybdate (CaMoO₄) colloidal nanoparticles. The crystalline phase, particle morphology and optical property of the colloidal nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and Raman spectroscopy. The produced stable colloidal suspensions consisted of the well-dispersed nanoparticles showing a spherical shape. The mechanism for the laser ablation and nanoparticle forming was discussed under consideration of photo-ablation process. Nanoparticle tracking analysis using optical microscope combined with image analysis was proposed to determine the size distribution function of the prepared colloidal nanoparticles. The mean size of the CaWO₄ and CaMoO₄ colloidal nanoparticles were 16 and 29 nm, with a standard deviations of 2.1 and 5.2 nm, respectively.     

Pressure dependence of the thermal conductivity of aluminium

The thermal diffusivity, a, of aluminium has been measured at pressures up to 2.5 GPa at room temperature, and from these results the pressure dependence of the thermal conductivity, λ, has been calculated. Both quantities increase with pressure. The increase in a amounts to 4.6% to 1 GPa and 10.4% to 2.5 GPa. The initial pressure coefficient of the electronic thermal conductivity λ_e is found to be [λ_e]^-1?λ_e/?P = 3.7 × 10^-2GPa^-1, which agrees very well with a recent theoretical calculation.     

High-pressure X-ray diffraction study of dimedone

Abstract

Dimedone (i.e. 5.5-dimethyl-I,3-cyclohexanedione) crystals, C₈HI₁₂O₂, have been studied at high pressures by X-ray diffraction using a Merrill-Bassett diamond-anvil cell. The unit-cell dimensions have been measured to 1.20(5) GPa and the structure has been determined at 0.95(5) GPa. The crystal compressibility is strongly anisotropic and non-linear, relatively strong compressibility of the crystals is observed along the helices of the hydrogen-bonded molecules. Small anomalous changes of the unit-cell dimensions are observed between 0.1 and 50 MPa. The main structural changes are compression of intermolecular contacts, but also an alongation of the O=C bond—accompanied with the compression of the hydrogen bond involving the carbonyl oxygen atom—has been observed. This elongation is consistent with similar effects reported on compression of the hydrogen bonds in 1,3-cyclohexanedione and 2-methyl-1,3-cyclopentanedione. Crystal data for the dimedone structure at 0.95 GPa: monoclinic, P2₁/c, a=9.909(6), b= 6.505(3), c=12.313(6) Å, β=14.51°, V=722.1(5) Å, Z=4, R=0.139 for 336 independent reflections.     

In-Situ High Pressure Raman Spectrum and Electrical Property of PbMoO4

In-situ high pressure Raman spectra and electrical conductivity measurements of scheelite-structure compound PbMoO4 are presented. The Raman spectrum of PbMoO4 is determined up to 26.5 GPa on a powdered sample in a diamond anvil cell （DAC） under nonhydrostatic conditions. The PbMoO4 gradully experiences the trans- formation from the crystal to amorphous between 9.2 and 12.5 GPa. The crystal to amorphous transition may be due to the mechanical deformation and the crystalographic transformation. Furthermore, the electrical conductivity of PbMoO4 is in situ measured accurately using a microcircuit fabricated on a DAC based on the van der Pauw method. The results show that the electrical conductivity of PbMoO4 increases with increases of pressure and temperature. At 26.5 GPa, the electrical conductivity value of PbMoO4 at 295K is 1.93 - 10-4 S/cm, while it raises by one order of magnitude at 430K and reached 3.33 - 10-3 S/cm. However, at 430K, compared with the electrical conductivity value of PbMoO4 at 26.5 GPa, it drops by about two order magnitude at 7.4 GPa and achieves 2.81 × 10^-5 S/cm. This indicates that the effect of pressure on the electrical conductivity of PbMoO4 is more obvious than that of temperature.