Investigation on relationship between charge transfer position and dielectric definition of average energy gap in Eu3+-doped compounds

The dielectric definition of average energy gap E-g of the chemical bond has been calculated quantitatively in Eu3+-doped 30 lanthanide compounds based on the dielectric theory of chemical bond for complex structure crystals. The relationship between the experimental charge transfer (CT) energy of Eu3+ and the corresponding average energy gap E-g has been studied. The results show that the CT energy increases linearly with increasing of the average energy gap E-g. The linear model is obtained. It allows us to predict the CT position of Eu3+-doped lanthanide compounds with knowledge of the crystal structure and index of refraction. Applied to the Ca4GdO(BO3)(3):Eu and Li2Lu5O4(BO3)(3):Eu crystals, the predicted results of CT energies are in good agreement with the experimental values, and it can be concluded that the lowest CT energy in Li2Lu5O4(BO3)(3):Eu originates from the site of Lu1.

Deposition of GdVO4 : Eu3+ nanoparticles on silica nanospheres by a simple sol-gel method

The deposition and coating of GdVO4: Eu3+ nanoparticles on spherical silica was carried out using a simple sol - gel method at low temperature. The GdVO4: Eu3+-coated silica composites obtained were characterized by differential thermal analysis (DTA), thermogravimetric (TG) analysis, x-ray diffraction (XRD), Fourier-transform IR spectroscopy (FT-IR), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), photoluminescence spectra, and kinetic decay. It is found that the similar to 5 nm GdVO4: Eu3+ nanoparticles coating the silica spheres are crystal in the as-prepared samples and the crystallinity increases with increasing annealing temperature. The composites obtained are spherical in shape with an average size of 100 nm. The GdVO4: Eu3+ nanoparticles are linked with silica cores by a chemical bond. The photoluminescence spectra of the obtained GdVO4: Eu3+-coated silica composites are similar to those of the bulk GdVO4: Eu3+ phosphors. The strongest peak is near 617 nm, which indicates that Eu3+ is located in the low symmetry site with non-inversion centre.

Silica-coated Y2O3 : Eu nanoparticles and their luminescence properties

Crystalline Y2O3:Eu is of paramount significance in rare earth materials and research on luminescence spectra. In this work, the nanocrystalline Y2O3:Eu was coated with silica by a facile solid state reaction method at room temperature. The transmission electron microscope (TEM) photographs showed that the prepared Y2O3:Eu particle is polycrystalline with the size of 20 nm, the size of silica-coated particle is about 25 nm. The XPS spectra indicated that the silica layer is likely to interact with Y2O3:Eu by a Si-O-Y chemical bond. The luminescence spectra showed that the intensity of ground samples is lower than that of unground ones, the intensity of silica-coated phosphors is higher than that of the ground samples, while almost the same as that of the unground ones. Therefore, the silica coating decreases the surface defects of nanoparticles of the nanocrystalline Y2O3:Eu, thus increasing their luminescent intensity.

Coating Gd2O3 : Eu phosphors with silica by solid-state reaction at room temperature

Silica coating on Gd2O3:Eu particles was obtained by a simple method, e.g. solid-state reaction at room temperature. The urea homogeneous precipitation method was used to synthesize the Gd2O3:Eu cores. Transmission electron microscopy (TEM) shows that the core particles are spherical with submicrometer size which is the soft agglomerates with nanometer crystallites. The TEM morphology of coated particles shows that a thin film is coated on the surface of Gd2O3:Eu cores. Scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS) analysis indicate that the coating of silica can be used to avoid agglomeration of Gd2O3:Eu particles to obtain smaller particles. X-ray photoelectron spectra (XPS) show that silica is coated on the surface of core particles by forming the chemical bond. Photoluminescence (PL) spectra conform that Gd2O3:Eu phosphors remain well-luminescent properties by the silica coating.

Barycenter of energy of lanthanide 4f(N)-(1)5d configuration in inorganic crystals

A semiempirical method for the evaluation of the barycenter of energy of 4f(N-1)5d configurations is presented. The environmental factors affecting the barycenter are given to be the bond volume polarization, fractional covalence of the chemical bond between the central ion and the nearest anion, and presented charge of the nearest anion in the chemical bonds. The barycenter energies of 4f(N-1)5d configurations of Eu2+ and Ce3+ are calculated in various crystals, and the results are in good agreement with the experimental values. A relationship is found between the barycenter of energy of the 4f(N-1)5d configuration on Eu2+ method offers the advantage of applicability to a broad class of luminescence materials and initiates a link between macroscopic properties and microscopic structure.

Dependence of charge transfer energy on crystal structure and composition in Eu3+-doped compounds

We report a method for estimating the positions of charge transfer (CT) bands in Eu3+-doped complex crystals. The environmental factor ( he) influencing the CT energy is presented. he consists of four chemical bond parameters: the covalency, the bond volume polarization, the presented charge of the ligand in the chemical bond, and the coordination number of the central ion. These parameters are calculated with the dielectric theory of complex crystals. The relationship between the experimental CT energies and calculated environmental factors was established by an empirical formula. The calculated values are in good agreement with the experimental results. Such a relationship was confirmed by detailed analysis. In addition, our method is also useful to predict the charge-transfer position of any other rare earth ion.

Calculation of the thermal expansion coefficient for Bi2Sr2CaCu2O8

An estimation method of thermal expansion coefficient in term of lattice energy which was developed earlier for simple materials is extended to a complex material of Bi2Sr2CaCu2O8 (Bi-2212). The calculation of the chemical bond property and thermal expansion coefficient of Bi-2212 has been carried out and the theoretical values were in good agreement with the corresponding experimental results. The dependence of the thermal expansion coefficient on the different structures and on the flexible oxidation states of Bi and Cu are investigated. The results indicate that the thermal expansion coefficients of Bi-2212 are insensitive to the low lattice distortion of the average structure and the changes of formal valences of Bi and Cu ions.

Predicting the position of the spin-forbidden band for Tb3+ ions in crystal hosts

The energy difference DeltaE between the spin-allowed and spin-forbidden states of Tb3+ in crystals is studied. The environmental factor he representing the character of the host is redefined by using the chemical band of complex crystals. The relationship between h(e) and DeltaE is found to be a linear relation. The results show that the energy difference between the spin-forbidden and spin-allowed states for Tb3+ ions in crystals can be predicted from the environmental factor.

Lattice energy estimation for inorganic ionic crystals

An empirical method based on chemical bond theory for the estimation of the lattice energy for ionic crystals has been proposed. The lattice energy contributions have been partitioned into bond dependent terms. For an individual bond, the lattice energy contribution made by it has been separated into ionic and covalent parts. Our calculated values of lattice energies agree well with available experimental and theoretical values for diverse ionic crystals. This method, which requires detailed crystallographic information and elaborate computation, might be extended and possibly yield further insights with respect to bond properties of materials.

Hardness of covalent crystals

Based on the idea that the hardness of covalent crystal is intrinsic and equivalent to the sum of the resistance to the indenter of each bond per unit area, a semiempirical method for the evaluation of hardness of multicomponent crystals is presented. Applied to beta-BC2N crystal, the predicted value of hardness is in good agreement with the experimental value. It is found that bond density or electronic density, bond length, and degree of covalent bonding are three determinative factors for the hardness of a polar covalent crystal. Our method offers the advantage of applicability to a broad class of materials and initializes a link between macroscopic property and electronic structure from first principles calculation.

Silicon dioxide coating of CeO2 nanoparticles by solid state reaction at room temperature

The synthesis Of SiO2 coated CeO2 nanoparticles by humid solid state reaction at room. temperature is described. Transmission electron microscope results show that CeO2 Particles were coated with a layer Of SiO2. Binding energy of Ce 3d(5/2) was shifted from 883.8 to 882.8 eV after coating in the XPS Ce 3d spectra. This confirms the chemical bond formation between SiO32- and Ce4+. Because the surface photovoltage property of CeO2 nanoparticles that were used as core materials in the experiment approaches to that of CeO2 macroparticles, peak P2 (electron transition from 0 2p on surface to Ce 4f) disappeared in the surface photovoltage spectrum of CeO2 nanoparticles. Also, the effect Of SiO2 on the electron transition from 0 2p to Ce 4f results in the lowering of surface photovoltage response intensity of P1 peak (electron transition from 0 2p in bulk to Ce 4f).

Bonding and Mossbauer isomer shifts in (Tl, Pb)-1223 cuprate

By using the clinical bond theory of dielectric description, the chemical bond parameters of (Tl.Pb) - 1223 was calculated. The results show that the Sr-O, Tl-O, and Ca-O types of bond have higher ionic character and the Cu-O types of bond have more covalent, character. Mossbauer isomer shifts of Fe-57 and Sn-119 doped in (Tl, Pb) -1223 were calculated by using the chemical environmental factor, h, defined by covalency and electronic polarizability. Four valence state tin and three valence iron sites were identified ill Fe-57, and Sn-119 doped (Tl, Pb) -1223 superconductor. We conclude that all of' the Fe atoms substitute the Cu at square planar Cu (H site, whereas Sn prefers to Substitute the square pyramidal Cu (2) site.

Investigation of covalency and spectrum shifts in 3d transition-metal compounds

By using a correction factor of d electron effects on bond, PV theory is applied to the calculation of chemical bond;parameters of d transition-metal compounds. Racah parameters and Mossbauer isomer shifts are calculated, and the results are agreement with the experimental values.

Theoretical studies of nonlinear optical properties of compounds K(4)Ln(2)(CO3)(3)F-4 (Ln=Pr, Nd, Sm, Eu, Gd)

K(4)Ln(2)(CO3)(3)F-4 (Ln=Pr, Nd, Sm, Eu, Gd) is a special type of frequency doubling compound, whose crystal structure exhibits a scarcity of fluorine ions. This leads to two different coordination polyhedrons in the general position of K(2) atoms: [K(2)O6F(1)(2)F(2)] and [K(21)O6F(1)(2)] in a 2/1 ratio. The chemical bonding structures of all constituent atoms of the compound K4Gd2(CO3)(3)F-4 (KGCOF) are comprehensively studied; moreover, the relationship between the chemical bonding structure and the nonlinear optical (NLO) properties is investigated from the chemical bond viewpoint. The theoretical prediction of the NLO tensor coefficient d(11) of KGCOF is in agreement with experimental observation. Theoretical analyses show that the nonlinearity of this crystal type mainly originates from K-O bonds. In addition, the correlation between the NLO tensor d(11) and the refractive index n(0) of KGCOF is discussed. (C) 2000 American Institute of Physics. [S0021-8979(00)07506-X].

Preparation and characterization of nanometer-sized CeO2/polystyrene hybrid material

Nanometer-sized CeO2/polystyrene hybrid material was prepared using reversed micelles microemulsion method. XRD analysis revealed that the CeO2 nanoparticles in polystyrene were amorphous. XPS patterns indicated that the hybrid material was not a simply physical mixture, but a certain strength of chemical bond between CeO2 nanoparticles and polystyrene existed. FTIR patterns revealed that the absorption of Ce-O bond in hybrid material was blue-shifted.