Structural and magnetic properties of (PrxSm1-x)Mn2Si2

Crystallographic and magnetic properties of intermetallic compounds (PrxSm1-x) Mn2Si2 (x = 0 similar to 0.80) have been investigated by X-ray powder diffraction, XPS and magnetic measurements. All the compounds crystallize in ThCr2Si2-type structure. Substitution of Pr for Sm leads to the increase of the lattice constants and the transition from antiferromagnetism (AFM) to ferromagnetism (FM). The valence-fluctuation in the compounds was observed and the relation between the change of electron binding energy and magnetic properties was also discussed preliminarily.

Luminescent properties of divalent samarium-doped strontium hexaborate

The valence change of samarium from trivalent to divalent in strontium hexaborate (SrB6O10) prepared in air is observed. The temperature dependence of the luminescence and vibronic transitions of Sm2+ are studied. The Sm2+ ions occupy three crystallographic sites. With increasing temperature, the D-5(0)-->F-7(0) transition line exhibits red shifts, and the half-width increases. At room temperature, due to the thermal population through the 4f(5)5d channel, the D-5(1)-->F-7(J) transitions are observed even though the vibrational energy is very close to the energy gap between the D-5(1) and D-5(0) levels in the host. A coupled phonon energy of about 108 cm(-1) is determined from the vibronic transitions of Sm2+ in the host.

Study on the bond covalency and bond susceptibility in NdCr1-xMxO3 (M=Mn, Fe, Co)

Bond covalency, bond susceptibility and macroscopic linear susceptibility in NdCr1-xMxO3 (M=Mn, Fe, Co, 0.0 less than or equal to x less than or equal to 1.0) are investigated by complex chemical bond theory. The results indicate the bond covalencies are insensitive to the doping level. With the increasing doping level, the macroscopic linear susceptibilities increase for M=Mn, Fe, decrease for M=Co. The valence state of Cr can be strongly influenced by the properties of the doping ions.

Semiempirical study on the valences of Cu and bond covalency in Y1-xCaxBa2Cu3O6+y

The valences of Cu and bond covalencies in Y1-xCaxBa2Cu3O6+y, have been investigated using complex chemical bond theory, This theory is the generalization of Phillips, Van Vechten, Levine, and Tanaka's scheme. The results indicate that the valences of Cu(1) and Cu(2) in our calculation agree well with those obtained by the bond valence sum method. The valences of Cu(1) and Cu(2) in our calculation also suggest that the holes introduced by Ca substitution only reside in CuO2 planes and there is a competing mechanism for the hole density in CuO2 planes between,Ca doping and oxygen depletion. These conclusions are in satisfactory agreement with experiments. The calculated ordering of covalencies is Cu(1)-O(4)>Cu(1)-O(1)>Cu(2)-O(2,3)>Cu(2)-O(1)>Ca-O>Y-O similar to Ba-O, regardless of the Ca doping level and oxygen content. [S0163-1829(98)03325-6].

Physico-chemical properties and catalytic behavior of LnSrNiO(4) mixed oxides for NO decomposition

A series of LnSrNiO(4)(A(2)BO(4), Ln = La, Pr, Nd, Sm, Gd) mixed oxides with K2NiF4 structure, in which A-site(Sr) was partly substituted by individual light rare earth element, was prepared. The solid state physico-chemical properties including crystal structure, defect structure, IR spectrum, valence state of H-site ion, nonstoichiometric oxygen, oxygenous species, the properties of oxidation and reduction etc. as well as the catalytic behavior for NO decomposition on these mixed oxides were investigated. The results show that all of these mixed oxide catalysts have high activity for the direct decomposition of NO(at 900 degrees C the conversion of NO is more than 90%). The effect of the substitution of light rare earth elements at A-site on catalytic behavior for NO decomposition was elucidated.

Bond-charge calculation of nonlinear optical susceptibilities of LiXO3 type complex crystals

Second order nonlinear optical (NLO) tensor coefficients of LiXO3 (X = I, Nb, Ta) type crystals have been evaluated on the basis of the dielectric theory of complex crystals and the modified bond charge model. The current method is capable of calculating single bond contributions to the total second order NLO susceptibility. The tenser values thus calculated agree well with experimental data. By introducing the subformula equation and the concept of the effective charge of one valence electron, we are able to successfully treat such complex crystals as LiXO3 type compounds. In addition, the bond charge expression is modified to a more reasonable form for complex crystals. (C) 1998 Elsevier Science B.V.

Theoretical investigation of LaC3n+ (n = 0, 1, 2) clusters by density functional theory

LaC3n+ (n = 0, 1, 2) clusters have been studied using B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method. The basis set is Dunning/ Huzinaga valence double zeta for carbon and [2s2p2d] for lanthanum, denoted LANL1DZ. Four isomers are presented for each cluster; two of them are edge binding isomers with C-2 upsilon symmetry, the other two are Linear chains with C-infinity upsilon symmetry. Meanwhile, two spin states for each isomer, that is, singlet and triplet for LaC3+, doublet and quartet for LaC3 and LaC32+, respectively, are also considered. Geometries, vibrational frequencies, infrared intensities, and other quantities are reported and discussed. The results indicate that at some spin states; the C-2 upsilon symmetry isomers are the dominant structures, while for the other spin states, linear isomers are energetically favored. (C) 1998 John Wiley & Sons, Inc.

Investigation of mechanism of nephelauxetic effect

By using the chemical bond theory of dielectric description and electronic structure of 3d elements, the mechanism of nephelauxetic effect is studied, and the main factors responsible for this effect are identified. These are: the covalency of chemical bond, polarizabilities of ligand bond volume for the host and the valence and spin state of the center ion. Relationships between these factors are given, and the results are discussed. (C) 1996 Elsevier Science Ltd. All rights reserved.

Perovskite-like mixed oxides La2-x(Sr,Th)(x)CuO4+/-lambda

Two groups of mixed oxides La2-xThxCuO4+/-lambda (0.0 less than or equal to x less than or equal to 0.4) and La2-xSrxCuO4+/-lambda (0.0 less than or equal to x less than or equal to 1.0) were prepared. Their crystal structures were studied with XRD and IR spectra, etc. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) was measured through chemical analyses. Catalysis of the abovementioned mixed oxides was investigated in phenol hydroxylation, good results were obtained for some mixed oxides, and found that the catalysis of these mixed oxides have close relation with their defect structure and composition. A radical substitution mechanism was also proposed for this catalytic reaction.

Nonlinear optical properties of (B3O7)(5-) and (B3O6)(3-) groups

From the chemical bond viewpoint, LiB3O5 (LBO) crystal has been studied by using the bond valence theory of complex crystals. Chemical bond parameters and linear and nonlinear optical (NLO) properties of each type of constituent chemical bonds are quantitatively determined. Because of the different crystal structure characteristics of LBO from those of beta-BaB2O4 (BBO), the two anionic groups, (B3O7)(5-) in LBO and (B3O6)(3-) in BBO, play different roles in contributions to their own total NLO tensor coefficients of LBO and BBO, respectively. By comparison, we find that planar (B3O6)(3-) groups are the ideal structure model, leading to little cancellation of contributions of each kind of bond in these groups, and this gives us a useful guide to design new NLO materials in the future.

Single crystal growth and spectroscopic properties of KZnF3:Eu3+

Single crystal of KZnF3 : Eu3+ has been grown by means of Bridgman-Stockbarger technique in Ar atmosphere, The emission and excitation spectra of europium ion were measured, The results show that a small amount of Eu2+ exists in the crystal, The existence of Eu2+ ions was also confirmed by ESR data, The valence change of Eu ions during the crystal growth is due to unequivalent substitution of Eu3+ ions for the lattice ions. The sites possibly occupied by Eu ions in this crystal were also discussed.

Comparison of non-linear optical susceptibilities of KNbO3 and LiNbO3

From the chemical bond viewpoint, second-order non-linear optical (NLO) tenser coefficients of KNbO3 and LiNbO3 crystals have been calculated. By using the bond-valence theory of complex crystals and the modified bond-charge model, we were able to determine contributions of each type of constituent chemical bond to the total second-order NLO susceptibility. The tenser values thus calculated are in good agreement with experimental data. From the comparison of NLO tenser coefficients of these two crystals, we found that the major NLO contributors are KO12 groups and LiO6 octahedra not the distorted NbO6 octahedra. The difference between their NLO properties arises from their different structural characters, and the high coordination number of constituent elements in KNbO3 makes its valence electrons become more delocalised compared with those of LiNbO3. (C) 1997 Elsevier Science Ltd. All rights reserved.

Characterization and catalytic behavior of La2-x(Sr,Th)(x)CuO4+/-lambda in reaction NO+CO

Two mixed oxide systems La2-xSrxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 1.0) and La2+xThxCuO4+/-lambda(0.0 less than or equal to x less than or equal to 0.4) with K2NiF4 structure were prepared by varying re values; Their crystal structures were studied by means of XRD and IR spectra. The average valence of Cu ion at B site, nonstoichiometric oxygen (A) and the chemical composition in the bulk and on the surface of the catalysts were measured by means of chemical analysis and XPS. The catalytic behavior in reaction CO + NO was investigated under the regular change of average valence of Cu ion at B site and nonstoichiometric oxygen (lambda). Meanwhile, the adsorption and activation of the small molecules NO and the mixture of NO + CO over the mixed oxide catalysts were studied by means of MS-TPD. The catalytic mechanism of reaction NO + CO over these oxide catalysts were proposed; and it has been found that, at lower temperatures the activation of NO is the rate determining step and the catalytic activity is related to the lower valent metallic ion and its concentration, while at higher temperatures the adsorption of NO is the rate determining step and the catalytic activity is related to the oxygen vacancy and its concentration.

Catalysis of the rare earth containing mixed oxides Ln(2)CuO(4) in phenol hydroxylation

Mixed oxides Ln(2)CuO(4+/-lambda)(Ln = La, Pr, Nd, Sm, Gd) with K2NiF4 structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (lambda) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln(2)CuO(4+/-lambda) has a great influence on their catalysis in the phenol hydroxylation.

The origin of nonlinearities in K[B5O6(OH)(4)]center dot 2H(2)O crystal

In this paper the origin of nonlinearities of the K[B5O6(OH)(4)].2H(2)O(KB5) crystal has been investigated from a comprehensive view-point by using the bond-valence theory of complex crystals. The results of the calculation (d(31) = -1.18 X 10(-10) esu, d(32) = 0.20 X 10(-10) and d(33) = -1.03 X 10(-9) esu) are in good agreement with experimental data. For the first time we pointed out that its nonlinearities come from the H(2)-O(2) bonds and the [B5O6(OH)(4)](-) group, and estimated its larger nonlinear optical (NLO) coefficient d(33).