Preliminary study on the charge transfer and bond ionicity of binary crystals

Charge transfer and bond ionicity of some monovalent, divalent, and trivalent binary crystals of A(N)B(8-N) type have been investigated using the self-consistent method. The method divides the binary crystal systems into two subsystems which contain only one kind of element each in physical space. The charge transfer values are obtained by adjusting the charge in a self-consistent way. Based on the obtained charge transfer values, an empirical formula for bond ionicity has been proposed. It has been shown that the present results for bond ionicity are in good agreement with the previous theoretical study delivered by Levine and Pauling. The results also indicate that a large magnitude of charge transfer (or less excess charge in the bonding region) gives rise to high bond ionicity (or low bond covalency); this agrees well with the viewpoint that the excess charge in the bonding region is the origin of the formation of bond covalency. (C) 1998 American Institute of Physics. [S0021-9606(98)00837-X].

The influence of muffin-tin approximation on energy band gap

The influence of muffin-tin approximation on energy band gap was studied using LMTO-ASA (Linear Muffin-Tin Orbital-Atomic Sphere Approximation) approach. Since the diverse data are available for LaX(X=N, P, As, Sb), they are presented in our research as an example in order to test the reliability of our results. Four groups of muffin-tin radii were chosen, they were the fitted muffin-tin radii based on the optical properties of the crystals (the first), 1 : 1 for La : X(the second), 1.5 : 1 for La : X(the third), and a group of radii derived by making the charge in the interstitial space to be zero(the fourth). The results show that the fitted muffin-tin radii (the first group) give the best results compared with experimental values, and the predicted energy band gaps are very sensitive to the choice of muffin-tin radius in comparison with the other groups. The second and the third delivered results somewhere in between, while the fourth provided the worst results compared with the other groups. For the same crystal, with the increase of muffin-tin radius of lanthanum, the calculated energy band gaps decreased, going from semi-conductor to semimetal. This again clearly indicated the sensitivity of energy band structure on muffin-tin approximation.

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.

Study on alternating LB films of charge-transfer complex of octadecyl-TCNQ and copper phthalocyanine derivative

Infrared spectra of alternating LB films of octadecyl-TCNQ/CuPc are studied. Charge-transfer complexes are formed in LB films and conductance increases about three orders than that of pure CuPc LB films.

Bond-charge calculation of electro-optic coefficients of diatomic crystals

A theoretical method has been set up to calculate the electrooptic tensor coefficients r(ijk), based on the Phillips-Van Vechten (PV) dielectric theory and the Levine bond charge model, Starting from the crystal structure data and only introducing the experimentally determined optical permittivity and dielectric constant, the electro-optic tensor coefficients r(ijk) can be quantitatively predicted, The theoretical calculations are in good agreement with experiment in the case of zinc blende and wurtzite crystals, For zinc blende crystals, the effects of covalent radii on the linear electro-optic coefficients are discussed. (C) 1997 Academic Press.

Charge transport of indigo-carmine doped polypyrrole

Charge transport in polypyrrole doped with indigo-carmine was investigated by the method of electrochemical alternating current impedance. By the nonlinear least square fitting, the equivalent circuit and parameter of each component are obtained. The apparent diffusion coefficients and heterogeneous electron transfer constants are given. It is found that, along with the increasing of film thickness, D-app and k(0) increase also.

SYNTHESIS AND CHARACTERIZATION OF POLYACRYLATES CONTAINING CHARGE-TRANSFER GROUPS

Polyacrylates containing para-nitro azobenzene have been synthesized by free radical polymerization. The influence of the length of the spacer of the homopolyacrylates (HPn, n=3,4,6), content of methyl acrylate in the copolyacrylates (CP6) with para-nitro azobenzene groups on the thermal properties, such as liquid crystallinity, Tg and Tm, was studied by DSC, WAXD and polarized optical microscopy. Among the polymers studied, only the homopolyacrylate (HP6)with six carbon atoms in the spacer exhibited a nematic phase. The second-harmonic generation (SHG) signal of the poled HP6 film was detected qualitatively by Maker-fringer method.

HIGHLY SENSITIVE AND SELECTIVE DETERMINATION OF RIBOFLAVIN BY FLOW-INJECTION ANALYSIS USING PARALLEL DUAL-CYLINDER MICROELECTRODES

A novel wall-jet cell with parallel dual cylinder (PDC) microelectrodes was constructed and used for flow injection analysis (FLA). The detector takes the advantages of ''redox recycling'' between bipotentiostated microcylinder electrodes (- 0.4 V/SCE an

A STUDY OF CHARGE SEPARATION AND ELECTRON-CAPTURE INDUCED DECOMPOSITION SPECTRA OF PHENYLENEDIAMINE ISOMERS

The structures and decomposition reactions of doubly charged phenylenediamines were studied by means of charge separation (CS) and electron capture induced decomposition (ECID) spectra. The deisomerization of the three isomers is prior to the metastable d

CHARGE COMPENSATION AND LUMINOUS CENTERS IN CAF2-CE3+

We synthesize some powder phosphors of CaF2:Ce3+ under different reaction conditions, find three luminous centres, and demonstrate that each luminous centre is formed with different charge compensation procedures.

CHARGE COMPENSATION AND VALENCY STABILITY OF EU(II)-DOPED KMGF3 CRYSTAL

The spectrochemistry of Eu2+-doped perovskite KMgF3 was examined and discussed. Eu2+ can replace some of the K+ in the KMgF3 crystal, and simultaneously the corresponding cation hole can be compensated with the F- or O2- in the matrix. The emission intensity of Eu2+ due to the f --> f transition increased when Na+, Rb+ or F- was doped in KMgF3:Eu2+. Two mechanisms of charge compensation were proposed. No obvious valence change of Eu2+ occurred in KMgF3:Eu2+ after calcinating at high temperature, e.g. 900-degrees-C. It was found that the valence stability of Eu2+ improved after incorporation into the matrix.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

THE CHARACTERIZATION OF 2 COPPER PHTHALOCYANINE LANGMUIR-BLODGETT-FILMS AND THEIR GAS-SENSITIVE PROPERTIES

The monolayer and deposition behaviour of a symmetrically substituted copper tetra-4-(2, 4-di-t-amylphenoxy) phthalocyanine (tapCuPc) and an asymmetrically substituted copper [tri-4-(2, 4-di-t-amylphenoxy)-mono-4-(-2-methoxyethoxy)]phthalocyanine (AsyCuPc) were investigated. The results on monolayer behaviour and spectroscopic characterization of the LB films show that both CuPc molecules in a monolayer at the air-water interface and the LB films are stacked and inclined. The gas-sensitive properties show that the responding speed of AsyCuPc LB film is faster than that of tapCuPc LB film.

THE CHARGE-DISTRIBUTION AND THE ELECTRIC-FIELD GRADIENT IN THE HIGH-TEMPERATURE SUPERCONDUCTOR TLBA2CAN-1CUNO2N+3 (N = 1 TO 3)

The net charges at atoms in the high-temperature superconductor TlBa2Can-1CunO2n+3 (n = 1 to 3) are calculated by means of the tight-binding approximation based on the EHMO method. The results indicate that the charge distribution in this kind of compounds possesses a specially layered arrangement. An insulating Ba-Ba layer is inserted between the Cu-O layer and the Tl-O layer. There may exist a weak coupling between the Cu-O layer and the Tl-O layer through the interaction of the same O(2) atom with both the Cu atom and the Tl atom. The existence of the Ca in the compounds can cause the valence fluctuation at the Cu atom. The calculated electric field gradients at atoms implies that the conducting electron or hole may move in the Cu-O layer, which is closest to the Tl-O layer, along the a-b plane.