Preparation and properties of nanocrystalline Yb2O3

Nanocrystalline Yb2O3 of various particle sizes was prepared using sol-gel method. XRD analysis shows that the prepared nanocrystalline Yb2O3 is cubic in structure with space group Ia3. TEM photographs indicate that Yb2O3 nanoparticles are basically spherical in shape. Calculation of crystallite size indicates that the average crystallite size of Yb2O3 increases with increasing calcination temperature, but the average crystal lattice distortion rate decreases with increasing calcination temperature and crystallite size. This result shows that the smaller the crystallite size, the bigger the crystal lattice distortion, and the worse crystal growth. Solubility test of Yb2O3 in nitric acid shows that the surface activity of Yb2O3 increases with decreasing crystallite size. Fourier Transform Infrared Spectrometer (FTIR) spectra reveal that nanocrystalline Yb2O3 has higher surface activity; than that of ordinary Yb2O3. Absorbance intensity of Yb-O bond of nanocrystalline Yb2O3 is weaker than that of ordinary Yb2O3, and the absorbance of Yb-O bond of nanocrystalline Yb2O3 is small blue-shifted.

Electrostatic-field-induced chain alignment of liquid crystalline copolyether TPP thin films

A liquid crystalline (LC) copolyether has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,11-dibromoundecane with a 50/50 (both in %) equal composition of the 7- and 11-methylene monomers [coTPP-7/11(5/5)]. A mono-domain with a homeotropic alignment can be induced by a thin film surface in the LC phase. When an electrostatic field is applied to the surface-induced mono-domains parallel to the thin film surface normal, the molecular alignment undergoes a change from the homeotropic to uniaxial homogeneous arrangement. However, when the field is applied to a direction perpendicular to the thin film surface normal. the molecular alignment is about 10 degrees -tilt with respect to the homeotropic alignment toward the a*-axis. This is because the permanent dipole moment of the copolyether is not right vertical to the molecular direction. The calculation of molecular dipoles indicates that the permanent dipole moment of this copolyether is about 70 degrees away from the molecular axis, which leads to a negative dielectric anisotropy. It is speculated that the 10 degrees- rather than 20 degrees -tilt is due to a balance between the alignment induced by the electrostatic field and the surface. In the electrostatic field, molecules are subjected to a torque tau, which is determined by the permanent dipole moment P and the electrostatic field E: tau = P x E. The molecular realignment in both parallel and perpendicular directions to the thin film surface normal is determined by satisfying the condition of tau = P x E = 0. (C) 2001 Elsevier Science Ltd. All rights reserved.

Influence of bond valence on bond covalency in calcium doped lanthanum chromite

The influence of bond valence on bond covalency in La1-xCaxCrO3(x =0.0, 0.1, 0.2, 0.3) has been studied by using semiempirical method. This method is the extension of the dielectric description theory proposed by Phillips, Van Vechten, levine and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. The first is the equal-valence scheme, and the second is Bond Valence Sums (BVS) scheme. Both schemes suggest that for the title compound bond covalency be mainly influenced by bond valence, and insensitive to the Ca doping level. Generally speaking, larger bond valences usually result in higher bond covalencies.

Structural analysis of nonlinearities of Ca4ReO(BO3)(3) (Re = La, Nd, Sm, Gd, Er, Y)

From the chemical bond viewpoint, second-order nonlinear optical (NLO) tensor coefficients of the family of new oxoborates Ca4ReO(BO3)(3) (CReOB, Re = La, Nd, Sm, Gd, Er, and Y) have been theoretically predicted. The d(11) tensor coefficient of CReOB is predicted to be -11 d(36)(KDP), which is the largest d(ij) tensor that has been found in borate crystals. From the structural characteristic of CReOB, we find the isolated BO33- clusters play a dominant role in contributions to the total nonlinearity, and the largest d(11) tensor of CReOB-type crystals is also ascribed to these BO33- clusters. We also find the NLO property of this family does not change dramatically for different rare-earth elements. The details of the calculation of CGdOB only are presented.

A ZINDO-SOS study on the nonlinear second-order optical properties of substituted silanes series molecules

On the basis of ZINDO methods,according to the sum - over - states( SOS) expression, we divise the program for the calculation of nonlinear second - order optical susceptibilities beta(ijk) and study how the different substituents on the phenyl ring attached to the atom silicon influence or; the nonlinear second - order optical properties for substituted silanes series molecules. The property of (CH3)(3)Si is Studied particularly. The effect of length of silica chains on the calculated beta values is studied too. The regularity summarized from calculated results has been explained micromechanically.

Study on computer perception of topological symmetry

A new algorithm for computer perception of topological symmetry is proposed. A node library containing various kinds of nodes is built, and the index number of the library is used as initial atom class identifier (CI) to discriminate the different types of non-hydrogen atoms. The path index (PI) and ringindex (RI) are calculated from the CI, and the global topological enviroment is defined as the sum of PIs and RIs. The topological symmetry can be detected by the iterative calculation of the global topological enviroment.

Nonlinearity of the complex crystals with O-H bond

A systematic and quantitative research on the structure-property correlation has been carried out in KH2PO4 (KDP), NH4H2PO4 (ADP) and HIO3, based on the dielectric theory of complex crystals and the Levine bond charge model. We, for the first time, successfully solve the problems in the calculation of the nonlinearities of the complex inorganic nonlinear optical (NLO) crystals, which have O-H bonds in their crystal structures. We do this by introducing the bond-valence equation we have set up, calculating the nonlinear optical tensor coefficients d(ijk) of these three compounds, quantitatively determining the contributions of each type of bond to the total second-order NLO tensor coefficient (d(ijk)) of the crystal, and presenting the bond parameters and the linear properties of each kind of bond. For the first time, the NLO coefficient d(36) for ADP was calculated. All calculated results are in good agreement with experimental data. We found that O-H bonds also play an important role in these crystals, except for in the important anionic groups (PO4 groups and IO3 groups). All the results thus calculated show that our method is useful in evaluating the NLO coefficients of the inorganic NLO crystals containing O-H bonds in their structures, and should be a useful tool toward the future research into new nonlinear optical materials of this kind.

A theoretical study on the nonlinear optical second-order properties of azobenzene series molecules

On the basis of AM1 and INDO/CI methods, we devise the program for the calculation of nonlinear second-order optical susceptibilities beta(ijk) and perform systematic theoretical studies on the nonlinear optical second-order properties of azobenzene series molecules, i. e. on the basis of [GRAPHICS] we induced different donors on the left side of phenyl ring, and different accepters on the right side of phenyl ring, and examined the rule of beta variation. The regularity summarized from the calculated results has been explained micromechanically. Finally, a molecule having a big nonlinear second-order optical susceptibility has been designed.

STRUCTURE-PROPERTY RELATIONSHIP BETWEEN HALF-WAVE POTENTIALS OF ORGANIC-COMPOUNDS AND THEIR TOPOLOGY

A significant correlation was found between half-wave potentials of organic compounds and their topological indices, A(x1), A(x2), and A(x3). The simplicity of calculation of the index from the connectivity in the molecular skeleton, together with the significant correlation, indicates its practical value. Good results have been obtained by using them to predict the half-wave potentials of some organic compounds.

CIAC COMPREHENSIVE INFORMATION-SYSTEM OF RARE-EARTHS

The CIAC (Changchun Institute of Applied Chemistry) Comprehensive information System of Rare Earths is composed of three subsystems, namely, extraction data, physicochemical properties, and reference data. This paper describes the databases pertaining to the extraction of rare earths and their physicochemical properties and discusses the relationships between data retrieval and optimization and between the structures of the extractants and the efficiency with which they are extracted. Expert systems for rare earth extraction and calculation of thermodynamic parameters are described, and an application of pattern recognition to the problems of classification of compounds of the rare earths and prediction of their properties is reported.

Population genetic structure of Sargassum thunbergii (Fucales, Phaeophyta) detected by RAPD and ISSR markers

Genetic variation of four populations of Sargassum thunbergii (Mert.) O. Kuntze and one outgroup of S. fusiforme (Harv.) Setchell from Shandong peninsula of China was studied with random amplified polymorphic DNA (RAPD) and inter-simple sequence repeat (ISSR) markers. A total of 28 RAPD primers and 19 ISSR primers were amplified, showing 174 loci and 125 loci, respectively. Calculation of genetic diversity with different indicators (P%, percentage of polymorphic loci; H, the expected heterozygosity; I, Shannon's information index) revealed low or moderate levels of genetic variations within each S. thunbergii population. High genetic differentiations were determined with pairwise Nei's unbiased genetic distance (D) and fixation index (F-ST) between the populations. The Mantel test showed that two types of matrices of D and FST were highly correlated, whether from RAPD or ISSR data, r=0.9310 (P = 0.008) and 0.9313 (P=0.009) respectively. Analysis of molecular variance (AMOVA) was used to apportion the variations between and within the S. thunbergii populations. It indicated that the variations among populations were higher than those within populations, being 57.57% versus 42.43% by RAPD and 59.52% versus 40.08% by ISSR, respectively. Furthermore, the Mantel test suggested that the genetic differentiations between the four populations were related to the geographical distances (r > 0.5), i.e., they conformed to the IBD (isolation by distance) model, as expected from UPGMA (unweighted pair group method with arithmetic averages) cluster analysis. As a whole, the high genetic structuring between the four S. thunbergii populations along distant locations was clearly indicated in the RAPD and ISSR analyses (r > 0.8) in our study.

Interbasin freshwater, heat and salt transport through the boundaries of the East and South China Seas from a variable-grid global ocean circulation model

The monthly and annual mean freshwater, heat and salt transport through the open boundaries of the South and East China Seas derived from a variable-grid global ocean circulation model is reported. The model has 1/6degrees resolution for the seas adjacent to China and 30 resolution for the global ocean. The model results are in fairly good agreement with the existing estimates based on measurements. The computation shows that the flows passing through the South China Sea contribute volume, heat and salt transport of 5.3 Sv, 0.57 PW and 184 Ggs(-1), respectively (about 1/4) to the Indonesian Throughflow, indicating that the South China Sea is an important pathway of the Pacific to Indian Ocean throughflow. The volume, heat and salt transport of the Kuroshio in the East China Sea is 25.6 Sv, 2.32 PW and 894 Ggs(-1), respectively. Less than 1/4 of this transport passes through the passage between Iriomote and Okinawa. The calculation of heat balance indicates that the South China Sea absorbs net heat flux from the sun and atmosphere with a rate of 0.08 PW, while the atmosphere gains net heat flux from the Baohai, Yellow and East China Seas with a rate of 0.05 PW.

The ion-molecule reaction after multiphoton ionization in the binary cluster of ammonia and methanol

The binary cluster (CH3OH)(n)(NH3)(m) was studied by using a multiphoton ionization time-of-flight mass spectrometer (MPI-TOFMS). The measured two series of protonated cluster ions: (CH3OH)(n)H+ and (CH3OH)(n)NH4+ (1 less than or equal to n less than or equal to 14) were attributed to the ion-molecule reaction in the binary cluster ions. The mixed cluster of CH3OD with ammonia was also studied. The results implied that the proton transfer probability from the OD group was larger than that from CH3 group. The ab initio calculation of the binary cluster was carried out at the HF/STO-3G and MP2/6-31G** levels of theory, and indicated that the latter process of the proton transfer must overcome a barrier of similar to 29 kcal/mol. (C) 1999 Elsevier Science B.V. All rights reserved.

Prediction of GC retention values under various column temperature conditions from temperature programmed data

A numerical approach has been developed for the correlation of retention limes (total retention lime) with temperature in gas chromatography, which allows the calculation of retention parameters including retention index from data acquired under two or more different temperature program conditions. By using this procedure the optimization of temperature condition can be further achieved, especially when a temperature-programmed run is the most suitable mode in the preliminary development of an analytical method for the analysis of an unknown sample.

Resolution prediction and optimization of temperature programme in comprehensive two-dimensional gas chromatography

A model is developed for predicting the resolution of interested component pair and calculating the optimum temperature programming condition in the comprehensive two-dimensional gas chromatography (GC x GC). Based on at least three isothermal runs, retention times and the peak widths at half-height on both dimensions are predicted for any kind of linear temperature-programmed run on the first dimension and isothermal runs on the second dimension. The calculation of the optimum temperature programming condition is based on the prediction of the resolution of "difficult-to-separate components" in a given mixture. The resolution of all the neighboring peaks on the first dimension is obtained by the predicted retention time and peak width on the first dimension, the resolution on the second dimension is calculated only for the adjacent components with un-enough resolution on the first dimension and eluted within a same modulation period on the second dimension. The optimum temperature programming condition is acquired when the resolutions of all components of interest by GC x GC separation meet the analytical requirement and the analysis time is the shortest. The validity of the model has been proven by using it to predict and optimize GC x GC temperature programming condition of an alkylpyridine mixture. (c) 2005 Elsevier B.V. All rights reserved.