A STUDY OF TEMPERATURE-DEPENDENT VALENCE BOND STRUCTURE OF TITANIUM

On the basis of energy and shape method for the determination of the valence bond （ VB ） structures of crystal, the valence bond structure of titanium is redetermined at room temperature and calculated in the whole temperature range of 0-1943K. The outer shell electronic distribution of Ti is ec^29907. （sc^0.4980 ＋ dc^2.4927） ef^1.0098 in crystal. The temperature dependences of the VB structures of hcp and bcc phases are the same. The VB structures of hcp and bcc phases monotonically increase or decrease with the increase in temperature, but show discontinuous changes at the phase-transformation temperature 1155K.

Valence bond structure of Ta-W alloys

The valence bond structure of substitutional BCC based Ta-W alloys is studied using characteristic crystal （CC） theory. This theory is based on cluster statistics of random alloys. By studying the correlativity between energy and volume of the CC in Ta- W alloys, the valence bond structure of CC is determined by the energy and shape method. Then, following additive law of CC, the valence bond structure of Ta-W alloys is calculated. It is found that the outer shell valence electronic distribution of Ta-W Mloys shows a continuous change in the whole composition range. The covalent electrons ec （dc, sc, and pc） increase, whereas near free electrons ef decrease with increasing W concentration. The bond length and single-bond radius decrease, whereas bond energy and bond valence increase with increasing W concentration. The mechanism of solid solution strengthening of Ta-W alloys is analyzed based on their valence bond structure.

Structure and property of metal melt Ⅳ——Evolution of titanium melt residual bond structure and its effect on dynamic viscosity

Based on the concept of melt residual bonds, a calculating model quantitatively describing the evolution of the residual bond structure of titanium melt at the melting point or in a certain range above the melting point was established; i.e., both the size ds and the bond number n of the residual bond structure decrease monotonously with the increase of temperature. By mathe- matical deduction, a linear relationship between the residual bond structure size ds and the dynamic viscosity 17 of Titanium melt was revealed, i.e., η= 0.876 ＋ 0.471·ds, which is of great significance to the investigation of the relationship between the melt microstructure and the macroscopic properties of metals with high melting temperature.

Effect of Aluminum Addition on Microstructure and Properties of SiO_2-B_2O_3-Al_2O_3-CaO Vitrified Bond

Influence of aluminum addition on the structures and properties of SiO_2-B_2O_3-Al_2O_3-CaO vitrified bond at low sintering temperature and high strength was discussed. FTIR and XRD analyses were used to characterize the structures of the basic vitrified bond with different contents of aluminum. The bending strength and the thermal expansion coefficients were also tested. Meanwhile, the microstructures of composite specimens at sintering temperature of 660 ℃ were observed by scanning electron microscope（SEM）. The experimental results showed that the properties of vitrified bond with 1wt% aluminum were improved significantly, where the bending strength, Rockwell hardness, and thermal expansion coefficient of the vitrified bond reached 132 MPa, 63 HRB, and 6.73×10^（-6） ℃^（-1）, respectively.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.

LOCALIZED STUDIES ON ELECTRONIC STRUCTURE AND CHEMICAL BOND FOR [NCCuS_2MoS_2]^(2-) CLUSTER

The canonical and locatized molecutar orbiters of [NCCuS_2NoS_2]^(2-) cluster were calculated by means of CNDO quantum chemistry method. Then the energy and properties of corresponding chemicat bonds were discussed, especially, Cu-Sb-No three center conjugated π bonds and No-St-No conjugated π bonds were accounted for.

A classification scheme for inorganic cluster compounds based on their electronic structures and bonding characteristics

A novel classification scheme for inorganic cluster compounds is presented based on the characteristics of their electronic structures.In the classification scheme,five distinct categories have been introduced,including Jellium clusters,Wadian clusters,electron-precise clusters,π-donor ligated metal-metal bonded clusters,and antiferro-magnetically coupled high-spin metal clusters.

Composition and Microstructure of Magnetron Sputtering Deposited Ti-containing Amorphous Carbon Films

Ti-containing carbon films were deposited by using magnetron sputtering deposition. The composition and microstructure of the carbon films were characterized in detail by combining the techniques of Rutherford backscattering spectrometry （RBS）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. It is found that carbon films contain Ti 18 at pct; after Ti incorporation, the films consist of titanium carbide; C1s peak appears at 283.4 eV and it could be divided into 283.29 and 284.55 eV, representing sp2 and sp3, respectively, and sp2 is superior to sp3. This Ti-containing film with dominating sp2 bonds is nanocomposites with nanocrystalline TiC clusters embedded in an amorphous carbon matrix, which could be proved by XRD and TEM.

Synthesis,Crystal Structure and Theoretical Calculations of a Zinc(Ⅱ) Coordination Polymer Assembled by Pyrazine-2,3-dicarboxylic Acid and Bis(imidazol) Ligands

A new metal-organic coordination polymer [Zn（pzdc）（mbix）]n·nH2O（H2pzdc = pyrazine-2,3- dicarboxylic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a = 8.5519（6）, b = 14.8764（10）, c = 16.4108（11） A, β = 103.4520（10）o, V = 2030.5（2）A^3, C（20）H（18）N6O5Zn, Mr = 487.77, Dc = 1.596 g/cm^3, F（000） = 1000, Z = 4, μ（MoK α） = 1.257 mm^-1, the final R = 0.0260 and w R = 0.0706 for 3445 observed reflections（I 〉 2σ（I））. The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital（NBO） analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn（Ⅱ） ion.

Synthesis and Structure Analysis of a Tripeptide Containing N-methyl Group Amino Acid

A convenient method of synthesizing a tripeptide-containing N-methyl group amino acid was developed using O-benzotriazole-N,N,N＇,N＇-tetramethyluronium-hexafluorophosphate as the condensing agent. The crystals of tripeptide had white needles belonging to the orthorhombic space group P2_12_12_1. The conformational preference for homochiral tripeptides with one N-methylated amide bond was also investigated. Crystal-structure analysis showed that homochiral tripeptides with an internal N-methylated amide bond preferred a trans-amide form, thereby giving the peptide β-fold characteristics. Intermolecular C-H···O and N-H···O hydrogen bonds linked the molecules into a one-dimensional chain and stabilized the structure.

Synthesis,Crystal Structure and Thermal Decomposition of a New Energetic Dipotassium 3,3'-Dinitro-5,5'-bis-1,2,4-triazole-1,1'-diolate

A new energetic dipotassium 3,3-dinitro-5,5-bis-1,2,4-triazole-1,1-diolate [K2（DNOBT）] was synthesized, and structurally characterized by elemental analysis, IR spectra, 13 C NMR and single-crystal X-ray diffraction. K2（DNOBT）·2H2O crystallizes in monoclinic system, space group P21/n with a=6.0446（10）, b=15.999（3）, c=6.4169（11） , β=99.421（2）°, V=612.21（18） 3, Z=4, Dc=2.009 g·cm（-3）, F（000）=372, μ=0.838 mm（-1）, S=1.012, the final R=0.0248 and w R（I 〉 2σ（I））=0.0604. Thermal decomposition of the title compound was studied by using DSC and TG-DTG, and there is primarily one exothermic decomposition process at 371.5 ℃.

A New Cd(Ⅱ) Coordination Polymer Constructed by 3-(2-Pyridyl)pyrazole and 5-Nitroisophthalic Acid：Synthesis, Crystal Structure and Theoretical Calculations

A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539（6）, b = 11.6252（8）, c = 12.2472（8） A^°, α = 80.011（2）, β = 80.3850（10）, γ = 86.773（2）°, V = 1237.37（14） A^°3, Z = 2, Dc = 1.987 g/cm^3, μ = 1.780 mm^-1, Mr = 740.25, F（000） = 724, the final R = 0.0295 and wR = 0.1015 with I 〉 2σ（I）. Two H2NIPH as monodentate and bidentate ligands and two L ligands link four Cd（Ⅱ） ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.

Hydrogen Bonded 3D Molecular Self Assembly Constructed from [(Ni(nicotinamide)_2(thiocyanate)_2(H_2O)_2] Complex Showing Spin Canted Anti-ferromagnetic Character

A new three-dimensional nickel（Ⅱ） hydrogen-bonded molecular self assembly containing [（Ni（nicotinamide）2（thiocyanate）2（H2O）2] complex has been synthesized and characterized by single-crystal X-ray diffraction,FTIR spectroscopy,thermal analysis and magnetic measurements.Structural analysis reveals that the complex crystallizes in triclinic space group P1（crystal data a = 7.5574,b = 8.2683,c = 9.0056 A,α = 73.010,β = 69.698,γ = 66.51） and exhibits a distorted octahedral coordination sphere.Most interesting point in its structure is the involvement of sulphur atom of thiocyanate moiety in the trifurcated hydrogen bonding to build up the hydrogen-bonded self assembly.The magnetic behavior as determined by squid magnetometer（2~300 K temp.range） reveals dominating antiferromagnetic interaction followed by spin canting behavior below 20 K.

Refinement of the Crystal Structure of Aconitine

The crystal of aconitine has been obtained through an unexpected spontaneous change of the solid power of aconitine in air and characterized by single-crystal X-ray diffraction analysis and elemental analysis. Crystallographic data： orthorhombic, space group P2_12_12_1 with a = 17.0745（6）, b = 15.5990（6）, c = 12.2443（6） ？, V = 3261.2（2） ？~3, Z = 4, C_（34）H_（47）NO_（11）, M_r = 645.73, D_c = 1.315 g/cm^3, F（000） = 1384, μ（MoKa） = 0.098 mm^（-1）, R = 0.0605 and wR = 0.1311. Aconitine is diester diterpenoid alkaloid, and its main structure is composed of four six-membered and two five-membered rings. The intramolecular and intermolecular O–H···O and C–H···O hydrogen bonds extend the adjacent molecules into a one-dimensional chain and a two-dimensional framework, which may be the essential reason for the change.

Field-Induced Structural Transition in the Bond Frustrated Spinel ZnCr2Se4

The effect of an external magnetic field on the structural and magnetic properties of bond frustrated ZnCr2 Se4 at low temperatures is investigated using magnetization, dielectric constants and thermal conductivity experiments. With an increase in the magnetic field H, the antiferromagnetic transition temperature TN is observed to shift progressively toward lower temperatures. The corresponding high temperature cubic （Fd3m） to low temperature tetragonal （I41amd） structural transition is tuned simultaneously due to the inherent strong spin-lattice coupling. In the antiferromagnetic phase, an anomaly at Hc2 defined as a steep downward peak in the derivative of the M-H curve is dearly drawn. It is found that TN versus H and Hc2 versus T exhibit a consistent tendency, indicative of a field-induced tetragonal （I41amd） to cubic （Fd3m） structural transition. The transition is further substantiated by the field-dependent dielectric constant and thermal conductivity measurements. We modify the T-H phase diagram, highlighting the coexistence of the paramagnetic state and ferromagnetic clusters between 100K and TN.

Structural Probing on the Sn-C(C5 ring)Bond of the Sn(Ⅱ)Metallocenes in Both the Solid State and the Temperature-dependent Solution Relaxation State

Various bond modes of the M-C（C5 ring） exist in metallocene compounds of group 14 heavier elements,mostly due to an intricate interaction between the lone electron pairs at the M center and the 6 p-electrons of the C5 ring.The tin（Ⅱ） metallocene complexes LSn R（L = HC[CMe（N-2,6-iPr2C6H3）]2,R = cyclopentadienyl,C5H5（1）; indenyl,C9H7（2）; fluorenyl,C（13）H9（3）） stabilized by the β-diketiminato ligand were prepared and utilized in the study on their solid and solution state structures.X-ray single-crystal diffraction data revealed an η~1-mode of the Sn-C（C5 ring） bond in each 1~3.However,the room temperature ~1H NMR spectral studies disclosed such a fluxional bonding mode in solution.The 119 Sn NMR studies suggested a quadruple coordination nature of the Sn center in 1 while the triple coordination manner was for the Sn atom in both 2 and 3.Then the variable-temperature（25~–75 ℃） ~1H NMR spectral studies for each 1~3 were performed,which detected the relaxation state structures of 1~3 at lower temperature.All of these results indicate a stereochemical activity of the lone electron pairs at the tin（Ⅱ） atom that definitely has an electronic interaction with the 6 p-electrons of the C5 ring.The observed Sn-C（C5 ring） bond modes appear influenced by either the metallocene size or the compound state existed.

Crystal Structure of the Coordination Polymer of Sodium with Hydrazone Derivant of Acetoacetanilide

One new polymer, [Na（NPHSNPAB）（CH3OH）]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex： C（17）H（17）N4NaO9S, Mr = 476.39, triclinic system, space group P1, a = 8.8741（18）, b = 10.942（2）, c = 12.039（2） A, α = 65.74（3）, β = 77.49（3）, γ = 84.30（3）o, V = 1040.3（4） A3, Z = 2, Dc = 1.521 g/cm^3, λ = 0.71073 A, F（000） = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 〉 2（I）. X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium（I） center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units（3.768 A） indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.

Synthesis, Crystal Structure and Theoretical Calculations of a New Two-dimensional Co(Ⅱ) Coordination Polymer Based on Oxalic Acid and Bis(imidazol) Ligands

A new Co（ll） coordination polymer has been successfully synthesized under hydrothermal conditions [Co（C2O4）（mbix）]n （1, H2C2O4 = oxalic acid, mbix = 1,3-bis（imidazol- l-ylmethyl）benzene）. Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group PI with a = 8.8666（7）, b = 9.5859（8）, c = 10,8537（9） A,α = 67.6810（10）,β= 66.1260（10）, γ = 77.1300（10）°, V= 777.77（11）, CI6HI4CoN404, Mr = 385.24, Dc = 1.645 g/cm3, F（000） = 394, Z= 2,/z（MoKa） = 1.134 mm% the final R = 0.0482 and wR = 0.1231 for 2968 observed reflections （I〉 2σ（I））. It shows a two-dimensional （2D） network structure. The intermolecular C-H…O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture and play an important role in stabilizing 1. In addition, Natural Bond Orbital （NBO） analysis was performed by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co（II） ion.

Raman and Infrared Spectra for All-trans-astaxanthin in Dimethyl Sulfoxide Solvent

The Raman and infrared spectra of all-trans-astaxanthin （AXT） in dimethyl sulfoxide （DMSO） solvent were investigated experimentally and theoretically. Density functional cal-culations of the Raman spectra predict the splitting of the υ1 band into υ1-1 and υ1-2 compo-nents. The absence of splitting in Raman experimental spectra is ascribed to the competition between the two symmetric C=C stretching vibrations of the backbone chain. The υ1 band is very sensitive to the excitation wavelength： resonance excitation stimulates the higher-frequency υ1-2 mode, and off-resonance excitation corresponds to the lower-frequency υ1-1 mode. Analyses of the intramolecular hydrogen bonding between C=O and O-H in the AXT/DMSO system reveal that the C4=O1...H1-O3 and C4＇=O2...H2-O4 bonds are strengthened and weakened, respectively, in the electronically excited state compared with those in the ground state. This result reveals significant variations of the AXT molecular structure in different electronic states.

Supramolecular Network Obtained from the Interaction of Dihydrophosphate Anions and Thiourea-based Receptors

Two crystals of receptor 1, C（42）H（52）N（10）O4S2（anthracene-9,10-dicarbaldehyde bis-（phenyl-semithiocarbazone）） and-1-H2PO4, C（68）H（114）N（10）O（10）P2S2 were obtained at room temperature successfully, and their structures were characterized by X-ray crystallography diffraction. X-ray diffraction reveals that, receptor 1 crystallizes in monoclinic, space group P21/c, with a = 9.487（3）,b = 20.674（6）, c = 11.821（4）A, β = 113.416（8）o, Mr = 825.06, V = 2127.5（12） A^3, Z = 2, Dc = 1.288g/cm^3, μ = 0.18 mm^-1, F（000） = 876, MoK α radiation（λ = 0.71073 A）, the final R = 0.0472 and wR = 0.0930. A total of 3758 unique reflections were collected, of which 3313 with I 〉 2σ（I） were observed. Compound 1-H2PO4^-crystallizes in triclinic, space group P21/n, with a = 8.767（1）, b =13.6190（15）, c = 16.615（2） ？, α = 98.727（14）, β = 103.061（14）, γ = 91.382（16）°, Mr = 1357.75, V =1906.6（4） A^3, Z = 1, Dc = 1.183 g/cm^3, μ = 0.17 mm-（-1）, F（000） = 734, MoK α radiation（λ = 0.71073？）, the final R = 0.0769 and wR = 0.1884. A total of 6699 unique reflections were collected, of which 2989 with I 〉 2σ（I） were observed. As it was observed in the crystal structure of 1-H2PO4^-, 1bound H2PO4^-at a 1：2 ratio by intermolecular interaction of N-H···O hydrogen bond obviously.Another interesting feature was that H2PO4--groups assembled chains themselves via intramolecular hydrogen bond O-H···O and connected the 1 molecules together through the interaction of H-bonds,which improved the planarity of 1 and increased the stability of the entire structure.