Calculations of the electronic structures of cage molecules using free-electron orbitals as a basis

A non-empirical molecular orbital method, particularly suitable for calculations on cage-like molecules, is described. The method uses as basis functions the set of free-electron functions which are the solutions of Schrödinger's equation for an electron confined between two concentric, spherical potential energy barriers. Application of the theory to the SCF calculation of the energies of the delocalized electrons in benzene and tetrasulphur tetranitride shows that the model is capable of interpreting the properties of such systems. However, it does highlight a difficulty in the calculation of excited state energies with one-centre models which appears to be largely unrecognized.Extension of the method to a consideration of all the valence electrons, using P₄ as an example, reveals problems the origin of which is an inadequate treatment of the core electrons. It is suggested that these problems may best be dealt with by use of a suitable pseudo potential.     

Experimental and theoretical study of vibrational spectra and structure of dihalogermylene and dihalostannylene complexes with 1,4-dioxane and triphenylphosphine

Vibrational (Raman and IR) spectra of the 1:1 complexes of dihalogermylene and dihalostannylene with 1,4-dioxane and PPh₃ have been reported, the structures of the complexes Cl₂Ge·C₄H₈O₂ and Cl₂Ge·PPh₃ updated using high-resolution X-ray method. Quantum-chemistry calculations of the geometry and normal mode frequencies and eigenvectors were carried out for some of the complexes. The results show that in the structure of the polymeric solid complexes of X₂M with 1,4-dioxane, intermolecular coordination XM plays a prominent role, whereas the corresponding complexes with PPh₃ are monomeric. In the vibrational spectra of all the complexes, an inversion of symmetric and antisymmetric stretching νXM (X=Cl, Br; M=Ge, Sn) frequencies, found for ‘free’ X₂M^II particles, still persists, suggesting that the X₂M moieties preserve their specifity as carbene analogues also in the complexes.     

Preparation and crystal structure of the La2Ni12P5 and isotypic ternary lanthanoid—Nickel phosphides

The new ternary phosphide La₂Ni₁₂P₅ has been prepared by direct arc melting of the components as pure metals and red phosphorus. The crystal structure has been determined using X-ray single crystal diffraction data. The compound exhibits a new type of crystal structure, P2₁/m with lattice parameters a = 10.911(3), b = 3.696(2), c = 13.174(4) Å, β = 108.02(2)°, V = 505,2(6) ų, Z = 2. Atomic parameters least squares refinement of 116 independent variables (anisotropic approximation for thermal vibrations) employed 1 284 independent I_o(hkl); R_F = 0.0278 and R_W = 0.0287. The crystal structure is characterized by trigonal prismatic arrangement of phosphorus atoms stacking variant of infinite (with phosphorus centered) columns built by metal trigonal prisms ‖ [010]. Two or three such columns are connected through common edges (lanthanum atoms). The compounds RE₂Ni₁₂P₅ (where RE = Ce, Pr, Nd and Eu) display the same with La₂Ni₁₂P₅ crystal structure. Lattice parameters of these compounds have been refined using powder diffraction data.     

人工神经网络X射线荧光光谱法测定钢中酸溶铝

建立了一种人工神经网络-X射线荧光光谱法测定钢中酸溶铝的方法，用X射线荧光光谱法测定低合金钢中总铝值，应用所建立的ANN-BP网络模型，输入总铝含量直接预测出酸溶铝含量。同时使用改进的BP算法，避免了神经网络学习中可能产生的麻痹现象。该方法用于钢中酸溶铝的测定，结果满意。     

Adsorption of water molecules in slit pores

We report molecular dynamics (MD) simulations on the adsorption of water in attractive and repulsive slit pores, where the slit and a bulk region are in contact with each other. Water structure, surface force and adsorption behavior are investigated as a function of the overall density in the bulk region. The gas–liquid transition in both types of pores occurs at similar densities of the bulk region.     

Synthesis and Structure of the New Ammonium Indium Phosphate (NH4)In(OH)PO4

A new ammonium indium phosphate (NH₄)In(OH)PO₄ was prepared by hydrothermal reaction in the In₂O₃-NH₄H₂PO₄-NH₃/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH₄)In(OH)PO₄ was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH₄)In(OH)PO₄ crystallizes in the tetragonal system with space group P4₃2₁2 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) ų; Z=8. The crystal structure was refined by the Rietveld method (R_w=6.35%, R_p=5.10%). The second-harmonic generation study confirmed that structure of (NH₄)In(OH)PO₄ does not have a center of symmetry. The cis-InO₄(OH)₂ octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH₄⁺ ions along the c-axis. (NH₄)In(OH)PO₄ is isostructural with RbIn(OH)PO₄.     

On the symmetry of iron(III) tris-acetylacetonate crystals

The crystal structure of iron tris-acetylacetonate is re-determined. Crystal data at 293 K are: a = 15.4524(5) Å, b = 13.5876(4) Å, c = 16.5729(7) Å, Z = 8; at 150 K: a = 15.2541(4) Å, b = 13.4451(3) Å, c = 16.4256(5) Å, Z = 8. The structure is molecular and comprises isolated molecules. The coordination polyhderon of iron is an almost regular octahedron, Fe-O bond lengths are 1.977–2.003 Å (293 K) and 1.982–2.006 Å (150 K). In the crystalline state, the molecules are arranged in layers, and iron atoms are located on a plane yielding an almost regular trigonal net with the Fe...Fe separations of 7.558–8.103 Å (293 K) and 7.472–8.017 Å (150 K). The adjacent layer is positioned exactly over the first one with a Fe...Fe distance of 8.303 Å (293 K) and 8.236 Å (150 K).     

双核银络合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成与结构

二-(二苯基膦)甲烷(dppm)是一种易与金属形成多核络合物的有机膦配体。我们用dppm作为配体合成了一系列银的多核络合物,并对其结构进行了研究。本文报导了其中一个双核化合物[Ag_2(dppm)_2(Py)_2(μ-Cl)]ClO_4的合成及晶体结构、分子结构的测定。     

Hydrothermal synthesis and crystal structure of a layered vanadium oxide with an interlayer metal coordination complex: [Co(phen)3][V10O26]·H2O

A novel compound, [Co(phen)₃][V₁₀O₂₆]·H₂O, was hydrothermally synthesized and characterized by single-crystal X-ray diffraction. This compound crystallizes in the orthorhombic space group Ccca with a=13.447(3), b=29.936(6), c=23.252(5) Å, V=9360(3) Å³, Z=8 and R=0.0285. Data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K in the range of 1.36<θ<24.99°. The structure of the compound consists of vanadium oxide layers, which are built up from the infinite VO₄ chains by corners and edges sharing. The [Co(phen)₃]²⁺ complexes occupy the interlayer space and contact each other via π−π stacking interactions of the phen groups to form infinite one-dimensional chains.     

Waugh-型镍钼杂多酸的量子化学计算

采用半经验INDO法，完成了Waugh-型镍钼杂多酸（NH44）6〔NIMO9O32〕·6H2O的量子化学计算，得到146个成键轨道和78个反键轨道，轨道能级，电荷和键序等数据。通过对这些数据的分析，表明杂多酸分子中端氧和Ni都可能为化学活性中心，各原子轨道在分子轨道中都占有一定比例，其HOMO和LUMO能级皆为负值，其体系具有进一步接受电子的能力。这些结论与实验事实一致。