Double-stranded helical lanthanide(III) supramolecular networks with rigid diimine ligands: Synthesis, structure, and physical properties

Two lanthanide coordination complexes [Nd(NO₃)₃(CH₃OH)₂(4,4′-bipy)₂] (1) (4,4′-bipy=4,4′-bipyridine) and [4,4′-Hbipy][La(NO₃)₄(H₂O)₂(4,4′-bipy)] (2), with a salt of cationic diprotonated 4,4′-bipy, [2(4,4′-H₂bipy)][4(NO₃)] (3), have been identified and isolated from a methanol solution of Ln(NO₃)₃·6H₂O, 4,4′-bipyridine and pyrazine in 1:2:1 ratio. Their structures have been determined by single-crystal X-ray diffraction analyses, which reveal that 1 has an interesting three-dimensional supramolecular architecture containing 2₁ double-stranded helical chains through hydrogen bonding and π–π interactions, while 2 and 3 have well defined infinite chiral 3D open networks that undergo self-interpenetration. The electrospray ionization mass spectra (ESI-MS) indicate that the covalent complex has higher stability than the electrostatic bonding one. ESI-MS/MS of these ions reveal that the Ln–O bond forms a stronger coordinated bonding than that of Ln–N system and the nitrate anion remains bound to the lanthanide centers after complete dissociation in methanol solution.     

垂直入射几何条件下氦原子(e,2e)反应的理论研究

用BBK模型和修正后的BBK模型在电子垂直入射几何条件下对氦原子的三重微分散射截面进行了理论计算,并把计算结果与实验测量结果进行比较,对截面的结构进行了分析,并对交换效应进行了系统的研究. 关键词： DS3C模型 中间峰 屏蔽效应 交换效应     

Cation disorder in NaW2O6+δ·nH2−zO post-ion exchange with K, Rb, Sr, and Cs

The structure of the defect pyrochlore NaW₂O_6+δ·nH_2−zO after ion exchange with K, Rb, Sr or Cs for Na has been investigated using thermal analysis, solid-state nuclear magnetic resonance, laboratory X-ray and neutron diffraction methods. Neutron diffraction studies show that both the A-type cations (Na⁺, K⁺, Rb⁺, and/or Cs⁺) and the water molecules reside within the channels that form in the 111 direction of the W₂O₆ framework and that these strongly interact. The analytical results suggest that the water and A-type cations compete for space in the tunnels within the W₂O₆ pyrochlore framework, with the total number of water molecules and cations being approximately constant in the six samples investigated. The interplay between the cations and water explains the non-linear dependence of the a lattice parameter on the choice of cation. It appears that the ion-exchange capacity of the material will be controlled by the amount of water initially present in the sample.     

Influence of deposition pressure on structural, optical and electrical properties of nc-Si:H films deposited by HW-CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) thin films were deposited using HW-CVD technique at various deposition pressures. Characterisation of these films from Raman spectroscopy revealed that nc-Si:H thin films consist of a mixture of two phases, crystalline phase and amorphous phase containing small Si crystals embedded therein. We observed increase in crystallinity in the films with increase in deposition pressure whereas the size of Si nanocrystals was found ∼2 nm over the entire range of deposition pressure studied. The FTIR spectroscopic analysis showed that with increasing deposition pressure the predominant hydrogen bonding in the films shifts from, Si-H to Si-H₂ and (Si-H₂)_n complexes and the hydrogen content in the films was found in the range 6.2-9.3 at% over the entire range of deposition pressure studied. The photo and dark conductivities results also indicate that the films deposited with increasing deposition pressure get structurally modified. It has been found that the optical energy gap range was between 1.72 and 2.1 eV with static refractive index between 2.85 and 3.24. From the present study it has been concluded that the deposition pressure is a key process parameter to induce the crystallinity in the Si:H thin films using HW-CVD.     

Structural investigations of the xTeO2-(1−x)GeO2 (x=0, 0.2, 0.4, 0.6, 0.8 and 1) tellurite glasses: A composition dependent Raman spectroscopic study

Raman spectra of xTeO₂-(1−x)GeO₂ (x=0, 0.2, 0.4, 0.6, 0.8 and 1) germanium tellurite glasses were measured and analyzed in an effort to follow the structural changes caused by mixing two typical glass formers. Systematic Raman intensity measurements have been performed in an effort to elucidate the composition induced structural changes and a possible mechanism accounting for these changes was proposed. The network structure of the glass is characterized by TeO₄ trigonal bipyramid mixed with TeO₃ trigonal pyramid units, while GeO₄ tetrahedral units are also present. Changing the GeO₂ content results in the conversion of the TeO₄ units to TeO₃ units with a neutral doubly bridged oxygen atom, while the existence of charged terminal oxygen atoms is questionable. The measured relative Raman intensities are semi-quantitatively correlated to the transformation of the TeO₄ trigonal bipyramid to TeO₃ trigonal pyramids.     

Densification mechanism of polyacrylonitrile-based carbon fiber during heat treatment

Polyacrylonitrile (PAN)-based carbon fibers were heat treated at various temperatures for varying durations to simulate the graphitization process in the manufacture of C/C composites. Densification of the resulting fibers was confirmed by density measurement. The composition and structure of the fibers were investigated by means of elemental analysis, X-ray diffraction and Raman spectroscopy. For specified isothermal heat treatment time, the structural parameters depended strongly on heat treatment temperature. The nitrogen content decreased with increased heat treatment temperature and extended time at constant temperature. Nitrogen loss was complete at temperatures above 1900 °C. The graphite crystallite size increased rapidly with increasing heat treatment temperature, and slowly with extended isothermal heat treatment time. At 2100 °C a more ordered graphitic structure appeared. Denitrogenation induced “puffing”, which made the fibers expand. Decrease in density in the heat treatment temperature range 1500-1900 °C originated from the abrupt evolution of nitrogen, and above 1900 °C the graphitization transition induced steadily increasing density. Densification of the carbon fibers was determined both by the rate of denitrogenation and the rearrangement of carbon atoms.     

球面散布数据点插值的误差估计

讨论球面上散布数据点插值的误差估计问题．一方面用深刻的新概念——正规生成集对插值节点集的特性进行刻画,同时给出它与基本系统、网格范数间的关系;另一方面得到了插值误差及导数的点态估计．     

Miura transformation for the “good” Boussinesq equation

It is well known that each solution of the modified Korteveg–de Vries (mKdV) equation gives rise, via the Miura transformation, to a solution of the Korteveg–de Vries (KdV) equation. In this work, we show that a similar Miura-type transformation exists also for the “good” Boussinesq equation. This transformation maps solutions of a second-order equation to solutions of the fourth-order Boussinesq equation. Just like in the case of mKdV and KdV, the correspondence exists also at the level of the underlying Riemann–Hilbert problems and this is in fact how we construct the new transformation.     

Generaton of tunable 16 μm radiation by stimulated hyper-raman effect in strontium vapour

The generation of tunable 16 μm radiation by stimulated hyper-Raman scattering from atomic strontium vapour is reported. The infrared radiation has a linewidth of 0.4 cm⁻¹ which corresponds to that of the nitrogen laser pumped dye laser used as a pump source. Due to relatively low pump intensity the infrared power was only 20 mW. However, the system is easily scalable to a higher conversion efficiency.     

Diffusion-limited energy transfer from Tb3+ → Nd3+ and Tb3+ → Ho3+ in DMSO

The energy transfer phenomenon has been studied from Tb³⁺ → Nd³⁺ and Tb³⁺ → Ho³⁺ in DMSO. A diffusion limited dipole-dipole mechanism of energy transfer is suggested for both systems. At high acceptor concentrations, P_da depends linearly on C² consistent with the Fong and Diestler theory of energy transfer. However, at low acceptor concentrations the observations of time evolutions of Tb³⁺ luminescence decay following flash excitation has enabled us to examine diffusion limited energy transfer from Tb³⁺ to Nd³⁺ and Tb³⁺ to Ho³⁺ in DMSO.