Ground state parameters of BiH3 from infrared and millimeter-wave spectra: ground state and equilibrium structures

Unstable, short-lived BiH₃ has been synthesized and investigated by rotational spectroscopy in the range 158 (J=1-0) to 1280 GHz (J=8-7). Quadrupole and spin-rotation hyperfine structures (eQq=584.676(96) MHz), and the A₁A₂ splitting of the K=3 ground state level, have been resolved. By merging the pure rotational data with 1764 ground state combination differences obtained from the analysis of high resolution Fourier transform infrared spectra of the ν₁-ν₄ bands [J. Mol. Spectrosc. (2004) (in press)] spanning J and K values up to 16 and 14, respectively, with 0?ΔK?9, the ground state rotational and centrifugal distortion constants up to octic and sextic terms for reductions A and B, respectively, have been determined. Of the reductions of the ground state rovibrational Hamiltonian, reduction B including ε rather than h₃ as off-diagonal element is clearly favored. An experimental r₀ structure of the very-near spherical oblate symmetric top BiH₃, r(BiH)=178.82 pm and α(HBiH)=90.320°, has been deduced from the rotational constants B₀=2.64160172(18) and C₀=2.6010403(31) cm⁻¹. The derived experimental r_e structure, r_e(BiH)=177.834(50) pm and α_e(HBiH)=90.321(10)°, was determined. This is in excellent agreement with the most recent ab initio structure, r_e(BiH)=177.84 pm, and α_e(HBiH)=90.12°.     

掺Perylene的PVK薄膜荧光谱及发光机理

用高荧光效率的有机染料芘(perylene)掺杂聚乙烯咔唑(PVK),其荧光光谱与芘的发射光谱基本一致,而且亮度比纯芘发光提高十多倍,说明发光主要来自芘分子,并在PVK和perylene之间存在十分有效的能量传递或电荷转移过程,荧光谱强度随掺杂浓度的变化关系说明存在一个最佳的掺杂浓度比.分析PVK和perylene之间可能发生的能量转移过程,认为从PVK到perylene这种能量转移与实验不符;分析PVK和perylene薄膜的光致发光过程,认为从(PVK+)→(perylene+)和从(PVK-)→(p     

Yb2.75C60价带光电子能谱

用角积分紫外光电子能谱技术测量了Yb2 75C6 0 薄膜的价带电子态密度分布 .相纯Yb2 75C6 0 样品通过C1s芯态x射线电子谱峰的位移表征 .结果表明Yb2 75C6 0 是半导体 ,在费米能级处几乎没有电子态分布 .Yb 6s电子态和C6 0 LU MO能带的杂化效应不可忽略 ,有部分Yb 6s电子分布在Yb C6 0 杂化能带上 .     

稀土及杂质元素对ZA27合金晶间腐蚀的影响

为了从本质上了解杂质与稀土元素对锌铝合金晶间腐蚀的影响 ,探索抑制合金晶间腐蚀的有效途径 ,依据晶界的大角度重位点阵理论编制出相应计算机软件 ,建立含稀土、杂质及 η相颗粒的α相大角度晶界原子集团模型 ,采用递归法计算了α相晶界间的电荷转移 ,由此讨论了杂质 (Pb、Sn、Cd)及稀土元素 (La、Y)对Zn、Al电极电位的影响 .结果表明 ,杂质Pb、Sn、Cd增大原子间的电荷转移量 ,提高Zn、Al电极电位差 ,加速合金的腐蚀 ,稀土元素减小原子间的电荷转移量 ,降低Zn、Al电极电位差 ,具有抑制晶间腐蚀的作用 .     

Orientational Ordering of the Near-Surface Layers of Nitrobenzene

Two types of absorption centers, one being related to monomers and the other to dimers, have been revealed by the method of statistical analysis of the normalized absorption spectra of a superthin interlayer of nitrobenzene of variable thickness formed on activated surfaces of quartz and barium fluoride and measured for different thicknesses of the interlayer. On a decrease in the interlayer thickness the concentration of dimers increases.     

Tetradecanol dehydrogenation over CuO catalyst supported on BaO, CaO and MgO

Bimetallic Cu/Mg, Ca, Ba mixed oxide compounds acted as catalyst in the dehydrogenation of tetradecanol into tetradecanal, and were characterized by thermal gravimetric analysis, surface area, X-ray diffraction, temperature-programmed reduction and desorption of CO₂. Alkaline earth oxides increased the total basic site concentration in the order of Mg>Ca>Ba. A correlation was found between the total basic site concentration and initial dehydrogenation rate. This revised version was published online in June 2006 with corrections to the Cover Date.     

Integral Method o Reciprocity in the Spectroscopy of Laser Crystals with Impurity Centers

A new method of determining the stimulated emission cross-section spectra from the absorption cross-section spectra, which we call the integral method of reciprocity, is suggested it does not require knowledge of the structure of the impurity-center electron levels. Based on this method, formulas for calculating the radiation lifetime of impurity centers in crystals have been derived. The effectiveness of the integral method of reciprocity was demonstrated in determining the stimulated emission cross sections and radiation lifetime of an ytterbium ion in the laser crystals Yb³⁺:KYW and Yb³⁺:KGW.     

Solid state phase equilibria in the Gd-Si-B system at 1270 K

Solid state phase equilibria in the ternary Gd-Si-B phase diagram have been proposed at 1270 K using X-ray diffraction, scanning electron microscopy and electron probe microanalysis. Prior to this work, the binary systems Gd-B, Gd-Si and Si-B have also been reinvestigated. The main characteristic of the ternary diagram is the occurrence of two new ternary compounds Gd₅Si₂B₈ and Gd₅Si₃B_0.64. The former crystallizes in tetragonal symmetry, space group P4/mbm with unit cell parameters a=7.2665(3), c=8.2229(7) Å, the second one presents hexagonal symmetry, space group P6₃/mcm with unit cell parameters a=8.5080(4),c=6.4141(2) Å. The X-ray structures of the two structurally related phases Gd₅Si₃B_0.64 and host binary Gd₅Si₃ have been refined from three-dimensional single-crystal intensity data to the final R values of 0.036 (R_w=0.046) and 0.046 (R_w=0.055) for 457 and 401 reflections, respectively with [F>4σ(F)]. Both structures exhibit the Mn₅Si₃-type structure, with in addition for Gd₅Si₃B_0.64 a partial occupancy by boron of the normally vacant interstitial site at the center of the Gd₆ octahedron, which corresponds to the origin of the unit cell. Bonding between the interstitial boron atoms and the gadolinium ones forming the Gd₆B polyhedra is indicated by the decrease in the corresponding Gd-Gd distances and consequently in the unit cell volume. Finally, the Gd-Si-B phase diagram is compared with the previously reported Er-Si-B, at 1070 K.     

Morphology and spectral properties of thin films of benzoxazole derivatives of biphenyl

We have studied the spectral properties and morphology of thin films (TVD films) formed by thermal vacuum deposition of 4,4′-bis[(E)-1-(1,3-benzoxazol-2-yl)-2-ethenyl]-1,1′-biphenyl and its substituted derivatives. We have shown that introducing bulky 2,2′-oxyhexyl substituents into the biphenyl units leads to a shift of the fluorescence maximum for the TVD films toward shorter wavelengths, a decrease in their photostability, and aggregation of the films during storage. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 300–303, May–June, 2007.     

五种氨基酸钆络合物的ESR波谱

迄今未见任何稀土氨基酸络合物的ESR波谱报道,本文在合成Gd³⁺分别与甘氨酸、β-丙氨酸、谷氨酸、天冬氨酸和天冬酰胺五种氨基酸络合物的基础上,测定了不同温度下,水溶液、粉末及分子筛吸附样品的ESR谱,讨论了络合物中晶体场强,对称性及成键特性。