不饱和类锗烯H2C=GeNaBr的密度泛函理论研究

应用密度泛函理论DFT方法,在B3LYP/6-311G(d,p)水平上研究了不饱和类锗烯H2C=GeNaBr的结构及异构化反应.结果表明,不饱和类锗烯H2C=GeNaBr有3种平衡构型,其中非平面的p-配合物型构型能量最低,是其存在的主要构型.并对平衡构型间异构化反应的过渡态进行了计算,求得了转化势垒,预言了最稳定构型的振动频率和红外强度.     

METAL COMPLEXES OF POLYCYCLIC TERTIARY AMINES. PART VI. PREPARATION AND CRYSTAL STRUCTURE OF HEXAMETHYLENETETRAMINE-SILVER(I) BROMIDE (1/4)

<正> C6H12N4Br4Ag4,Mr = 891.31, orthorhombic, Pnma, a = 8.778(2),b = 9.80.5(2), c = 16.906(3) A, V = 1455.1(4) A3, Z = 4, Dx = 4.069, Dm (displacement of H2O) = 4.03 g cm-3 , A(Mo-Ka) = 161.3 cm-1 , F(OOO) = 1615.77,T = 295°, final R = 0.052 arid Rw = 0.062 for 1472 observed reflections.All four lone pairs of each (CH2)6N4 molecule serve as ligand sites in a polymeric framework comprising octahedral AgBr5N, tetrahedral AgBr3N, and tetragonal pyramidal AgBr4N coordination polyhedra. The Ag-N and Ag-Br bond lengths lie in the ranges 2.366(12)-2.454(12) and 2.640(2)-3.178(2) A, respectively.     

不饱和硼烯HClN=B:重排反应的DFT研究

采用量子化学中的密度泛函方法, 在B3LYP/6-311G**水平上研究了不饱和硼烯HClN=B:的重排反应机理。结果表明, 无论是氢原子H迁移还是氯原子Cl迁移都经过1个三元环过渡态,生成直线型产物。但氢原子H迁移是在面内进行, 而氯原子Cl迁移是在面外进行。根据计算结果,详细研究了不饱和硼烯HClN=B:重排反应的热力学及动力学函数, 在此基础上讨论了不饱和硼烯HClN=B:的存在寿命问题。     

MORPHOLOGICAL OBSERVATION OF SINGLE-CHAIN POLY (METHYL METHACRYLATE) PARTICLES*

Tapping mode atomic force microscope has been applied to observe single-chain PMMAparticles which were stored for six months at room temperature after sprayed from verydilute solutions in good solvents, good/poor mixed solvents, and a theta solvent. Monodis-perse PMMA standards of molecular weights ranging from 7.90×10~4 to 1.3×10~6 wereused to investigate the effect of molecular weight oh the size of the single-chain PMMAparticles. These single-chain particles showed close to spherical shapes. The morphologyof single-chain PMMA particles of a given molecular weight was found to be identical inspite of different solvents used for solution spraying. Molecular weigh dependence of theparticle dimension was also found. The diameters of single-chain PMMA particles aftercorrection of tlp-geometry effect were compared to the values estimated from molecularweight and density.     

飞行时间型质量分析器(TOFMS)的研制及应用

自行研制了电子碰撞离子化的飞行时间型质量分析器（ＴＯＦＭＳ），用于物质的化学分析。用研制的ＴＯＦＭＳ测量了Ａｒ离子化的飞行时间谱和离子的部分电离截面积比与碰撞电子能量的依赖关系，将它与Ｓｔｅｐｓｈａｎ等人的实验结果进行了比较。     

四氯化碳ν_1振动在费米共振光谱特性参数中的作用

研究了CCl4的ν1+ν4与ν3的费米共振现象。结果表明ν1振动频率是影响费米共振红外和拉曼光谱特性参数(峰位差Δ,耦合系数W,光谱强度比R,非谐力常数K等)的主要因素,而其光谱强度大小却与这些参数无直接关系。本文用Berttran理论和群论对这一结果给以解释。该研究对理解费米共振现象和分子结构研究中的谱线归属等有参考价值。     

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture (dimethyl sulfoxide + water) by concentration-dependent Raman study and ab initio calculation

In this study,our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content.The Raman peak position of the v(S=O) stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water.In addition,the two vibrational modes,namely,the CH 3 symmetric stretching mode and the CH 3 asymmetric stretching mode have been analysed under different concentrations.We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study.The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.     

液芯光纤光谱仪

液芯光纤可以使拉曼光谱强度提高103倍。将液芯光纤既作为样品池又作为前置放大系统,研制成功了体积小、重量轻、成本低、灵敏度高的小型拉曼光谱仪。结果表明:通过对液体及溶在液体中的样品进行自发拉曼光谱、共振拉曼光谱的测量,获得了理想的拉曼光谱。     

火炮立楔式炮闩抽筒系统的动态特性

针对火炮立楔式炮闩抽筒系统中的卡壳和构件动态断裂等抽筒故障,以动力学理论为基础,将其转化为系统动态特性的定量研究。分析了抽筒系统的工作机理并建立了连续接触动力学模型,定量地推导出药筒及系统内接触构件的运动规律和碰撞载荷。建立了杠杆式抽筒子在抽筒过程中的弹性波动模型,采用该模型能够定量地得出抽筒子的动应力分布和力学参数的影响。进行了理想抽筒工况下理论模型的数值计算和实体模型的仿真模拟,同组比较结果验证了定量分析模型的合理性。所建模型可为解决抽筒故障提供理论依据,也可为抽筒系统的动力学和结构优化设计作铺垫。