聚氧乙烯-高氯酸锂-水复合物体系的固体核磁共振研究

运用13C和7Li固体高分辨核磁共振(NMR)技术对一系列以水作溶剂制备的不同配比聚氧乙烯(PEO)-高氯酸锂(LiClO4)复合物样品的相态结构进行了研究.发现在样品中有一定量水存在的条件下,随着LiClO4含量的增加,复合物体系经历了PEO的结晶逐渐被破坏,PEO与LiClO4形成的新的晶型逐渐增加的过程,当PEO单体与LiClO4的摩尔比在6/1与8/1之间时,样品完全非晶,水的存在对PEO与Li+的相互作用起到了明显的阻碍作用.     

超声射流冷却CCl2自由基的激光诱导荧光激发谱

在497—517nm波长范围观测超声射流冷却CCl₂自由基的激光诱导荧光激发谱。得到CCl₂在?←X跃迁中(v₁,v₂,0)←(0,0,0)振动带清晰的K结构。对近80个子谱带作了归属。振动分析给出较精确的v＇₁和v＇₂振动频率和非谐性常数;从K结构的分析得出(A＇-B＇)和(A″-B″)的值,文献未曾报道过。 关键词：     

Ar原子偶宇称3p5(2P1/2)nl'[K']J(l'=1,3)自电离态激发谱线形研究

The even-parity autoionizing resonance series 3p⁵np''[3/2]_1,2, 3p⁵np''[1/2]₁, and 3p⁵nf''[5/2]₃ of Ar have been investigated exciting from the two metastable states 3p⁵4s[3/2]₂ and 3p⁵4s''[1/2]₀ in the photon energy range of 32500-35600 cm^-1 with an experimental bandwidth of ~0.1 cm^-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile index and resonance widths, resonance lifetime and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index q and the resonance widths Γ are shown to be approximately proportional to the effective principal quantum number n^*. The line separation of the 3p⁵np'' autoionizing resonances is discussed.     

Analysis of the LIF Spectroscopy of Nickel Hydride in 19000-21400 cm-1

采用放电溅射出的镍原子与甲醇气体在超声射流条件下产生NiH分子,获得了NiH分子在15000~21400 cm-1的激光诱导荧光激发谱．首次报道了NiH分子在19000~21400 cm-1的光谱．将观测到的24个谱带归属到7个不同的电子跃迁,并对每个谱带进行了转动分析．观测到了A、B、D、E、F和G态的高振动能级,得到了这些电子态的振动频率、非谐性常数、转动常数和平衡键长等较完整的光谱常数．并重新标识了一些谱带．     

Laser-induced Fluorescence and Dispersed Fluorescence Spectroscopy of NiB: Identification of a New 2II State in 19000-22100 cm-1

The laser-induced fluorescence excitation spectra of jet-cooled NiB radicals have been recorded in the energy range of 19000-22100 cm^-1. Eleven bands have been assigned to the [20.77]²II-X²∑⁺ transition system for the first time. The dispersed fluorescence spectra related to most of these bands have been investigated. Vibrationally excited levels of the ground electronic state, with v" up to 6, have been observed. In addition, the lifetimes for almost all the observed bands have also been measured.     

草酰氯的激光诱导荧光激发谱

本文报道草酰氯C₂O₂Cl₂在358—372.5nm范围的激光诱导荧光(LIF)激发谱。对60多条振动谱带进行了归属,其中24条是吸收光谱中没有的。由振动结构得到C₂O₂Cl₂分子在X基态和?激发态的部分振动频率,其中v＂₇=84cm^-1和v＇₇=164cm^-1是新的数据。对4₀¹振动带的转动结构的分析给出转动常数A=0.190cm^-1,B=0.114cm^-1,C=0.048cm^-1。 关键词：     

HCF(X~1A’)+SO2反应的动力学研究

用激光光解-激光诱导荧光方法研究了室温下(T＝293 K) HCF(X^~1A^’)自由基与SO₂分子的反应动力学. 实验中HCF(X^~1A^’)自由基是由213 nm激光光解HCFBr₂产生的, 用激光诱导荧光(LIF)检测HCF(X^~1A^’)自由基的相对浓度随着反应时间的变化, 得到此反应的二级反应速率常数为: k＝(1.81±0.15)×10^－12 cm³•molecule^－1•s^－1, 体系总压为1862 Pa. 高精度理论计算表明, HCF(X^~1A^’)和SO₂分子反应的机理是典型的加成-消除反应. 我们运用RRKM-TST理论计算了此二级反应速率常数的温度效应和压力效应, 计算结果和室温下测定的二级反应速率常数符合得较好.