激光作用产生的CnH^-、CnF^-、CnF3^-及其结构分析

作者在自制的仪器上, 以脉冲激光(波长532nm, 能量密度10^8W/cm^2)在10^-^4Pa的真空中溅射合适的样品, 产生了一系列CnH^-、CnF^-和CnF3^-, 记录了它们的飞行时间质谱。     

氯分子束与钛表面激光化学反应动力学

本文采用飞行时间质谱技术测定了在紫外(355nm), 可见(560nm)和近代红外(1064nm)脉冲激光作用下, 氯分子束与Ti表面反应产物的质量分布和速度分布。所得结果表明, 不同波长激光诱导反应的主要产物相同, 有Ti, TiCl, TiCl3和TiCl4。在高能量密度的紫外激光作用下, 首次测得具有很高动能的原生Ti+。各种含Ti氯化物的飞行时间谱, 能满意地用单组分或多组分Maxwell-Boltzmann公式拟合和分析。上述激光诱导气-固表面反应的机理主要由氯分子在Ti表面上的解离吸附,吸附态氯原子在表面上生成TiClx(X=1～4)的连串反应以及激光诱导脱附所组成。近红外激光主要引起热脱附, 而紫外激光的作用还原可能有非热脱附过程。     

Characteristics of excited-state intermediates of TiO2–Y-Zeolite and MCM41 encapsulating photosensitive molecules: design of new photocatalysts

Some photosensitive molecules, such as p-N,N′-dimethylaminobenzoic acid (DMABA), Nile Red, heteropolytungstic acid (H₃PW₁₂O₄₀, HPA) and metalloporphyrins, have been entrapped onto nano-scale pores or channels of TiO₂-modified Y-Zeolite (TiO₂-Y-Zeolite) and MCM41 (TiO₂-MCM41) and their excited-state intermediates have been characterized in terms of the excited-state dynamics by using laser spectroscopic techniques. Through these studies, it has been found that the photo-induced electrons are generated from the intramolecular charge transfer (ICT) state of DMABA, Nile Red or metalloporphyrin (MnTPP(Cl)), followed by transferring to the TiO₂-Y-Zeolite or TiO₂-MCM41 more efficiently as compared to the bulk TiO₂, NaY-Zeolite or MCM41. The efficient photoinduced interfacial electron transfer causes the rapid formation of radicals of those photosensitive molecules (a few tens ps). It has been also found that these photophysical properties can be applied to develop the new photocatalyst as observed by the efficient photocatalytic activities of the DMABA or Nile Red-entrapped TiO₂-Y-Zeolites for the photoreduction of an azo-dye such as Methyl Orange in water. On the other hand, in case of HPA-entrapped TiO₂-Y-zeolite, the electron generated from the excited-state TiO₂ is transferred to HPA, followed by formation of the reduction product, heteropoly blue (HPB) which is also generated by UV irradiation of HPA. This electron transfer is analogous to the Z-scheme mechanism of plant photosynthetic systems showing two photon reactions. Because of this photoelectron transfer mechanism, the HPA-entrapped TiO₂-Y-zeolite has demonstrated the synergistic enhancement of the photocatalytic decomposition of Methyl Orange and hydrogen generation from photolysis of water.     

天花粉蛋白的化学VI.用液光拉曼光谱研究天花粉蛋白的二级结构

由天花粉蛋白的水和重水溶液的激光拉曼光谱,测得酰胺III谱带1240cm[-1]和酰胺I谱带1632,1660cm[-1]对CH2弯曲模式1448cm[-1]的强度比值,按Lippert等建立的方程组作定量计算,求得天花粉蛋白的二级结构含量为α-螺旋43.5%,β-折叠31.3%和无序25.2%,它们与4A分辨率天花粉蛋白单晶X射线衍射法的结果相一致,同时,研究了上述溶液的冻干粉状固体的二级结构,经过冻干,使其中约10%的β-折叠转变成无序构象,而α-螺旋含量无明显变化,在水溶液中,由测得的I850/I830比值计算,天花粉蛋白中的酪氨酸残基约有805呈"暴露式"。     

苯甲酸钠团簇离子的形成和结构

用串级飞行时间质谱(Tandem TOF)仪研究了激光蒸发方法产生的苯甲酸钠及裂解产物团簇离子的形成和可能的构型。通过对苯甲酸钠团簇离子的紫外光解的研究, 决定了反应通道及分支比, 并定性地讨论了其结构特征。     

Simulating the Performance of Michelson- and Sagnac-based Laser Interferometric Gravitational Wave Detectors in the Presence of Mirror Tilt and Curvature Errors

We model the behaviour of single-bounce delay-line dual recycled Sagnac-based interferometer and compare its performance with that of single-bounce Michelson-based system. Geometric imperfections such as mirror tilt and curvature mismatch can strongly influence the performance of the Sagnac device due to the inherently smaller free spectral range (FSR) and higher order mode spacing. This leads to a greater number of higher order modes near, or within the signal band in the signal recycling cavity of the instrument. The important consequence of that is, in general, a greater sensitivity of a Sagnac system to nonideal parameters and imperfections of various kind affecting the performance of a real interferometer. A number of optical configurations have also been examined numerically to determine the best possible optical arrangement, in the presence of such geometric imperfections. We show that there is an optimum choice for the nominal radius of curvature of the end mirrors which results from balancing the loss due to mirror tilt against that due to curvature mismatch.     

六氟化铀振动激发态的紫外吸收变化

本文以脉冲CO2激光激发SF6分子,经碰撞V-V传能产生UF6振动激发态,在波长220-330nm范围内研究其紫外吸收瞬时变化.在静态池的条件下,分别测定了脉冲CO2激发能量以及SF6和UF6的分压对紫外吸收变化的影响,曾对2.0TorrSF6和2.0TorrUF6混合气体在激光脉冲能量为160mJ时,振动受激的UF6分子的紫外吸收变化与波长的关系作了研究,发在在240,248,290和313nm处有明显的吸收变化的峰值,这可能系几种不同的高振动态SF6分子的吸收截面的变化所引起的.     

XeCl准分子激光引发香芹酮的化学反应

本文报道了用XeCl准分子激光引发香芹酮(1)化学反应的研究结果.根据反应产物香芹酮樟脑(2)和1-挂,5-二甲基-顺2-[(乙氧羰基)甲基]双环[2.1.1]己烷(3)与激光照射能量的关系,得出香芹酮的1→2→3的反应过程.实验表明,在低激光强度照射时,每照射1焦耳能量生成2和3的量随着激光强度的增加而增加,并显示出饱和趋势.同时在照射过程中观察到浓度效应和发光.     

二价钐激活复合氟化物磷光体的合成及光谱特性

报道了合成二价钐激活的复合氟化物的简单方法。用H~2作还原剂, 用高温固相反应直接制得Sm^2+激活磷光体: KMgF~3, LiBaF~3, BaBeF~4, SrMgF~4和BaMgF~4等, 其中BaBeF~4, SrMgF~4和BaMgF~4中掺入Sm^2+为首次报道。在KCaF~3,CaBeF~4, SrBeF~4和CaMgF~4中只观察到Sm^3+发射而无Sm^2+发光。分析了钐离子价态与其质组成结构间关系, 讨论了钐离子(Sm^2+和Sm^3+)的光谱特征。