电喷雾萃取电离质谱在线监测 Friedl?nder 缩合反应

质谱在线监测有机化学反应能够实时捕捉反应过程中反应物、中间体、产物的信号及其变化情况,从而推测有机反应机理,并加深对反应本质的认识。本研究利用电喷雾萃取电离质谱(EESI-MS)技术在线监测草酸催化的邻氨基苯乙酮与乙酰丙酮间的Friedlnder缩合反应。在反应的不同时间点,分别捕捉到了反应物(m/z 136)、中间体(m/z 218、m/z 236)和产物(m/z 200)的准分子离子信号,并记录了它们的信号强度随反应时间的变化趋势,推测出了反应机理。     

60Co辐照损伤对发光二极管性能影响的研究

通过引入散射理论建立了发光二极管模型,并考虑低计量率电离辐照损伤影响,建立了器件材料散射因子与辐照损伤的关系模型.在输入电流宽范围变化的条件下,测量了器件在不同辐照条件下的电学特性,实验结果与理论模型符合良好.通过对测量结果和以上模型的分析,深入研究低剂量电离辐照损伤和发光二极管性能衰减的关系.证实由于复合中心上的电子浓度增加,导致界面态浓度和散射几率的略微增大,从而造成其I-V和L-V特性的略微衰减.同时由于重离子辐照可直接产生位移效应,使界面态浓度明显上升,因此其对发光二极管的影响较电离辐照大很多.     

Phenomenological model of multiphoto-production of charged pion pairs on the proton

The production of charged pion pairs via multiphoton absorption from an intense X-ray laser wave colliding with an ultrarelativistic proton beam is studied. Our calculations include the contributions from both the electromagnetic and hadronic interactions where the latter are described approximately by a phenomenological meson-exchange potential. Order-of-magnitude estimates for π⁺π⁻${\pi }^{+}{\pi }^{-}$ production on the proton by two- and three-photon absorption from the high-frequency laser field are obtained and compared with the corresponding rates for μ⁺μ⁻${\mu }^{+}{\mu }^{-}$ pair creation.     

氨/乙醇混合团簇多光子电离质谱

用多光子电离技术结合飞行时间质谱仪对氨与乙醇混合团簇进行了研究。在脉冲激光波长分别为266,355nm和532nm条件下,仅在355nm作用下观测到团簇离子。主要的电离产物为质子化的（C2H5OH）n（NH3）mH＋（n=0—3,m=0—4）混合团簇离子,且各个序列的离子强度随m的增大而减小。经分析,氨与乙醇混合团簇电离后团簇离子发生内部质子化转移反应是形成质子化团簇离子的主要原因。不同尺寸团簇离子信号强度随电离激光光强变化的光强指数曲线显示,团簇均发生四光子电离过程。通过理论计算得到其中性和离子团簇的稳定结构,解离能,解离通道。并证实团簇发生电离解离时发生了团簇内质子转移反应。     

基于多光子激发荧光-毛细管电泳的DNA分析新技术

研制了一套新型毛细管电泳-连续光多光子激发荧光检测系统,并用该系统对含有多种荧光染料的样品进行了电泳分离和多光子激发荧光检测.结果表明:该系统具有分离效率高、质量检测限低和宽谱激发等特点,适合生物体系等复杂样品的测量并实现了DNA样品的分离分析.     

Theoretical study of tricyclo[3,3,1,1]decane, tricyclo[3,3,1,1]decsilane molecules and their halogen derivatives, C10H12X4 and Si10H12X4 (X=F, Cl, Br, I)

The B3LYP/3-21G* ab initio molecular orbital method from the program package was applied to study tricyclo[3,3,1,1^3,7]decane and tricyclo[3,3,1,1^3,7]decsilane molecules and their halogen derivatives (1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane, C₁₀H₁₂X₄ and Si₁₀H₁₂X₄ respectively). The optimized structures of these compounds were obtained. Ionization potentials, HOMO and LUMO energies, energy gaps, heats of formation, atomization energies and vibration frequencies were calculated. The calculations indicate that these molecules are stable and have T_d symmetry. Tricyclo[3,3,1,1^3,7]decsilane and its halogen derivatives (Si₁₀H₁₂X₄) are found to have higher conductivity than tricyclo[3,3,1,1^3,7]decane and its halogen derivatives (C₁₀H₁₂X₄). 1,3,5,7-Tetrafluorotricyclo[3,3,1,1^3,7]decane (C₁₀H₁₂F₄) and 1,3,5,7-tetrafluorotricyclo[3,3,1,1^3,7]decsilane (Si₁₀H₁₂F₄) were found to be the easiest compounds to form and the most difficult to dissociate of all 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane compounds, respectively.     

Theoretical investigation of the GaF molecule and its positive ion

Coupled pair approximation and configuration interaction calculations were carried out on the gallium fluoride molecule and its positive ion with flexible basis sets. Spectroscopic constants of these species were examined in detail through step-wise extensions of correlating space. The contribution from correlations of the semi-core 3d electrons in Ga was found to be sizable. The bonding character was revealed to be highly ionic even for the positive ion. Received: 13 June 1998/Accepted: 28 August 1998 / Published online: 7 December 1998     

丁酮分子3d态的共振增强多光子电离

酮类分子含有羰基,其价电子跃迁主要涉及ＣＯ成键π轨道,Ｏ原子的非键２ｐｙ轨道和ＣＯ反键π轨道,它们的能量顺序为π＜２ｐｙ＜π,里德堡态由最高占有轨道２ｐｙ(ｎ０)的一个孤对电子向各里德堡轨道跃迁产生［１］．ＶＵＶ吸收谱［１,２］和电子能谱［１,３］都显...     

Cooper极小值对基态原子多光子电离谱的影响

考虑到残留离子势对末态光电子的影响利用ＨＦＳ自洽场方法和改进的ＫＦＲ方法,研究了在圆偏振强激光场中,基态原子外壳层电子的多光子电离过程。发现在现有条件下,Ｃｏｏｐｅｒ极小值对ｐ、ｄ态电子的多光子电离谱没有影响,或者影响甚微,对ｓ态电子多光子电离谱的影响是广泛和深刻的,而且这一影响的程度与光子的能量和光场强度有较强的依赖关系。