时间分辨电子自旋共振及其应用

简要介绍了作者研制的高时间分产电子自旋共振（ＴＲＥＳＲ）波谱仪的结构与特点。报道了均相与微复相体系中光解自由基的自旋相关自由基极化;在对苯醌的乙二醇／水／硫酸溶液中,观察到苯醌自由基与溶液中质子发生交换效应。综述了ＴＲＥＳＲ在光诱导极化与光诱导电子转移研究方面的应用。     

激光光解苯甲醛自由基的时间-分辨ESR研究

利用高时间分辨ESR波谱仪,对苯甲醛为光敏分子的各体系进行了CIDEP(化学诱导动态电子极化)研究,揭示了苯甲醛体系的CIDEP信号的产生过程,并进一步确认了其产生过程中的极化特征.     

二苯酮与胺光化夺氢反应的时间分辨ESR研究

报道用时间分辨ESR方法研究了二苯酮与典型胺类化合物体系紫外光照产生的瞬态自由基及化学诱导动态电子自旋极化效应,得出的反应机理可与稳态ESR结果相互补充.     

激光光解自由基的TR-ESR研究

时间分辨电子自旋共振（TR-ESR）技术是探测和鉴定光化学反应过程中顺磁性中间体的强有力工具,利用TR-ESR技术观察到的化学诱导动态电子极化 (CIDEP) 可以为我们提供丰富的光化学反应机理、反应动力学等信息. 该文较为详细地介绍了CIDEP的4种机理和自行研制的一种零差拍平衡混频的时间分辨ESR波谱仪,总结了TR-ESR技术在光解自由基反应方面的应用.     

链接琥珀酰亚胺的线性硝酮的合成与ESR研究

该文设计并合成一种新的线性硝酮自由基捕获探针DSC-PBN(N-(4-(((2,5-dioxopy-rrolidin-1-yloxy)-carbonyloxy)methyl)benzylidene)-2-methylpropan-2-N-oxide),并采用UV、MS、1H NMR等一系列手段表征分子结构.进一步通过自由基捕获实验显示,DSC-PBN可与多种活泼自由基反应生成稳定的氮氧自由基加合物,且所得ESR谱图易于解析和分辨.由于DSC-PBN自由基捕获探针链接琥珀酰亚胺基团,可望通过与蛋白质(或多肽)N端的共价键合而应用于生物体系自由基分析.     

时间分辨CIDNP技术

简要综述了时间分辨CIDNP（Time Resolved Chemically Induced Dynamic Polarization Effect）技术的发展概况、原理、实验及其应用.     

时间分辨动态LIBS测量方法

针对激光诱导击穿光谱(LIBS)研究对时间分辨动态光谱测量方法的需求,建立了基于多通道光纤束的动态LIBS测量方法。该方法首先利用不同长度的光纤组成多通道光纤束,对瞬态LIBS信号进行差异延迟,使按照特定时间序列发射的光谱信号同步到达探测器,而后采用面阵ICCD相机对同步到达的多通道光谱信号进行高时间分辨探测。该方法单次测量即可获得LIBS辐射不同时刻的时间分辨光谱。为了验证基于多通道光纤束的动态LIBS测量方法,研制了具有19个通道的光纤束,光纤束中包含的各个单根光纤长度呈等差数列排布,长度差设置为10 m,对应测量的时间间隔约为50 ns,单次测量记录的总时间长度近900 ns。分别基于短脉冲激光光源和标准光源,开展了系统时间响应和光谱响应特性研究,获得了系统的时间响应数据和光谱响应曲线。用YAG激光器的二倍频激光(532 nm)诱导Si产生等离子体辐射光谱,在线测量了辐射光谱的时间演化历程,获得了Si等离子体辐射过程中SiⅠ390.52 nm,SiⅡ385.51 nm,SiⅡ413.12 nm谱线从0～898 ns时间范围内19个时刻的光谱信息,获得了特征光谱的演化规律,验证了该...     

激光诱导的钛酸钡等离子体的时间分辨光谱

利用光学多通道分析仪（ＯＭＡⅢ）研究脉冲激光沉积钛酸钡薄膜过程中的激光诱导等离子体的时间分辨发射光谱，利用各种粒子不同时刻发射的谱线强度描绘成该粒子的飞行时间谱，表征了等离子体中该粒子的空间浓度分布，根据飞行时间谱的特征，推算了粒子束脉冲（等离子体）的空间宽度及其与缓冲气体压力的关系，提出了在激光沉积多元氧化物薄膜过程中的合适的缓冲气体压力范围，解释了激光原位沉积高温超导薄膜中所需氧气分压达３０Ｐ     

丙酮/1,2-丙二醇体系的化学诱导动态电子自旋极化研究

285 nm紫外激光照射下,用时间分辨电子自旋共振(TRESR)波谱仪研究了光解丙酮/1,2-丙二醇(ACETONE/PG)体系,得到了丙酮羰自由基(CH3)2.COH和1,2-丙二醇羰自由基CH3.COHCHOH的发射/吸收(E/A)型极化信号,这是一个自由基对(RPM)极化过程。在酸性环境中,溶剂分子的CIDEP谱明显减弱,(CH3)2.COH的CIDEP谱无明显变化,由此可判断光解ACETONE/PG体系是一个夺氢反应;在碱性环境中,(CH3)2.COH反应生成负离子基(CH3)2.CO-.     

InGaN薄膜中电子自旋偏振弛豫的时间分辨吸收光谱研究

采用飞秒时间分辨圆偏振光抽运-探测光谱对In_01Ga_09N薄膜的电子自旋注入和弛豫进行了研究.获得初始自旋偏振度约为02,此结果支持在圆偏振光激发下,重、轻空穴带的跃迁强度比为3∶1,而不支持1∶1或1∶094的观点同时获得自旋偏振弛豫时间为490±70ps,定性分析了自旋弛豫机理,认为BAP机理是电子自旋弛豫的主要机理. 关键词： 电子自旋 InGaN 自旋极化 自旋弛豫     

Analysis of the Mechanism of Photolysis of Methanol-d4 Solutions of Acetylpropionyl Peroxide with the Use of Chemically Induced Dynamic Nuclear Polarization

On the basis of the effects of chemically induced dynamic nuclear polarization of ¹H and ¹³C and the yields of reaction products, the photolysis of methanol-d ₄ solutions of acetylpropionyl peroxide is investigated within the temperature interval 193–333 K. Polarization of all the protons of ethylethanoate is detected; it is shown that the latter is formed in several chemical reactions. The role of different excited states of the peroxide in the mechanism of its photolysis is discussed.     

Theoretical study of the intensity of chemically induce dynamic electron polarization of radical-triplet pairs

Considering the interaction between encited triplet molecule and cloublet radical,based on the second-order perturbation theroy and the motion equation of density matrix,the polarzation intersity of RTPM were theoretically calculated with the overpopulated doublet spin states and quartet spin states of radical0triplet paris as initial conditions the radical result from the zero-field-splitting(zfs)and the multiplet A/E and E/A polarization result from hyperfine (hf) interactions of the triplet molcule,The hyperfine ralated A A/E or E E/A CIDEP on the radical were the overpopulation of the net abscrptive or emissive polarization and multiple A/E or E/A polarization.     

Mott散射和电子极化术

文章回顾了Mott散射过程及其物理图像,介绍了Sherman函数的定义、计算和测量,简述了探测自旋极化电子的仪器——Mott电子极化仪的一般设计,列举了获得自由极化电子的几种方法和原理.     

Mott散射和电子极化术

文章回顾了Mott散射过程及其物理图像，介绍了Sherman函数的定义、计算和测量，简述了探测自旋极化电子的仪器——Mott电子极化仪的一般设计，列举了获得自由极化电子的几种方法和原理．     

Electron Spin Resonance of Free Radicals Produced by Ultraviolet Photolysis in Some Vegetables and Their Juices

Abstract

Paramagnetic species produced by ultraviolet photolysis in various vegetables of domestic origin have been investigated by electron spin resonance technique. The ESR spectra of the small cut pieces of the vegetable fleshes and their frozen juices have been investigated before and under UV photolysis. The samples of potato and carrod exhibit too complex ESR spectra, but parsley, dill, white radish and green pepper do not exhibit any ESR signal before UV photolysis at 113 K. However both the small cut pieces of fleshes of potato, carrot, parsley, dill, white radish and green pepper and their juices exhibit ESR spectra during UV photolysis that we attributed to the H?O and CO^? ₂ radicals. The ESR parameters of these radicals have been obtained and the origins of these radicals have been shown to be the glucose molecules in the carbohydrate chains of these substances.     

Spin concentration in a possible ESR dosimeter: An electron spin echo study on X-irradiated ammonium tartrate

Several single crystals and powder samples of ammonium tartrate, recently proposed as a possible ESR dosimeter, have been X-irradiated with different doses. The total radical concentration has been determined by quantitative cw ESR, by comparison with a standard. The samples have been studied by electron spin echo spectroscopy. The two-pulse echo decay has been obtained and simulated by a single exponential function for different values of the microwave power of the pulses and for different pulse lengths. The dependence of the phase memory time TM on the microwave power has been exploited to get information on the contribution of the instantaneous diffusion to spin dephasing. At room temperature in the range of radical concentrations of 10(18)-10(19) spins/cm3 the instantaneous diffusion is the dominant spin dephasing mechanism. The linear dependence of the instantaneous diffusion on the total concentration of the radicals is in agreement with the theory. From the latter result we conclude that the average radical-radical distance corresponds to a random distribution of the radicals in the matrix. A simple method of measuring the radical concentration by the ESE decays in powder samples of irradiated ammonium tartrate is described.     

ESR studies on the pressure and temperature dependence of electron self-exchange kinetics between tetrathiafulvalene (TTF) and its radical cation in ionic liquids and organic solvents

The question whether chemical reactions and diffusion processes in ionic liquids are comparable with those taking place in classical organic liquids is a current issue in the literature. Pressure- and temperature-dependent investigations on simple electron self-exchange reactions between the two partners of a redox couple are good tools to get a better understanding of how the solvent influences such reactions. The electron self-exchange reaction between tetrathiafulvalene (TTF) and its radical cation has been investigated in two ionic liquids and two organic solvents using electron spin resonance (ESR) line broadening experiments at variable temperature and pressure. Rate constants are reported for the ionic liquids 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim⁺][Tf₂N^?]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim⁺][Tf₂N^?]) within a temperature range of 298 K ≤ T ≤ 368 K and a pressure range of 0.1 MPa ≤ p ≤ 100 MPa. The self-exchange reaction of the redox couple [TTF/TTF^?+] has been found to be diffusion-controlled in the used ionic liquids over the entire temperature range. The observed rate constants in ionic liquids at higher pressures are larger than those predicted by common diffusion, and suggest that the electron transfer takes place within a solvent cage. Also, the self-exchange reaction of the [TTF/TTF^?+] redox couple in classical solvents (dimethylphthalate (DMP) and acetonitrile) was investigated and compared to the results with those obtained in ionic liquids. The high viscosity of the ionic liquids makes it difficult to extract the electron transfer rate constants reliably, making interpretation within the framework of the Marcus Theory impossible.