飞行时间质谱仪中激光解离的Ni^＋与醇类化合物分子束流气 …

将分子束流,激光解离和飞行时间质谱结合起来,在一个石英反应室内,让激光解离的Ｎｉ＾２＋与连续喷入的醇分子不流发生反应,产物经飞行时间质谱仪检测,研究了Ｎｉ＾＋一Ｃ２～Ｃ６等五种醇分子的气相反应。用如下的插入机理解释反应：（１）选择性的插入醇分子共价键;（２）β－Ｈ迁移至Ｎｉ＾＋;（３）失去一中性分子形成产物离子。     

A high-resolution time-of-flight mass spectrometer for the detection of ultracold molecules

We have realized a high-resolution time-of-flight mass spectrometer combined with a magneto-optical trap. The spectrometer enables excellent optical access to the trapped atomic cloud using specifically devised acceleration and deflection electrodes. The ions are extracted along a laser beam axis and deflected onto an off-axis detector. The setup is applied to detect atoms and molecules photoassociated from ultracold atoms. The detection is based on resonance-enhanced multi-photon ionization. Mass resolution up to m/Δm_rms=1000 at the mass of ¹³³Cs is achieved. The performance of this spectrometer is demonstrated in the detection of photoassociated ultracold ⁷Li¹³³Cs molecules near a large signal of ¹³³Cs ions. PACS 07.75.+h; 32.80.Rm; 37.10.Gh     

Time-of-flight mass spectrometer coupled to a position sensitive detection

In this article we present the first results that we have obtained with a time-of-flight mass spectrometer coupled to a position sensitive detector. This new spectrometer provides a three-dimensional imaging (X and Y positions and time-of-flight) of the ion packet on the detector, with a high acquisition rate and a high resolution on both the mass and the position. This new apparatus is used to measure the electric deflection of PABA (p-amino benzoic acid) and PABA dimer beams and to study the kinetic energy release of the photofragmentation of the PABA dimer.     

Modification of Reflectron Time-of-Flight Mass Spectrometer for Photodissociation of Mass-Selected Cluster Ions

介绍了一种改进的反射式飞行时间质谱装置用于光解质量选择的团簇离子. 该装置中采用了\选质-减速-解离-再加速"的方式. 团簇离子在反射式飞行时间的一级聚焦点被选质,接着被减速,并且立即被光解,光解所产生的碎片以及没有被光解的母体离子被重新加速,这一系列过程都在靠近一级聚焦点的位置完成. 相对文献中报道的其他方式,采用这一方式更利于光解碎片和母体离子的分离,更容易确定光解激光的触发时间,同时,由于母体离子在一级聚焦点的空间分布比较窄,也有利于光解激光束照射到所有的团簇离子,从而提高光解效率. 对母体离子、碎     

时间、能量分辨的光电离质谱技术研究气相自由基反应

闪光光解流动管反应器与同步辐射光电离质谱技术两者相结合组成实验平台用于探测气相自由基反应动力学。外触发的脉冲激光光解流动管反应器内的先驱物来产生待反应的自由基;自由基与反应气体发生反应后,由流动管侧壁小孔取样、取样后的混合气体被同步辐射光电离;飞行时间质谱探测光电离产生的离子。同时脉冲信号触发脉冲发生器使其产生一连串的脉冲,间隔40~50μs,此脉冲外触发质谱的采集,连续采集覆盖单次光解反应过程。质谱的时间分辨率为40μs,满足微秒时间内探测反应动力学过程。通过同步辐射光电离反射飞行质谱能直接探测自由基反应产物,并利用光电离效率曲线获得其电离能并区分不同的异构体。实验利用光解产生Cl自由基并与1-丁烯和异丁烯反应,测得反应的加成和消除产物,并获得其加成产物的电离能。     

Time-of-flight mass spectrometry studies of an ion beam generated by the titan source

The TITAN source generates wide-aperture beams of gas and metal ions of different materials. This is achieved because of two types of cold-cathode arc discharges, which operate simultaneously in the discharge system of the source. For metal ions to be obtained, use is made of the vacuum arc initiated between an ion-forming cathode and a hollow anode. To produce gas ions, a constricted low-pressure arc discharge is initiated with the same hollow anode. The constitution of ion beams generated by the TITAN source has been investigated using a homemade time-of-flight spectrometer. This paper describes the design of the latter and the principle of its operation, and discusses the physical peculiarities of the spectrometer operation, which affect the ion beam constitution. Institute of High Current Electronics. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 21–28, February, 2000.     

氯苯的同步辐射光电离研究

利用真空紫外同步辐射和反射式飞行时间质谱仪对氯苯进行了光电离研究,通过测量各离子的光电离效率(PIE)曲线,得到了氯苯的电离势为(9.11±0.05)eV及两种主要碎片离子C6H+5和C4H+3的出现势分别为(12.96±0.05)和(16.27±0.05)eV.结合有关文献的热力学数据,推导出C6H5Cl+、C6H+5及C4H+3的离子生成焓及一些键的解离能.实验获得了118.0nm同步辐射光电离下氯苯的质谱图.     

飞行时间质谱峰值的漂移

飞行时间质谱仪(time-of-flight mass spectrometer, TOF-MS)在分子团簇的激光电离/解离动力学研究中广泛使用。文章报道了在用脉冲355 nm的YAG激光进行水/甲醇二元团簇的多光子电离研究中,发现在电离激光相对于脉冲分子束的不同延时下,即激光作用于脉冲束的不同位置,飞行时间质谱仪测得的离子的质谱峰值发生漂移。在激光作用于脉冲束的中段时,离子的信号最强,同时离子的峰值漂移达到最大。分析认为：这种峰值漂移不是因为新质量数谱峰的出现,而是离子在穿越质谱仪的离子引出区和加速区极板时发生部分离子吸附,引起极板间电压的起伏造成的。离子在电场起伏下的数值模拟与实验中观测到的离子峰值漂移规律一致。     

A NEW EXPERIMENTAL METHOD IN THE STUDY OF IONIC RYDBERG STATES BY RESONANCE IONIZATION MASS SPECTROSCOPY

We report a new method for detecting highly excited ions. With a strong constant electric field ionization following the extracting of ions by a pulsed electric field in a time-of-flight mass spectrometer, the direct multi-photon ionization background can be eliminated in laser multi-step resonance ionization mass spectroscopy of ionic Rydberg states. A high detection efficiency call be obtained for law members of ionic Rydberg states by use of this method. We have applied the method in the study of the spectroscopy of ionic Rydberg states ia ytterbium.     

Secondary Electron and Negative-Ion Emission from Metal Surface under the Bombardment by Positive Ions (H<Superscript>+</Superscript>, Cl<Superscript>+</Superscript>, HCl<Superscript>+</Superscript>)

A trap for positive ions (H⁺, Cl⁺, HCl⁺) is created within a time-of-flight mass spectrometer. The yields of secondary electrons and negative ions (HCl^?, H^?) formed due to forward and backward scattering of positive ions by steel wire at different kinetic energies (200–750 eV) are measured.     

Influence Factors on Particle Growth for On-line Aerosol Matrix-assisted Laser Desorption/Ionization Time-of-flight Mass Spectrometry

利用自行研制的蒸发/冷凝实验装置作为基质辅助激光解吸/电离飞行时间质谱仪的特种接口,通过冷凝方式在线添加基质,冷凝管出口处的最终粒子直接引入空气动力学粒径分析仪或自行研制的飞行时间质谱仪,可对实验室产生的生物气溶胶粒子进行实时检测. 同时研究了最终粒子粒径大小的决定因素：加热池温度、初始粒子大小及其粒子数浓度及基质种类,获得了探测分析物分子离子峰所需的实验条件.     

Analytical method for computing the electrostatic field distribution in the reflector of the time-of-flight mass spectrometer

The method of analytical calculation of a nonlinear electrostatic mirror of the time-of-flight mass spectrometer and the numerical method of computation of a nonlinear mirror are analyzed. We present the results of simulating of the devices with nonlinear focusing mirrors, which are calculated analytically and by the numerical method, and of the device with a linear reflectron. It is concluded on the basis of the results of simulation that the proposed analytical method for calculating a nonlinear electrostatic mirror of the time-of-flight mass spectrometer is much better than the existing numerical method.     

410～355 nm内四甲基硅的多光子解离和电离研究

利用平行板电极装置研究了四甲基硅在410～378 nm内的MPI光谱;利用TOF质谱仪研究了该分子在402～371 nm内若干个波长点处的TOF质谱;利用四极质谱装置研究了它在355 nm处的MPI质谱.测得了355 nm下Si(CH3)+n(n=1,2,3,4)及Si+的激光光强指数,以及其信号强度占总信号强度的分支比随光强的变化关系.据此,讨论了该分子MPI过程的可能通道,得出了Si+主要来自于母体分子的多光子解离-硅原子的电离、Si(CH3)+n(n=1,2,3)主要来自于Si(CH3)n(n=1,2,3)的自电离、Si(CH3)+4来自于母体分子的(3+1)电离的结论.     

Dissociation of Cyclotrimethylenetrinitramine Under 1064-nm Laser Irradiation Investigated by Time-of-Flight Mass Spectrometer

Laser-induced dissociation pathways of cyclotrimethylenetrinitramine have been investigated with a focused laser of 1064 nm by use of a time-of-flight mass spectrometer. The ions produced from the cyclotrimethylenetrinitramine surface were detected and the mass spectra of both positive and negative ions were obtained. According to the possible distribution of the decomposition products, possible dissociation paths of cyclotrimethylenetrinitramine were proposed. The influence of the intensity and the delay time of the laser beam to the decomposition have also been studied. The results may possibly throw some light on our understanding of the reactions taking place in laser ignition.     

自由钨团簇与氮分子反应性的尺寸相关性

用激光蒸发团簇源产生Wn团簇束 ,团簇通过一个充有N2 气体分子的低压反应池 ,利用飞行时间质谱探测反应产物 ,在单次碰撞条件下研究了W+ 10 —W+ 50 和N2 分子的反应性 ,在室温条件下测量了N2 分子与W+ n 团簇反应的反应几率 .n =10— 2 6的团簇与N2 分子的反应几率与团簇尺寸有很强的相关性 ,n =16 ,2 2 ,2 3的团簇有较高的反应性 .W+ n 与N2 分子的反应性与Wn与N2 分子的反应性显示出相似的规律性. A beam of tungsten clusters, seeded in He gas, is produced in a pulsed laser vaporization source. We have studied the size-dependent reactivity of positive tungsten cluster ions with N 2 under single-collision conditions by using laser-vaporization source, low-pressure reaction cell and time-of-flight mass spectrometer. The reaction probability with N 2 molecule was measured as a function of cluster size, W + 10-W + 50, for clusters produced at room temperature...     

基于自适应共振神经网络的单粒子激光电离质谱数据分析

气溶胶激光飞行时间质谱仪(ALUOFMS)可以在线地对气溶胶单粒子进行物理和化学特性分析,利用双束连续激光对单个粒子的空气动力学粒径进行测量,并通过飞行时间完成单粒子化学成分的检测。该仪器在运行过程中将产生海量的实验数据,对这些数据快速、自动处理并提取有价值的信息是整机系统的关键之一。文章介绍了基于神经网络的自适应共振算法(ART-2a)在随机混和的氯化钠、氯化钙、邻苯二甲酸二正辛酯(DOP)和2,5二羟基苯甲酸(DHB)气溶胶单粒子聚类分析中的成功运用。同以往的质谱分析方法相比,ART-2a可以实现对任意多和任意复杂的输入模式进行自组织,自适应和自稳定的快速识别,更有利于质谱数据的分析。实验结果表明,当警戒值为0.40,学习速率为0.05以及迭代次数为6时,ART-2a可以成功地对这四种物质进行分类,同时得到4类物质的聚类中心,每类的聚类中心都能很好的代表该类物质的特征。     

Ionic Angular Distributions Induced by Strong-Field Ionization of Tri-Atomic Molecules

Angular distributions of fragment ions from ionization of several tri-atomic molecules(CO_2, OCS, N_2O and NO_2) by strong 800-nm laser fields are investigated via a time-of-flight mass spectrometer. Anisotropic angular distributions of fragment ions, especially those of atomic ions, are observed for all of the molecules studied.These anisotropic angular distributions are mainly due to the geometric alignment of molecules in the strong field ionization. Distinct different patterns in ionic angular distributions for different molecules are observed. It is indicated that both molecular geometric structure and ionization channels have effects on the angular distributions of strong field ionization/fragmentation.     

Compensation of large ion energy spreads by multigap grid reflectors in time-of-flight mass spectrometers

The problem of compensation of the initial ion energy spread by a multigap grid reflector of the time-of-flight mass spectrometer is considered. It is shown mathematically that the problem can be reduced to analysis of properties of catastrophes A_n under additional conditions of positive geometrical gaps of the reflector. Examples of design of reflectors corresponding to catastrophes A₂ and A₃ are analyzed. The advantage of a three-gap reflector over a two-gap reflector in the compensation of a large energy spread of ions for the same value of the resolution of the device is demonstrated. The application of the three-gap reflector improves the sensitivity of the time-of-flight mass spectrometer. The results of calculations are confirmed experimentally.     

Use of Soft Plasma Ionization Source at Evacuated Air Atmospheres in Time-of-Flight Mass Spectrometry to Suppress Fragmentation of Volatile Organic Compounds

This study describes a measuring system for mass spectrometry, consisting of a glow discharge ionization source for soft plasma ionization and a time-of-flight mass spectrometer, to detect toxic volatile organic compounds rapidly and easily. It is the most important to determine how the complicated fragmentation of such compounds can be suppressed to occur so as to recognize the mass spectra of the volatile organic compounds as their fingerprints. The novelty of this work is that the optimal discharge condition for the soft plasma ionization–time-of-flight mass spectrometer system could be selected, so that the parent mass peak of analyte molecules could be observed both with high sensitivity and with little or no fragmentation of them. Use of air gas at a pressure of 1000 Pa provided the most favorable result for these criteria, whereas, in a previous report, the soft plasma ionization source operating with argon at a pressure of 346 Pa had yielded additional mass peaks of the fragmented species. The reason for this would be explained by the fact that energetic electrons in the plasma, which principally cause the fragmentation of the volatile organic compounds, have lower number density at higher gas pressures, through de-accelerated collisions with the plasma gas.