A momentum imaging microscope for dissociative electron attachment

We describe an experimental approach to image the three-dimensional (3D) momentum distribution of the negative ions arising from dissociative electron attachment (DEA). The experimental apparatus employs a low energy pulsed electron gun, an effusive gas source and a 4π solid-angle ion momentum imaging spectrometer consisting of a pulsed ion extraction field, an electrostatic lens, and a time- and position-sensitive detector. The time-of-flight and impact position of each negative ion are measured event by event in order to image the full 3D ion momentum sphere. The system performance is tested by measuring the anion momentum distributions from two DEA resonances, namely H(-) from H(2)O(-) ((2)B(1)) and O(-) from O(2)(-) ((2)Π(u)). The results are compared with existing experimental and theoretical data.     

计算化合物分子式的五种方法

计算化合物分子式的五种方法包括高分辨质谱法 ( HRMS) ,高分辨质谱数据法 ( HRMS data) ,元素分析法 ( EA) ,1 3 C-核磁共振 ( COM,DEPT)数据法 ( 1 3 C-NMR( COM,DEPT) data)和三相似法。第一种方法 :根据 HRMS测得的分子量精确值 M和环加双键数 ( r+db) ,推断出化合物的分子式。第二种方法 :计算分子式的方法与第一种方法相类似 ,只不过是首先应按照测得的精确分子量的尾数 ,估算出分子式的总含氢原子数 ,然后再确定分子式。第三种方法 :按照 HRMS测量的 M、( r+db)和 EA测量的化合物的组成元素百分比含量 ,计算分子式。第四种方法 :根据 1 3 C-NMR测量的化合物分子各组成功能团的数目来确认分子式。第五种方法 :通过被测化合物的特征离子质谱与共同的分子式 CH3 ( CH2 ) n COR进行比较后 ,推断出分子式 ,例如柱晶白霉素、麦地霉素和生枝霉素具有共同的分子式 C3 5H56NO1 3 RR1 R2 ,其差别仅是它们的 R、R1 和 R2 不同。     

Design of and data reduction from compact Thomson parabola spectrometers

Thomson parabola spectrometers are used to characterize MeV ion beams produced in high intensity laser interactions. These spectrometers disperse multiple ion species according to their charge to mass ratio through the use of parallel electric and magnetic fields. Analytical solutions for ion deflection in electric and magnetic fields have been used to extract ion spectra with the assumption that fringing effects are negligible. Experimental space restrictions and dynamic range requirements necessitate designs that stress the analytical assumptions. Depending on design parameters, the error in the analytical assumption can be comparable to the energy resolution. Estimates are provided to approximate the error on the total ion deflection. A method for modeling ion trajectories including fringing effects is presented using software freely available or in common use. The magnetostatic fields are modeled in 3D, including material properties of nearby magnetic materials using RADIA. Electrostatic fields are modeled in 2D for a spectrometer implementing angled plates using the partial differential equation toolbox in MATLAB(?). Using these models to calculate the ion trajectory allows for analysis of a Thomson parabola spectrometer with an arbitrary field configuration.     

小型飞行时间质谱装置的构建

飞行时间质谱仪（TOF MS）在准确度、分辨率、灵敏度、质量上限、分析速度等方面具有优势,在生命科学等领域发挥着重要作用。目前商用飞行时间质谱仪已经比较成熟,但仪器尺寸普遍较大,且价格昂贵,维护困难;而小型仪器则面临分辨率较低等问题。提高小型飞行时间质谱仪的分辨率,降低购置成本和维护成本,对于飞行时间质谱仪的大范围推广有着重要意义。本工作构建了一套分辨率较高的小型飞行时间质谱装置,包括真空系统、离子源、锥孔、引出加速及偏转模块、离子反射镜模块、探测器模块、电路系统等。该仪器主体尺寸较小（0.5 m×0.5 m×0.7 m）,飞行管长度仅0.25 m。由于采用了模块化设计思路,各个模块之间独立封装,仪器的维护、升级工作简单易行。该仪器的关键模块采用创新设计,使得在m/z 2 000处分辨率可达4 200。     

A magnetic-bottle multi-electron-ion coincidence spectrometer

A novel multi-electron-ion coincidence spectrometer developed on the basis of a 1.5 m-long magnetic-bottle electron spectrometer is presented. Electrons are guided by an inhomogeneous magnetic field to a detector at the end of the flight tube, while a set of optics is used to extract counterpart ions to the same detector, by a pulsed inhomogeneous electric field. This setup allows ion detection with high mass resolution, without impairing the high collection efficiency for electrons. The performance of the coincidence spectrometer was tested with double ionization of carbon disulfide, CS(2) → CS(2)(2+) + e(-) + e(-), in ultrashort intense laser fields (2.8 × 10(13) W/cm(2), 280 fs, 1030 nm) to clarify the electron correlation below the rescattering threshold.     

飞行时间质谱和高性能电子学控制技术

飞行时间质量分离器是飞行时间质谱仪的主要组成部分。飞行时间质谱（TOF MS）具有分析质量范围宽、分析速度快、仪器结构简单等优点,但离子初始动能和初始位置容易分散是影响其分辨率的核心因素。本综述根据本课题组多年的研制经验,着重介绍离子束垂直引入方式的反射式有栅网飞行时间质谱的离子光学以及相关电子学控制的核心技术原理。离子光学核心技术涉及到离子加速场和离子反射场的机械加工控制和精密装配控制等,电子学控制核心技术主要包括高压电源和高压脉冲电源的精密制作。     

Small mass spectrometer with extended measurement capabilities at high pressures

For the in situ investigation of planetary atmospheres a small Mattauch-Herzog mass spectrometer has been developed. Its high-pressure performance has been improved by incorporating differential pumping between the ion source and the analyzing fields, shortening the path-length as well as increasing the extraction field in the ion source. In addition doubly ionized and dissociated ions are used for mass analysis. These measures make possible operation up to 10(-2) millibars. Results of laboratory tests related to linearity, dynamic range, and mass resolution are presented, in particular for CO(2).     

辉光放电质谱仪Element GD的应用

A newest high resolution glow discharge mass spectrometer (HR-GD-MS) was developed by Thermo Electron Bremen Manufactory. Combine of a glow discharge ion source with a successful high resolution mass spectrometer, Element GD become the ultimate tool for direct analysis of conductive materials. Every part of Element GD: GD ion source, mass spectrometer, detection system and software are designed for high throughput analysis: measure 50 elements at less than 10-9 within 5 minutes. Application in microelectronics, aerospace, medical/pharmaceutical/food and nuclear will be shown.     

激光电离碘甲烷中空间电荷对飞行时间质谱峰的影响研究

利用飞行时间质谱（TOFMS）研究碘甲烷分子激光电离的过程中,发现I⁺离子峰的峰形随激光光强增大逐渐加宽,且CH_q⁺ (q=0~3)离子峰位置随光强增大而发生移动。激光功率密度从1.4×10¹⁰ W/cm²增加到5.2×10¹⁰ W/cm²时,I⁺离子峰的半高全宽W_1/2从113 ns增加到426 ns,同时CH₃⁺离子的峰位置向前位移了52 ns。通过对I⁺离子峰的半高全宽W_1/2和CH₃⁺离子峰位置与碘离子强度I_I⁺关系的分析,发现I⁺离子峰的半高全宽W_1/2正比于I_I^+0.5,而CH_q⁺ (q=0~3)的峰位移与碘离子的强度I_I⁺成正比。激光焦点处离子间的库仑排斥作用随着离子强度的增大而增大,由于这种空间电荷效应造成的库仑势能的增加对离子的初始平动能有一定影响,并导致离子到达检测器的时间发生改变,因而半高全宽的增大和离子峰位移随离子强度的变化规律,可以用空间电荷效应来解释。     

Pulsed ion cyclotron resonance mass spectrometer for studying ion-molecule reactions

A pulsed ion cyclotron resonance mass spectrometer utilizes the cyclotron resonance principle for mass analysis of ions trapped at low pressures by electric and magnetic fields. Both mass analysis and ion trapping are accomplished in a one-region device called a trapped ion analyzer cell. A pulsing sequence is described which allows for generation of ions by electron impact, reaction with added gases, and mass analysis of the products of ion-molecule reactions. Methods are described for measuring rate constants and equilibrium constants for ion-molecule reactions. The high ion trapping efficiency and open geometry of the analyzer cell make it well suited for studying the interaction of laser radiation with gaseous ions and may also be useful for high-accuracy isotope ration mass spectrometry.     

Note: Integration of trapped ion mobility spectrometry with mass spectrometry

The integration of a trapped ion mobility spectrometer (TIMS) with a mass spectrometer (MS) for complementary fast, gas-phase mobility separation prior to mass analysis (TIMS-MS) is described. The ion transmission and mobility separation are discussed as a function of the ion source condition, bath gas velocity, analysis scan speed, RF ion confinement, and downstream ion optical conditions. TIMS mobility resolution depends on the analysis scan speed and the bath gas velocity, with the unique advantage that the IMS separation can be easily tuned from high speed (~25 ms) for rapid analysis to slower scans for higher mobility resolution (R > 80).     

非对称三角形电极离子阱的单向出射性能模拟研究

三角形电极离子阱（triangular-electrode linear ion trap, TeLIT）是一种新型结构的线性离子阱,具有简单的电极结构和良好的分析性能。为进一步提高TeLIT的离子探测效率,本实验将离子出射方向的2个电极设置为不同角度,建立非对称结构的TeLIT,通过引入非对称场实现离子单向出射。通过分析电极角度差与其内部电场分布的关系,并模拟离子运动轨迹,获得离子出射情况和模拟质谱峰。理论模拟结果显示：当离子出射方向三角电极的角度差Δα=15°时,在优化的AC频率条件下,三角形电极离子阱的m/z 610离子单向出射率可达95%以上,且质量分辨率达到2647。经优化几何参数后的非对称三角形电极离子阱可在几乎不损失分辨率的情况下实现离子单向出射,大幅提高了单检测器模式下TeLIT的离子探测效率和仪器的灵敏度,使其在小型化质谱仪的开发中具有显著优势。     

SYNAPT G2 HDMS高清质谱性能特点及应用简介

SYNAPT~(TM) G2 HDMS质谱分析系统是沃特世公司第二代基于高效离子淌度(ion mobility spectrometry,IMS,也称离子迁移)技术的高性能四极杆-飞行时间质谱仪。通过两种技术的结合与升级,SYNAPT G2 HDMS不仅能按离子的质荷比分离检测,还可根据离子的大小、形状等将其分离。因此,此质谱系统不但可以提高传统质谱数据的准确性,更可以提供样品形态信息,从而得到样品活性、结构状态等信息。其在蛋白组学、代谢组学、糖及脂类分析、医学标志物发掘、药物开发与质控、食品安全检测、环境安全检测等方面有着广泛的应用空间,并已经表现出良好的性能优势,成为各领域工作者的有力的分析工具。本文简要介绍该系统的性能特点及应用。     

High mass resolution time of flight mass spectrometer for measuring products in heterogeneous catalysis in highly sensitive microreactors

We demonstrate a combined microreactor and time of flight system for testing and characterization of heterogeneous catalysts with high resolution mass spectrometry and high sensitivity. Catalyst testing is performed in silicon-based microreactors which have high sensitivity and fast thermal response. Gas analysis is performed with a time of flight mass spectrometer with a modified nude Bayard-Alpert ionization gauge as gas ionization source. The mass resolution of the time of flight mass spectrometer using the ion gauge as ionization source is estimated to m∕Δm > 2500. The system design is superior to conventional batch and flow reactors with accompanying product detection by quadrupole mass spectrometry or gas chromatography not only due to the high sensitivity, fast temperature response, high mass resolution, and fast acquisition time of mass spectra but it also allows wide mass range (0-5000 amu in the current configuration). As a demonstration of the system performance we present data from ammonia oxidation on a Pt thin film showing resolved spectra of OH and NH(3).     

基于离子阱原理的空间小型质谱仪理论模拟研究

当前空间探测活动日益频繁,其中对空间有机分子的探测是空间探测的一项重要任务。由于太空中特殊的工作条件,一般商品质谱仪的体积、功耗和分析能力等都不能满足要求,因此需要研发小体积、低功耗、高稳定性的质谱仪。本研究基于离子阱原理,提出了由多个环形电极构成的新型平方离子阱,这种多环高压结构能有效减小离子阱的体积,从而实现质谱仪器的小型化。通过采用成比例的直流电压分时段供电,成功扩展了该质谱仪的离子检测范围。经仿真计算,拟合出了离子振荡频率与其质量数的关系。该质谱仪对质量数在1~2000 u 范围内的分子,质量分辨大于1400,能够满足空间大分子质量分辨的基本要求。     

An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies

We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ～ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates.     

Secondary ion quadrupole mass spectrometer for depth profiling--design and performance evaluation

A quadrupole-based secondary ion mass spectrometer designed for depth profiling is described which combines ultrahigh vacuum construction with high sputtering rate, detection sensitivity, depth resolution, mass spectral purity, and abundance sensitivity. Impurities such as B and Al implanted in Si can be profiled to levels below one part per million atomic (ppma), at a depth resolution equal to that obtained by commercial ion microprobes. The primary beam consists of 5-keV, mass-analyzed (40)Ar(+) ions, focused to about 70 microm in diameter. Its high current density (>25mA/cm(2)) permits adequate beam rastering and electronic signal-gating to optimize depth resolution. A secondary ion extraction lens and spherical energy filter are responsible for achieving abundance sensitivities of five to six orders of magnitude on the low mass side of a matrix peak. The ultrahigh vacuum environment of the sample dramatically reduces molecular peaks containing H, C, and O, allowing even hydrogen to be profiled to concentrations below 10 ppma. Because large amounts of data are generated by multi-element depth profiling, means for automated instrument control and data acquisition have been developed.     

Quantitative analysis of transient surface reactions on planar catalyst with time-resolved time-of-flight mass spectrometry

A procedure for the quantitative analysis of transient surface catalytic reactions in millisecond time resolution has been studied constructing a specially designed apparatus employing (1) pulsed-gas valves for the injection of reactant molecules onto catalysts and (2) a time-of-flight mass spectrometer (TOF-MS) to detect every reaction product simultaneously. For a better understanding of the catalytic activity and selectivity for products quantitatively, a procedure for measuring an amount of reactant molecules injected onto catalyst surface and calibrating the intensity of mass signal were proposed and implemented. We tested the applicability of this procedure for the quantitative analysis of products of NO+H(2) reaction on Pt-Al(2)O(3) catalysts (a planar catalyst: Pt-Al(2)O(3)Si substrates inserted into a micro-tube-reactor with SiC balls). Although the surface area of the planar catalyst was very small, the mass signal intensities of the reaction products were found to be sufficient for the above procedure. We measured the fragmentation patterns and the inherent sensitivity factors in the TOF-MS using the mixture of the internal standard gas Ar and the N-containing gases. The relative sensitivity factors for NH(3), N(2), NO, and N(2)O and the relative intensities of fragment peaks to the molecular ion peak of H(2)O and N(2)O were estimated. The procedure constructed here has enabled us to analyze the transient consecutive secondary catalytic reactions as well as primary reactions based on the formation rate of product molecules per millisecond instead of the mass signal intensities of the reaction products.     

A homemade high-resolution orthogonal-injection time-of-flight mass spectrometer with a heated capillary inlet

We describe a homemade high-resolution orthogonal-injection time-of-flight (O-TOF) mass spectrometer combing a heated capillary inlet. The O-TOF uses a heated capillary tube combined with a radio-frequency only quadrupole (rf-only quadrupole) as an interface to help the ion transmission from the atmospheric pressure to the low-pressure regions. The principle, configuration of the O-TOF, and the performance of the instrument are introduced in this paper. With electrospray ion source, the performances of the mass resolution, the sensitivity, the mass range, and the mass accuracy are described. We also include our results obtained by coupling atmospheric pressure matrix-assisted laser deporption ionization with this instrument.     

Versatile cold atom target apparatus

We report on a compact and transportable apparatus that consists of a cold atomic target at the center of a high resolution recoil ion momentum spectrometer. Cold rubidium atoms serve as a target which can be operated in three different modes: in continuous mode, consisting of a cold atom beam generated by a two-dimensional magneto-optical trap, in normal mode in which the atoms from the beam are trapped in a three-dimensional magneto-optical trap (3D MOT), and in high density mode in which the 3D MOT is operated in dark spontaneous optical trap configuration. The targets are characterized using photoionization.