反射式飞行时间质谱仪结合纳升电喷雾电离源研究金属簇合物

An experiment facility has been set up for the study of metal cluster compounds in our laboratory, which consists of a nano-electrospray ionization source, an ion transmission and focus system, and a reflectron time-of-flight mass spectrometer. Taking advantage of the nano-electrospray ionization source, polyvalent ions are usually produced in the “ionization” process and the obtained mass resolution of the equipment is over 8000. The molecular ion peaks of metal cluster compounds [Au₂₀(PPhpy₂)₁₀Cl₂](SbF₆)₄, where PPhpy₂=bis(2-pyridyl)phenylphosphine, and [Au₆Ag₂(C)L₆](BF₄)₄, where L=2-(diphenylphosphino)-5-methylpyridine, are distinguished in the respective mass spectrum, accompanied by some fragment ion peaks. In addition, the mass-to-charge ratios of the parent ions are determi-nated. Preliminary results suggest that the device is a powerful tool for the study of metal cluster compounds. It turns out that the information obtained by the instrumentation serves as an essential supplement to single crystal X-ray diffraction for structure characterization of metal cluster compounds.     

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.     

基于FT-ICR质谱仪的光解离光谱自动化谱图采集程序的开发与应用

光解离光谱在气相离子结构及动力学研究中发挥着重要的作用.这种方法非常灵活,可在实验室中利用不同种类的激光器及质谱仪的结合来开展相应的研究.但也存在一些问题,例如,自动化水平低,费时,长时间的操作容易引入人为错误,使实验结果的可信度降低.为解决此类问题,该工作开发了一套可用于光谱自动采集和分析的程序AutoMS.该程序包...     

A New Concept for Time-of-Flight Mass Spectrometry with Slowed-down Short-Lived Isotopes

A new concept for direct mass measurements of short-lived nuclei with an electrostatic time-of-flight mass spectrometer is described. The spectrometer can be coupled to an in-flight separator such as SHIP or FRS via a gas stopping cell and a gas-filled linear Paul trap. The time required for mass measurement is of the order of a few milliseconds allowing one to investigate nuclei with these short half-lives. A mass-resolving-power m/Δm _FWHM=50 000 has been reached. First results of the range-focusing technique are presented, which is under development for the efficient stopping and extraction of relativistic exotic nuclei. This revised version was published online in July 2006 with corrections to the Cover Date.     

用于兰州彭宁离子阱的多反射飞行时间质量分析器的设计和优化

MRTOF-MS是最近几年发展起来的新型质谱仪,较传统的飞行时间质谱仪而言,MRTOF-MS质量分辨本领更高。开发了一种用于MRTOF-MS设计的新方法,该方法由参数设置部分和离子运动计算部分共同组成;分全局搜索和局部细化两个步骤,可用于优化MRTOF-MS的几何构型、计算不同条件下的最佳电压设置组合。基于这种方法,设计了一种机械结构与国际上同类设备不同的MRTOF-MS,该设备可用于高精度原子核质量测量,也可用于快速质量选择,为LPT提供纯净的目标核。通过优化,确定了其几何参数和电压参数,讨论了不同电极上的电压偏差对质量分辨本领的影响,定量地分析了电源的精度要求。优化结果表明:MRTOF-MS的最佳漂移长度约为400 mm;在最佳电压设置下,当40Ar1+的总飞行时间为6.5 ms时,其质量分辨本领可达1.3×105;要求电源精度好于50 ppm,最好达到20 ppm。Multi-reflection time-of-flight mass spectrometer (MRTOF-MS) has been developed as a new device which has a higher mass resolving power than traditional mass spectrometers in recent years. A new method including two sub-procedures, global search and local refinement, has been developed and applied to design a MRTOF-MS. It consists of two components, parameter configuration and ion motion simulation, and can be used to optimize the geometries of the spectrometer and the potentials applied on the electrodes to achieve the optimum in different conditions. By using this method, a different type of MRTOF mass analyzer has been designed for mass measurements and isobaric separation for Lanzhou Penning Trap (LPT). The geometry of this analyzer and potentials at different electrodes have been optimized, and the relations between resolving power and potentials and the power accuracy requirements have been analyzed and discussed quantitatively. The simulation shows that the optimal length of the drift-tube is about 400 mm; the maximal resolving power of 1.3×105 has been achieved with a total time-of-flight of 6.5 ms under the optimal potentials for an ion species of 40Ar1+; and the inaccuracy of the potentials applied to the mirror electrodes must be less than 50 ppm or preferably 20 ppm.     

离子光学系统简单数值计算方法在反射式飞行时间质谱仪中的应用

简要阐述了求解离子光学系统电场结构分布以及带电粒子在该电场中运行轨迹的通用数值计算方法,分析了在保证计算精度的前提下,节省磁盘空间、提高计算速度的PC级计算机上优化算法,并提出一种寻找最佳超松弛因子的可行性方法.在PC级计算机上应用该计算方法对一台无栅网结构高分辨率反射式飞行时间质谱仪进行计算,给出了电场分布、粒子飞行轨迹和设定各种不同条件对电场进行优化的结果.根据计算结果调整的反射式飞行时间质谱仪达到了其优化工作状态,所测得的质谱分辨率显著提高.     

用于团簇研究的激光反射式飞行时间质谱仪

报道了新建造的用于团簇研究的反射式飞行时间质谱仪 ,包括反射式飞行时间质谱仪的结构、原理、真空系统、控制系统等 .初步性能测试表明 :激光溅射 /分子束载带型团簇离子源能够产生丰富的一元、二元团簇离子 ;质谱仪对离子的质量分辨接近 2 0 0 0 ,并且质量门也有较高的质量选择性 .系统用于团簇研究 ,得到了一些初步实验结果 .     

氦喷嘴激光飞行时间质谱仪系统传输效率的测定

建立了一套氦喷嘴激光飞行时间质谱仪系统并进行了离线模拟研究.其工作原理是:首先在原子化室蒸发产生样品气态原子来模拟核反应产物,然后利用氦气传输和氦喷嘴技术,使样品原子形成准直原子束与激光作用.通过激光共振激发电离实现原子序数Z的选择,再利用飞行时间质谱技术来确定原子量A,实现样品原子的分离与鉴别.通过用²⁴Na的放射性测量的方法对谱仪系统效率进行了研究,其传输效率约为17%.     

小尺寸VmOn+团簇的激光光解和密度泛函计算

通过激光溅射法产生了V₂O_n⁺ (n=1, 2), V₃O_n⁺ (n=1, 2, 3)和V₄O₃⁺等缺氧的钒氧团簇,并采用532和266 nm波长的激光对它们进行了光解研究. 利用密度泛函理论计算与激光光解实验相结合确定了这些团簇的几何结构和可能的光解通道. 激光光解实验表明V相似文献   

用于二元合金团簇负离子研究的光电子能谱仪

报道了自行研制的磁瓶式飞行时间光电子能谱仪 ,它安装在自制的反射式飞行时间质谱仪的一级聚焦点的接口部位 ,将用于二元合金团簇负离子几何和电子结构的研究 .仪器测试的能量分辨好于 0 .1eV ,达到了设计指标 .对PbM-(M =Cu ,Ag ,Au)二元合金团簇负离子进行了光电子能谱的实验 ,获得的绝热电子亲合势与密度泛函的计算结果符合的很好 ,由此表明 ,该光电子能谱仪将适用于二元合金团簇负离子体系的研究 .     

邻碘甲苯分子光解动力学的飞秒时间分辨质谱研究

利用飞秒时间分辨质谱技术研究了邻碘甲苯分子在266 nm激发下的光解动力学. 光解产物碎片通过800 nm强激光场下的多光子电离实现探测. 拟合光解产物C₇H₇自由基和I原子随泵浦-探测延迟时间变化的信号,得到解离时间为38±50 fs,它反映的是266 nm同时激发nσ^*和ππ^*态后C-I键的平均解离时间. 此外,还利用基态碘原子的共振波长298.23 nm作为探测光,通过共振增强多光子电离方法对解离生成的基态碘原子进行了选择性探测. 拟合I⁺随泵浦-探测延迟时间变化的信号,得到解离时间为40±50 fs,这与通过800 nm多光子电离得到的解离时间一致,表明解离生成的主要产物是基态碘原子.     

甲基环己烷在9∽15.5 eV能量区的真空紫外光电离研究

利用具有同步辐射源的反射式飞行时间质谱仪,研究甲基环己烷的真空紫外光电离和光解离. 观测到母体离子C₇H₁₄⁺和碎片离子C₇H₁₃⁺,C₆H₁₁⁺,C₆H₁₀⁺,C₅H₁₀⁺,C₅H₉⁺,C₄H₈⁺,C₄H₇⁺和C₃H₅⁺的光电离效率曲线. 测定甲基环己烷的电离能为9.80±0.03 eV,通过光电离效率曲线确定其碎片离子的出现势. 在B3LYP/6-31G(d)水平上对过渡态、中间体和产物离子的优化结构进行表征,并使用G3B3方法计算其能量. 提出主要碎片离子的形成通道. 分子内氢迁移和碳开环是甲基环己烷裂解途径中最重要的过程.     

激光溅射-分子束法研究镁、铝离子与乙腈分子的气相化学反应

利用激光溅射 分子束技术研究了Mg+ 、Al+ 与乙腈分子的气相团簇反应 .根据反射式飞行时间质谱检测的结果发现 ,Mg+ 、Al+ 与乙腈分子反应形成不同尺寸的团簇离子产物 ,其中Al+ 与 (CHCN) n 的结合数n =1～10 ,而Mg+ 与 (CHCN) n 的结合数n =1～ 5 .Al+ (CHCN) n、Mg+ (CHCN) n 团簇离子产物的强度分布都存在明显的强度间隙现象 .Al+ 与 (CHCN) n 进行缔合时 ,出现了两个强度间隙 ;而Mg+ 与 (CHCN) n 进行缔合时 ,则只存在一个强度间隙 .Al+ 的第一强度间隙在n =4～ 5 ,第二强度间隙在n =6～ 7;而Mg+ 的强度间隙在n =2～ 3.     

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。     

近场光学用于激光解吸飞行时间质谱的亚微米级空间分辨成像

基于激光离子源的飞行时间质谱法作为一门新兴的成像方法,已经被广泛应用于材料、地质、环境、药物和生命科学领域中。但受限于光学衍射极限、聚焦透镜的焦距和数值孔径等因素,使其难以实现亚微米尺寸的高空间分辨率成像。近场技术的引入成功地解决了光学衍射极限的限制,将近场技术与激光电离技术相结合,可以实现对固体样品表面纳米级弹坑的剥蚀。此外,传统的质谱成像技术常常假设样品表面是平整的,忽略其表面形貌的高低起伏,但这往往会导致信号强度不稳定和成像假象。为此,不仅需要获得样品中的化学组成与空间分布,还需同时获得样品表面的形貌信息,才能实现多功能的原位表征。在自行研制的激光解吸/电离飞行时间质谱的基础上,采用近场纳米有孔针尖离子源代替传统的远场激光聚焦,以532 nm波长激光为第一束解析激光,355 nm波长激光为后电离激光,音叉式原子力显微镜控制系统针尖与样品之间的距离维持在近场范围内,对酞菁铜镀层样品表面进行了弹坑剥蚀实验,获得了直径为550～850 nm的弹坑点阵;并对7.5 μm×7.5 μm的标准酞菁铜网格样品进行了铜离子亚微米级的高分辨率成像;此外,纳米有孔针尖离子源作为原子力显微镜的一种变体,还可同时获得成像区域的表面形貌信息,这一结合优势大大拓展了质谱技术在微纳尺度下的原位表征能力。     

甲醇/水混合团簇的多光子电离质谱研究

利用多光子电离技术结合飞行时间质谱仪对甲醇/水混合团簇进行了研究.在脉冲激光波长为355 nm条件下观测到团簇离子.主要的电离产物为质子化的(CH3OH)n(H2O)H+(n=l-13)混合团簇离子与(CH3OH)nH+团簇离子,经分析(CH3OH)1o(H2O) H+和(CH3OH)3H+为幻数结构.甲醇水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.     

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.     

应用反射式飞行时间质谱仪研究氨团簇离子解离动力学

用直射式和反射式飞行时间质谱研究了氨分子团簇体系在３５５ｎｍ激光下的多光子电离,得到一系列的质子化团簇离子（ＮＨ３）ｎＨ＾＋,同时还观察到超价氨团簇离子（ＮＨ３）ｎＨ＾＋２。在反射式飞行时间质谱研究中观测到质子化氨团簇离子在自由飞行过程中的解离现象,表明在该实验条件下生成的质子化氨团簇离子是一些亚稳态团簇离子。对子离子产率的分析,得到质子化团簇离子解离速率常数,从而可以估计亚稳态团簇离子的寿命。团     

Mass resolution and ionization region within second-order compensation approach

Mass resolution and ionization region (Δx) was considered within the second-order compensation method for the time-of-flight mass spectrometer. The results estimated indicate that the resolution is proportional to inverse square root of Δx. From this behaviour, mass resolution with respect to Δx changes differently in the second-order compensation compared to the first-order compensation.