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相反应的研究

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+与连续喷入的醇分子束流发生反应 ,产物经飞行时间质谱仪检测 ,研究了Ni+与C2 ～C6 等五种醇分子的气相反应。用如下的插入机理解释了反应 :( 1 )选择性的插入醇分子共价键 ;( 2 ) β H 迁移至Ni+上 ;( 3)失去一中性分子形成产物离子。     

飞行时间质谱仪中的超声分子束特性

以氮气作为载气,利用266nm的YAG激光对三乙胺分子进行多光子电离研究.实验发现随着脉冲阀与skimmer距离x由小变大,到达电离中心的超声分子束强度先急剧下降,后趋于平缓,且激光相对于脉冲阀延时在一定范围的变化对超声分子束这种强度的变化趋势影响不大.分析认为,超声分子束强度的变化是由于x改变时,到达电离中心的分子数密度n和温度T的变化引起的.实验中观察到的超声分子束强度随x变化与n及T的理论数值模拟规律一致.     

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     

激光电离飞行时间质谱法研究Al原子与卤代甲烷气相化学反应

利用分子束和飞行时间质谱技术研究了激光烧蚀金属Ａｌ原子与４种不同的卤代甲烷：ＣＣｌ４，ＣＦ３Ｃｌ，ＣＦ３Ｂｒ，ＣＦ４的气相反应，由激光电离飞行时间质谱检测的结果表明，Ａｌ与ＣＦ３Ｃｌ反应生成ＡｌＣｌ，而与ＣＦ３Ｂｒ反应生成ＡｌＢｒ，与ＣＣｌ４及ＣＦ４反应分别生成ＡＣｌ及ＡｌＦ。     

氟利昂F1110分子在飞秒激光脉冲作用下的多光子解离动力学

含氟利昂在内的含氯化合物在太阳光辐射下解离生成破坏臭氧的游离态氯原子, 是破坏大气臭氧层的主要元凶. 本文利用飞行时间质谱技术及离子速度成像技术研究了氟利昂F1110(四氯乙烯)分子在800 nm飞秒脉冲光作用下的多光子解离动力学. 利用飞行时间质谱探测技术, 得到了四氯乙烯在800 nm飞秒激光脉冲作用下发生多光子解离产生的碎片质谱, 发现了两个主要碎片离子C₂Cl₃⁺和 C₂Cl₂⁺. 对应的解离机理分别为单个C-Cl键断裂直接生产氯自由基C₂Cl₄⁺→C₂Cl₃⁺ +Cl 和两个C—Cl 键断裂C₂Cl₄⁺→C₂Cl₂⁺+2Cl: 利用离子速度成像技术对这两种机理产生的碎片离子进行成像, 得到了C₂Cl₃⁺ 和C₂Cl₂⁺ 离子的速度影像. 分析发现这两个碎片离子的动能分布均可由两个高斯分布曲线拟合, 说明这两种解离机理分别还对应了两种解离通道. 通过影像分析得到了解离的平动能分布和角向分布各向异性参数等详尽的动力学信息. 通过高精度密度泛函理论计算对解离动力学进行了进一步的分析和讨论.     

溅射原子化激光共振电离-飞行时间质谱仪的研究及应用进展

自行设计和研制了国内唯一的一套溅射原子化激光共振电离－飞行时间质谱仪，并增设了微米级液态金属镓离子源、框架式压电陶瓷亚微米级微动样品台、二次电子成象和离子束自动定点打靶以及真彩色大屏幕图像显示等系统。利用该谱仪探测了地矿样品中的金和钢标样中的铜，其检出限分别达４０ｎｇ／ｇ和μｇ／ｇ量级。同时，还对其他相关领域进行了初步研究。     

脉冲激光离子源飞行时间质谱计的设计与研制

目前国内外的飞行时间质谱计，大多采用双电场加速的方式改善其质谱分辨率。通过较详尽的计算，讨论了双电场飞行时间质谱计中各参数对质谱分辨率和灵敏度的影响及其选择的方向，并在此基础上选定了仪器的主要参量，为飞行时间质谱计的设计与改进提供了依据。还介绍了在此基础上设计与建立的脉冲激光离子源飞行时间质谱计。     

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 .     

高离化态S^q＋与H2碰撞中H2^r＋的库仑爆炸及解离过程研究

采用位置灵敏探测器和散射离子-反冲离子飞行时间技术测量了900keV的S^q H2碰撞产生的H^ 碎片的能量分布，实验表明部分H2^r 发生解离。基于蒙特卡罗方法，建立了程序模拟离子与分子碰撞中的反冲离子飞行时间谱。模拟结果与实验(S^2 H2，S^2 He)测量到的TOF谱进行了分析比较，并进行了定性讨论。     

用飞行时间法研究Si溅射离子簇质谱的结构效应

通过对200kV离子注入机的改造,设计出一台飞行时间(TOF)谱仪,在提高脉冲束时间分辨方面,做了很大努力。测量了单晶、多晶及非晶硅的正、负离子簇飞行谱(质量谱)。比较这三种不同结构Si样品的谱数据,发现溅射离子簇质谱分布与靶物质结构密切相关,这为理论上研究Si离子簇的溅射形成机制提供了实验依据。 关键词：     

Laser spectroscopy on molecular beam with a time-of-flight mass spectrometer operating in a strong magnetic field

Experimental set-up for studying effects of a strong magnetic field on a structure and a decay dynamics of molecules, was designed and constructed. A vacuum chamber, in which a molecular beam propagated, was mounted in a bore of a superconducting magnet. Laser light crossed the molecular beam in the magnetic field and excited the molecules. Fragment or parent ions produced through sequential decay processes, were extracted by an electric field parallel to the magnetic field and detected by a microchannel plate. By measuring the time-of-flight from the photo-excitation to the ion-detection, a species of ions —mass and charge state— was identified. A performance of the set-up was demonstrated using the resonance enhanced multiphoton ionization process through the X²Π-A²Σ⁺ transition of nitric oxide (NO) molecules. A mass resolution m/Δm ≥180±6 was obtained in the field up to 10 T. This was the first successful result demonstrating the sufficient mass resolution obtained by the time-of-flight technique in the strong magnetic field up to 10 T. Parent NO⁺ ions were selectively detected by the mass spectrometer and the ion current was measured as a function of the frequency of the laser light. Rotational transition lines were measured with a sufficient S/N ratio in the field up to 10 T.     

浮地式反射飞行时间质谱计的设计

介绍了国家同步辐射实验室原子分子物理实验站自行研制的小型光电离反射式飞行时间质谱计(RTOFMS-Ⅲ).该仪器为浮地式结构,可用YAG激光器或同步辐射为激发光源.在质量数为107时,其质量分辨本领可达1034.     

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     

过渡金属离子Pt+和甲烷气相反应机理的理论研究

采用密度泛函理论(DFT)中的B3LYP方法研究了二重态和四重态Pt 与甲烷反应的机理.通过几何构型优化和频率计算,分别获得三个过渡态,并利用内禀反应坐标(IRC)计算进行了验证.在更高的基组水平上计算了单点能,并详细讨论了二重态和四重态的势能面.结果表明在二重态势能面上的反应具有比较低的能垒,是一个放热反应,所以该反应更易于在二重态上进行.氧化加成生成中间体HPt(CH3) 的步骤需要克服一个小小的能垒.     

Selection and design of the secondary electron channel of the time-of-flight mass spectrometer

Computer simulation is carried out for selecting a compact electron-optical system of the channel for detecting secondary electrons formed during the interaction of xenon atoms or ions with energy of 1-30 keV with Xe atoms. The solid angle of passage of secondary electron beams in a wide range of their initial energies is calculated. The energy spectrum of secondary electrons with various energies is determined by constructing their deceleration curve.     

Quantitative reference-free express analysis of some alloys on a laser time-of-flight mass spectrometer

A technique is proposed for analyzing the isotopic and elemental content of metals and alloys with the help of the LAZMA time-of-flight laser mass spectrometer. It is shown that for multicomponent alloys when working in the regime of the “main” maxima and recording all the ions in the energy spectrum the device enables one to perform quantitative measurements of sample composition and obtain valid results without the use of reference samples. Zh. Tekh. Fiz. 69, 138–142 (October 1999)     

过渡金属离子Pt+和甲烷气相反应的势能面研究

采用密度泛函理论（DFT）中的B3LYP方法研究了二重态和四重态Pt+与甲烷反应的机理。通过几何构型优化和频率计算,分别获得三个过渡态,并利用内禀反应坐标（IRC）计算进行了验证。在更高的基组水平上计算了单点能,并详细讨论了二重态和四重态的势能面。结果表明在二重态势能面上的反应具有比较低的能垒,是一个放热反应,所以该反应更易于在二重态上进行。氧化加成生成中间体HPt(CH3)+的步骤需要克服一个小小的能垒。     

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.     

An increase in the order of spatiotemporal focusing in the time-of-flight mass spectrometer with nonuniform field in the ion-acceleration regions

An algorithm for the calculation of electrostatic field in an arbitrary region of acceleration in the mass reflector using the criterion of an increase in the spatiotemporal focusing is presented. Nonuniform accelerating field providing spatiotemporal focusing of the third and fourth orders in the presence of uniform field in the reflector is calculated for a mass reflector with ionization on the surface of target. The effect of the size of input window of detector on the resolution in the presence of nonuniform field in (i) ion source and (ii) ion source and reflector is considered.