同分异构体挥发性有机物的放电离子淌度谱研究

离子淌度谱利用大气压下不同离子在电场中的运动速度不同来达到分离离子的目的。离子在电场中的运动速度不仅与离子的质量有关,也与离子的结构有关,因此离子淌度谱可以有效地用来区分同分异构体。文章报道了用自行研制的放电离子源离子淌度谱仪对碳骨架异构、官能团类别异构和官能团位置异构的三类同分异构体进行了实验研究,得到了九种挥发性有机物的离子淌度谱,测量了各离子的约化迁移率,与前人使用神经网络理论得到的计算值相一致。实验表明这些同分异构体有机物能够在高分辨的离子淌度谱中实现分离,而且对本实验所研究的九种同分异构体有机物而言,迁移率大小符合规律：醇类<酮类<芳香类,直链<分支<环状,对位<间位<邻位。实验中使用指数稀释法对样品进行了定量分析,利用该方法得到的检测限达到ng·L-1量级。其中对官能团类别异构的同分异构体以及丁醇同分异构体的放电离子淌度谱研究均为首次报道。     

酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法。在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱。实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道。实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级。     

Corona Discharge Ion Mobility Spectrometry of Ten Alcohols

利用电晕放电离子源离子迁移谱装置对十种醇类有机物的迁移谱进行了研究. 在质子化的水合氢离子为反应离子和纯净空气为迁移气体的条件下,各种醇类有机物在其离子迁移谱中都获得了不同的产物离子峰. 利用指数稀释法得到各种样品的检测限在几个pmol/L量级. 利用所得到的离子迁移谱,以硬球碰撞为模型,得到了大气压下离子-分子相互作用的多个化学物理参数,包括离子分子碰撞、扩散系数、碰撞速率常数和离子半径.     

基于UV-FAIMS的挥发性氯代苯检测方法

挥发性氯代苯是一类典型的环境有机污染物,离子迁移谱(IMS)是一种大气压下基于离子迁移率的快速现场检测技术。采用自制的真空紫外离子源-高场不对称波形离子迁移谱(UV-FAIMS),对空气中氯苯、对二氯苯、邻二氯苯、间二氯苯进行了检测。获取了不同分离电压条件下的CV-I谱图,并以此得到了四种物质的CV-DV指纹谱图。在指纹谱图支持下,设计了对二氯苯、邻二氯苯、间二氯苯三种同分异构体最优化分离检测参数,结果表明在800和1 000 V的分离电压下,通过特征峰的选取,在补偿电压(CV)为20.4 V(DV=800 V),3.2 V (DV=800 V)和11.9 V (DV=1 000 V)处三种物质的混合物可以得到有效的分离识别。研究了流速对谱图峰位置和峰形的影响,得到不同流速下灵敏度和识别精度关系,为优化流量的选取提供了依据。在特征识别前提下考察了DV=450 V条件下,CV=4.3 V的对二氯苯特征峰的UV-FAIMS检测限,结果高达0.05 mg·m-3。该研究为卤代苯等多同分异构体苯类环境污染物的快速高精度检测提供了一种方法参考。     

离子迁移谱系统的优化设计及其在甲苯检测中的应用

以对痕量甲苯的检测为例,研究了以激光作为电离源的离子迁移谱对痕量物质进行检测的方法.对离子迁移谱系统进行了优化,得到了最佳的迁移管长度和管内电场强度;同时研究了迁移信号和样品浓度的关系.结果表明,该方法行之有效,并能取得极高的灵敏度.     

二氯苯3种同分异构体及其阳离子的红外光谱研究

用从头算理论,在B3LYP/6-31G（d）基组水平上对二氯苯3种同分异构体及其阳离子进行了优化计算,得到其稳定构型,从而得到它们的红外振动光谱;计算结果显示,二氯苯的3种同分异构体的电离是对二氯苯中氯原子的电离。通过对所得红外光谱的分析得到,二氯苯3种同分异构体及其阳离子的红外振动谱有很大的差别,氯的位置的不同对偶极矩变化的大小有很大的影响;而且,分子的电离对振动偶极矩的变化产生了较大的影响。     

Na离子和Cl离子引起He原子直接多重电离过程的研究

利用2～8 MeV的Naq+、Clq+(q=2,3,4,5)轰击氦原子,对碰撞的直接多重电离过程进行研究.实验采用反冲离子-散射离子飞行时间符合技术,通过反冲离子飞行时间谱区分不同价态反冲离子;利用静电偏转和位置灵敏探测技术区分不同电荷态散射离子;结合CAMAC-PC多参数获取系统得到一定价态散射离子所对应的反冲离子电荷态分布谱;经分析该谱得到直接多重电离截面与直接单电离截面之比R21.讨论了R21随入射离子速度和电荷态的变化关系.     

Separation of Ions from Volatile Organic Compounds Using High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometer

对高场非对称波形离子迁移谱-质谱联用(FAIMS-MS)进行了分析. FAIMS将离子从气态的挥发性有机化合物中分离出来. 采用真空紫外灯离子源在常压下对样品进行电离,紫外灯发射的光子能量为10.6 eV,波长116.5 nm. 迁移区由两块平行的金属平板电极构成,尺寸为10 mm×8 mm ×0.5 mm. 采用频率1 MHz、电压峰值1.36 kV、占空比30%的高场非对称方波电压,对丙酮、丁酮和两者混合物进行FAIMS-MS实验. 质谱结果表明,离子和中性分子之间存在分子离子反应,同时在丙酮和丁酮的混合物中有质子转移. 调节补偿电压从-30～10 V以0.1 V的步长扫描,实现了在质谱仪之前进行离子分离的功能.     

苯的同步辐射光电离效率谱的研究

用合肥国家同步辐射实验室光化学站的实验装置研究了苯分子的光电离质谱，从所得光电离效率谱精确地定出了苯分子的电离势及苯离子的出现热，并首次报道了三个苯离子的离解能。     

CHCl3电子吸附速率常数的离子迁移谱

利用电晕放电离子迁移谱, 使用高纯氮气作为载气和迁移气体, 研究了电场强度在200～500 V/cm变化时CHCl₃的解离电子吸附速率常数, 得到样品所对应的电子吸附速率常数为1.26×10^-8～8.24×10^-9 cm³/(molecules s)．利用该装置测量了固定电场下,样品的电子吸附速率常数与样品浓度之间的关系．此外利用所获得的离子迁移谱图得到了不同电场强度下Cl^-与CHCl₃之间的离子分子反应速率常数.     

光电离-离子迁移谱快速监测一次性医疗器械中的环己酮

聚氯乙烯制成的一次性医疗器械在生产加工过程中,常使用环己酮作为部件粘结剂。由于残留的环己酮可释放到医疗器械管道和储存的溶液中,并可能对病人产生一定的副作用,因此,医疗器械中环己酮的快速检测日显重要。利用自主研制的紫外光电离-离子迁移谱装置对环己酮进行检测,检测限为15ppb,检测线性动态范围达到三个数量级。分别对三个品牌一次性输液器包装中的气体进行迁移谱测量,获得包装内环己酮的平均浓度分别为16.78,17.59和46.69ppm。该方法可以用于一次性医疗器械中环己酮等有机溶剂的快速检测,进行医疗器械产品的质量监控。     

Determination of electric transport properties in the pre- and post-breakdown regime ofp-germanium

Conductivity and Hall-effect measurements were performed on single-crystallinep-doped germanium, electrically driven into low-temperature avalanche breakdown via impurity impact ionization. The electric transport properties were determined as a function of the applied electric field in the pre- and post-breakdown regime. The characteristic field dependence of the carrier density, mobility, and drift velocity was found to be reflected in smooth variations of the integral current flow. The breakdown mechanism was demonstrated to involve a mobility which sensitively depends upon the density of the mobile charge carriers. Our experimental findings are qualitatively explained by simple model approaches developed from established breakdown theories.     

OHMIC MOBILITY OF ELECTRONS IN SILICON

Ohmic mobility of electrons in Si has been theoretically studied as a function of temperature. In our theoietical model many-valley structure of Si conduction band, intra-valley scattering of acoustic phonons and impurities and intervalley scattering of pholons and electrons were included. The Green's function approach developed by Lei and Ting was extended to evaluate the Trictional forces resulting from several scattering mechanisms. The numerical results compared with experimental data and indicated the effect of intervalley electron-electron interaction on the mobility of electrons.     

Free-carrier absorption and electron mobility in n-type PbTe

The theory of free-carrier absorption (FCA) of IR signals and of electron mobility in n-PbTe is developed, taking into account the anisotropic non-parabolic band structure and the corresponding wave function admixture. Computed values of both FCA and mobility are given for comparison with the available experimental results at 300 and 77 K. It is found that the experimental values of both FCA and mobility at 300 K may be fitted well with theory by choosing a value of 15 eV for the acoustic phonon deformation potential constant and a value of effective mass within 5% of the values reported earlier. For 77 K, the calculated value of FCA is close to the experimental value, but the values of mobility are about 1.5 times higher. These values may be made to agree with the experimental values only by choosing a value of effective mass which is 27% higher than the values obtained from magnetophonon experiments.     

Development of a comprehensive design tool for non-stoichiometric compound thin film solar cells: Calculations of the opto-electrical properties of multinary alloy and optimization of the cell performance

Based on our previously developed design methodologies which minimized the total free energy and the calculations of the defect/carrier concentrations and the carrier mobility of the non-stoichiometric CuInSe₂, CuGaSe₂, ZnO and ZnO:Al, good confirmation was obtained from our computed conductance of CuInSe₂ with the measured data, in which the total energy calculation was modified by considering the configurational entropy, and solving the coupled total free energy function and the charge neutrality equation self-consistently. In addition, a method to calculate the opto-electrical properties of CuIn_xGa_1−xSe₂ alloy, which is the most popular absorber for high efficiency thin film solar cells, was also effectively developed. Furthermore, the above electrical parameters of the non-stoichiometric window/absorber layers were used to optimize the cell structure, and their performances were correlated with the published experimental results.     

Der Einflu\ unipolarer elektrischer Ladungen auf die Beweglichkeit von natürlichem Aerosol

The size distribution of natural occuring aerosol particles with radii from 10^?6 to 10^?5 cm was measured by investigation of the distribution of thoron decay products on the mobility spectrum. In addition we used an artifical ionization of the particles traversing a corona discharge. Thus the efficiency of the mobility spectrometer could be increased by a factor of four (as a function of corona current). The electrical charge distribution on the particles having passed the corona is out of equilibrium. Therefore the mobility spectrum can be reduced to a size spectrum only by means of an experimentally determined calibration function.     

Hall mobility of undoped n-type conducting strontium titanate single crystals between 19 K and 1373 K

The Hall mobility of undoped n-type conducting SrTiO₃ single crystals was investigated in a temperature range between 19 and 1373 K. Field calculations were used to estimate the influence of sample shape and electrode geometry on the measured values. Between 19 and 353 K samples, which were quenched under reducing conditions, show an impurity scattering behavior at low temperature and high carrier concentrations and a phonon scattering mechanism at room temperature. In this temperature region, no carrier-density-dependent mobility was found. In conjunction with measurements of the mass difference before and after reoxidation, the oxygen deficiency and the oxygen vacancy concentration could be determined. The oxygen vacancies proved to be singly ionized. Above 873 K, Hall mobility and carrier concentration had been determined as a function of both oxygen partial pressure and temperature for the first time. In this temperature range the mobility does not depend on carrier concentration, but shows aT ^–1.5 dependence.     

Synthesis, Characterization, and Luminescence Spectroscopic Accessibility Studies of tris(2,2′-Bipyridine)Ruthenium(II)-Labeled Inorganic-Organic Hybrid Polymers

The modified tris(2,2-bipyridine)ruthenium(II) complex 2 was anchored via a sol-gel process to different polysiloxane matrices to give a series of novel inorganic–organic hybrid polymers. One of the bipyridine ligands of 2 was provided with a long-chain spacer carrying a triethoxysilyl function (T group) at the end, which enables almost free mobility of the transition metal center. The polymers were swollen in several organic solvents of different polarity to investigate the luminescence behavior in the presence of quencher molecules. The luminescence of 2 was quenched using anthracene and atmospheric oxygen in appropriate concentrations of 5 · 10^–4 to 5 · 10^–3 and 3 · 10^–3 M, respectively. The luminescence behavior of 2 was determined by steady-state and time-resolved luminescence experiments. Translational mobilities of molecular species dissolved in the liquid phase were investigated by the kinetics of luminescence quenching after laser excitation. Both the translational mobility of anthracene and atmospheric oxygen, specified with the rate constant k₂ and the percentage of accessible luminescent centers were determined. Translational mobilities and the accessibility for anthracene and atmospheric oxygen in hybrid materials are significantly higher than in conventional Q type polysiloxanes.     

Effects of edge chemistry doping on graphene nanoribbon mobility

Doping of semiconductor is necessary for various device applications. Exploiting chemistry at its reactive edges was shown to be an effective way to dope an atomically thin graphene nanoribbon (GNR) for realizing new devices in recent experiments. The carrier mobility limited by edge doping is studied as a function of the GNR width, doping density, and carrier density by using ab initio density functional and parameterized tight binding simulations combined with the non-equilibrium Green's function formalism for quantum transport. The results indicate that for GNRs wider than about 4 nm, the mobility scales approximately linearly with the GNR width, inversely proportional to the edge doping concentration and decreases for an increasing carrier density. For narrower GNRs, dependence of the mobility on the GNR width and carrier density can be qualitatively different.