Multi-electron processes in 4.15-11.08 keV/u(13)C(6+) on argon collisions

The relative partial cross sections for C-13(6+)-Ar collisions at 4.15-11.08 keV/u incident energy are measured. The cross-section ratios sigma(2E)/sigma(SC), sigma(3E)/sigma(SC), sigma(4E)/sigma(SC) and sigma(5E)/sigma(SC) are approximately the constants of 0.51 +/- 0.05, 0.20 +/- 0.03, 0.06 +/- 0.03 and 0.02 +/- 0.01 in this region. The significance of the multi-electron process in highly charged ions (HCIs) with argon collisions is demonstrated (sigma(ME)/sigma(SC) as high as 0.79 +/- 0.06). In multi-electron processes, it is shown that transfer ionization is dominant while pure electron capture is weak and negligible. For all reaction channels, the cross-sections are independent of the incident energy in the present energy region, which is in agreement with the static characteristic of classic models, i.e. the molecular Coulomb over-the-barrier model (MCBM), the extended classical over-the-barrier (ECBM) and the semiempirical scaling laws (SL). The result is compared with these classical models and with our previous work of C-13(6+)-Ne collisions

Multi-electron processes in C-13(6+) ions with neon collisions in energy region 4.15-11.08 keV/u

The cross-section ratios of double-, triple-, quadruple-, and the total multi-electron processes to the single electron capture process sigma(DE)/sigma(SC), sigma(TE)/sigma(SC), sigma(QE)/sigma(SC) and sigma(ME)/sigma(SC)) as well as the relative ratios among reaction channels in double-electron active, triple-electron active and quadruple- electron active are measured in C-13(6+) -Ne collision in the energy region of 4.15-11.08 keV/u by employing position-sensitive and time-of-flight coincident techniques. It is determined that the cross-section ratios sigma(DE)/sigma(SC), sigma(TE)/sigma(SC), sigma(QE)/sigma(SC) and sigma(ME)/sigma(SC) are approximately the constants of 0.20 +/- 0.03, 0.16 +/- 0.04, 0.06 +/- 0.02 and 0.42 +/- 0.05. These values are obviously smaller than the predictions of the molecular Coulomb over-the-barrier model (MCBM) [J. Phys. B 23 (1990) 4293], the extended classical over-the-barrier model (ECBM) [J. Phys. B 19 (1986) 2925] and the semiempirical scaling laws (SL) [Phys. Rev. A 54 (1996) 4127]. However, the relative ratios among partial processes of DE, TE and QE are found to depend on collision energy, which suggests that the collision dynamics depends on the collision velocity. The limitation of velocity-independent character of ECBM, MCBM and SL is undoubtedly shown.

低能He~(2+)与He原子碰撞转移电离出射电子能谱研究；Investigation on Electron Energy Spectra of Transfer Ionization Process in 70 and 100 keV He~(2+) Colliding on He

利用反应显微成像谱仪对70和100keV He2+与He原子碰撞转移电离(TI)过程中不同出射角度的电子能谱进行了测量,观测到出射电子能谱具有如下分布特征:出射电子速度分布介于0和入射离子速度vp之间;在不同出射角度电子能谱分布均有一极大值存在,随着出射角度的增大,能谱分布极大值逐渐减小;当电子出射角度等于45°时,多数电子集中在0eV附近。上述特征可由低能离子-原子碰撞"准分子"模型进行定性解释。在100keV He2+-He转移电离出射电子能谱中有靶电子被俘获至散射离子连续态(electron capture to continuum,简称ECC)电子的贡献,这可看做是动力学两步过程的作用。

Shell effect on stabilization processes following multi-electron transfer in slow Arq+-Ar (g=6-9, 11) collisions

We experimentally investigate the shell effect on the stabilization processes following the multi-electron transfer in slow collisions of Arq+-Ar (q = 6-9, It) The relative cross-section ratios of multi-electron transfer and of the subsequent stabilization with respect to single-electron capture are measured meanwhile compared with the theoretical results predicted by the classical over-barrier model. Our result indicates that the multi-electron transfer is dominant when the projectile charge is large and the subsequent stabilization shows a dramatic variation if the projectile L-shell configuration becomes open. It shows that the subsequent stabilization processes of multiply excited scattering ions have a strong dependence on the projectile shell. (C) 2010 Elsevier BV All rights reserved.

Influence of core property on multi-electron process in slow collisions of isocharged sequence ions with neon

Influence of core property on multi-electron process in the collisions of q = 6-9 and 11 isocharged sequence ions with Ne is investigated in the keV/u region The cross-section ratios of double-, triple-, quadruple- and total multi-electron processes to the single electron capture process as well as the partial ratios of different reaction channels to the relevant multi-electron process are measured by using position-sensitive and time-of-flight techniques The experimental data are compared with the theoretical predictions including the extended classical over-barrier model, the molecular Columbic barrier model and the semi-empirical scaling law Results show a core effect on multi-electron process of isocharge ions colliding with Neon, which is consistent with the results of Helium we obtained previously

紧聚焦的超短超强激光脉冲在真空中加速斜入射的相对论电子

研究了紧聚焦的线偏振飞秒超强高斯激光脉冲俘获并剧烈加速斜入射低能相对论电子的效应，发现被俘获的电子在激光脉冲纵向有质动力的强大加速作用下，可以获得GeV量级的能量，并详细研究了入射电子的初能量、斜入射角、电子与激光脉冲的相对延迟时间和激光脉冲宽度等条件对电子能量增益的影响，发现当激光脉宽超过10λ时，脉宽对电子能量增益影响不大．

Radiation damping effects on the ultrashort x-ray pulses generated by nonlinear Thomson backscattering

Nonlinear Thomson backscattering of an intense Gaussian laser pulse by a counterpropagating energetic electron is investigated by numerically solving the electron equation of motion taking into account the radiative damping force. The backscattered radiation characteristics are different for linearly and circularly polarized lasers because of a difference in their ponderomotive forces acting on the electron. The radiative electron energy loss weakens the backscattered power, breaks the symmetry of the backscattered-pulse profile, and prolongs the duration of the backscattered radiation. With the circularly polarized laser, an adjustable double-peaked backscattered pulse can be obtained. Such a profile has potential applications as a subfemtosecond x-ray pump and probe with adjustable time delay and power ratio. (c) 2006 American Institute of Physics.

Monitoring of organochlorine pesticides using PFU csystems in Yunnan lakes and rivers, China

Polyurethane foam unit (PFU) systems were collected from 11 lakes and three rivers in the Yunnan Plateau, China and, the PFU extrusion liquids, were analyzed for organochlorine pesticides (OCPs) by gas chromatography with electron capture detection (GCECD). The concentrations of pp'-DDE, HCB and HCHs were undetectable to 1.86 mu g l(-1) (mean 0.27 mu g l(-1)), undetectable to 0.72 mu g l(-1) (mean 0.11 mu g l(-1)), and 0.24-21.95 mu g l(-1) (mean 7.39 mu g l(-1)) respectively in lakes; and those in rivers were undetectable to 0.23 mu g l(-1) (mean 0.08 mu g l(-1)), 0.68-2.93 mu g l(-1) (mean 1.70 mu g l(-1)), and 2.71-37.56 mu g l(-1) (mean 17.01 mu g l(-1)) respectively. Notably, some residue levels of OCPs exceeded the US National Recommended Water Quality Criteria, implying Yunnan has levels of OCPs potentially harmful to human health. Further, the contamination by OCPs showed an obvious spatial distribution pattern. Amongst the lakes, Dianchi, Xingyun, Lugu and Yangzonghai had the highest OCP levels dominated by beta-HCH, whereas among rivers, Nujiang and Lancang Rivers had the highest contents of OCPs dominated by alpha-HCH. This demonstrates that HCHs are the predominant contaminants and some point sources of HCHs may still exist in Yunnan. The pollution levels in Yunnan were compared with other studies, suggesting the PFU method is suitable for long-term on-line monitoring of trace OCPs in aquatic ecosystems. Therefore, continuous studies monitoring OCPs in lakes and rivers are needed to further understand the future trend of contamination. (c) 2006 Elsevier Ltd. All rights reserved.

Biotransfer of persistent organic pollutants from a large site in China used for the disassembly of electronic and electrical waste

Samples of groundwater, river water, river sediment, paddy soil, rice seeds, hen eggs, fish, umbilical cord blood, and newborn meconium were collected from October 2002 to October 2003 near a large site in China used for the disassembly of obsolete transformers and other electronic or electrical waste. Six indicator PCB congeners, three non-ortho dioxin-like PCB congeners, and six organochlorine pesticides were determined in the samples by GC with electron capture detector. The results demonstrated that the local environment and edible foods had been seriously polluted by toxic PCBs and organochlorine pesticides. The actual daily intakes (ADIs) of these pollutants were estimated for local residents living in the area. The intake data showed that the contents of PCBs in these local residents were substantial, as the ADI estimates greatly exceed the reference doses set by the World Health Organization and the United States Agency for Toxic Substances and Disease Registry. The presence of the indicator PCB congeners in the cord blood and the meconium samples, as well as significant correlations (r(2) > 0.80, p < 0.05) between these levels, suggests a potential biotransfer of these indicators from mothers to their newborns. This preliminary study showed that obsolete transformers and other electronic or electrical waste can be an important source for the emission of persistent organic pollutants into the local environment, such as through leakage, evaporation, runoff, and leaching. Contamination from this source appears to have reached the level considered to be a serious threat to environmental and human health around the disassembly site.

A solid-phase microextraction fiber coated with diglycidyloxycalix[4]arene yields very high extraction selectivity and sensitivity during the analysis of chlorobenzenes in soil

A novel fiber coated with novel sol-gel (5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-diglycidyloxycalix[4]arene/hydroxy-terminated silicone oil; diglycidyloxy-C[4]/OH-TSO) was prepared for use with headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and electron capture detection (ECD), which was applied in order to determine nine chlorobenzenes in soil matrices. Due to the improved fiber preparation, which increases the percentage of calixarene in the coating, the new calixarene fiber exhibits very high extraction selectivity and sensitivity to chlorine-substituted compounds. Various parameters affecting the extraction efficiency were optimized in order to maximize the sensitivity during the chlorobenzene analysis. Interferences from different soil matrices with different characteristics were investigated, and the amount extracted was strongly influenced by the matrix. Therefore, a standard addition protocol was performed on the real soil samples. The linear ranges of detection for the chlorobenzenes tested covered three orders of magnitude, and correlation coefficients > 0.9976 and relative standard deviations (RSD) < 8% were observed. The detection limits were found at sub-ng/g of soil levels, which were about an order of magnitude lower than those given by the commercial poly(dimethylsiloxane) (PDMS) coating for most of the compounds. The recoveries ranged from 64 to 109.6% for each analyte in the real kaleyard soil matrix when different concentration levels were determined over the linear range, which confirmed the reliability and feasibility of the HS-SPME/GC-ECD approach using the fiber coated with diglycidyloxy-C[4]/OH-TSO for the ultratrace analysis of chlorobenzenes in complex matrices.

Analysis of organchlorine compounds in water by solid phase microextraction and gas chromatography

In this work, both,solid phase microextraction (SPME) and solid phase extraction(SPE) were used to enrich organochlorine compounds in water samples and analyzed by gas chromatography with electron capture detector. The operating conditions of SPME have been studied and different kinds of solid phase were compared. Linear alkybenzene sulfonate(LAS) was added to the samples to investigate its effect on the analysis. The results indicated that polyacrylate was better than other commercial solid phases in extraction of moderated polar organic compounds and the sensitivity of SPME was higher than SPE. LAS affect much in liquid-liquid extraction and headspace SPME; but it has little effect on SPE and direct-SPME method. The applications showed that SPME was a fast and effective method in sample preparation.

RELATION BETWEEN THE METASTABILITY OF EL2 AND THE PHOTOSENSITIVITY OF LOCAL VIBRATIONAL-MODES IN SEMIINSULATING GAAS

Recent infrared spectroscpic observations of local vibrational mode absorptions have revealed a number of photosensitive centers in semi-insulating GaAs. They include (OVAs) center which has three modes at 730 cm(-1) (A), 715 cm(-1) (B), and 714 cm(-1) (C), respectively, a suggested NH center related to a line at 983 cm(-1) (X(1)), and centers related to hydrogen, such as (H-O) or (H-N) bonds, corresponding to a group of peaks in the region of 2900-3500 cm(-1). The photosensitivity of various local vibration centers was observed to have similar time dependence under near-infrared illumination and was suggested to be due to their charge-state interconversion. Mainly described in this work is the effect of the 1.25-eV illumination. It is confirmed that this photoinduced kinetic process results from both electron capture and hole capture, which are closely related to the photoionization behavior and metastability of the EL2 center.

有机质谱裂解规律及智能解析方法研究

本学位论文分为四个部分，第一部分报道了用串联质谱快速分析合成药物中的微量杂质成分以及分析中药材中的化学成分。第二部分报道了通过质谱和串联质谱发现并合成新型的PdPincer 催化剂，同时对其活性进行测试。第三部分为串联质谱自动解析软件的设计及应用。第四部分概述了应用在质谱中的各种碎裂方式。 第一部分首先总结了5-溴粉防己碱及其类似物的裂解规律，并以此为根据推测出2 个微量杂质的结构。随后针对无患子（Sapindus mukurossi Gatren.）中的皂苷成分，由ESI-QTOF 得到各个皂苷成份的高分辨质量数据进而得到其分子式，然后利用ESI-IT 电喷雾串联质谱对无患子总皂苷中各皂苷成分的结构进行进一步的鉴定。进而以同样的方式，先通过ESI-QTOF 得到黄山药（Dioscoreapanthaica）总皂苷中各个组分化合物的分子式，然后对已有的薯蓣皂苷标准品做串联质谱分析，以得到该类化合物的裂解规律并给出解析该类化合物的流程图。在此利用计算化学的方法讨论了离子的丰度与裂解活化能之间的关系。然后应用APCI-MS/MS 方法探讨了四对同分异构体和几个已知的化合物，并最后用液质联用对其进行确认，同时还给出了4 个未知化合物的可能结构。 第二部分报道通过质谱和串联质谱发现并合成新型的PdPincer 催化剂，同时对其活性进行测试。钯催化的交联反应是有机合成中C-C 键形成的最有效的方法，且硫脲是一类对空气和水都稳定的化合物，因此我们设计并合成了一系列的硫脲钯催化剂并得到了很好的催化活性。我们在对其中一类环状双硫脲化合物进行质谱实验的时候，在正离子模式下发现了反常的[M.H]+，通过串联质谱进一步确定了它是一种新型的PdPincer 结构。我们将其合成出来并通过X-ray 衍射实验确定了它的结构。同时测定其催化活性并与未形成pincer 的类似物进行比较发现该类化合物具有较宽的底物适用性。 第三部分为串联质谱自动解析软件的设计及应用。通过前面两部分的启示，独立设计开发了AuMass（1.0）。其算法是：先通过查找特殊的碎片离子，中性丢失或碎片离子质量差来确定某类化合物的骨架结构，然后利用该类化合物的自动解析流程来对其周边取代基进行确认。通过它快速地对白芍中的化学成分进行解析，并对未知的化合物进行了推测。为了增加它的解析能力，我又对其它类型的化合物裂解规律进行总结，并给出了自动解析流程。实践证明该软件具有相当好的应用价值。 第四部分综述了应用在质谱上的各类母离子的碎裂技术。这里包括了碰撞诱导裂解（CID）、光诱导碎裂（LID）、电子捕获裂解/电子转移裂解（ECD/ETD）、红外多光子解离（IRMPD）、黑体辐射解离（BIRD）和PQD 裂解技术。 This dissertation consists of four chapters. The first chapter reports the rapidanalysis of trace impurities from synthetical medicine and analysis of the chemicalconstitutents from Chinese herb medicines. The second chapter elaborates the studieson the discorvery and synthesis of new type of Pd Pincer catalyst by using MS andtandem MS together with the testing of its catalyst activity. The third chapter dwellson the designation and development of automatic tandem mass spectrometry analysissoftware. The last chapter presents a review on the dissociation technique of massspectrometry. The first chapter reports the rapid analysis of trace impurities from synthesismedicine and analysis of the chemical constitutents from Chinese herb medicines. The fission mechanism of 5-bromotetrandrine was obtained by analysis of the dissociationpathways of major product, by using which the possible structure of the two traceimpurties was assumed. There are lots of saponins in Sapindus mukurossi. Except forthe good spumescence and decontamination，it possesses the bioactivity of antigenand antitch. First of all, the high resolution mass information was obtained by ESI-QTOF. Hence the possible molecular formulars were acquired too. Then weconducted the further detection of the structures of its saponins by using ESI-ITtechnology. In the same manner, first the molecular formulars of every constituentfrom Dioscorea panthaica in total saponins were obtained by ESI-QTOF, and thenacquired the fission mechanism of this type of compounds by tandem massexperiment on a series of known and available saponins. In the same time, theanalysis flowchart was concluded. Here the relationship between the ion intensity andthe corresponding dissiociation activation energy was studied by computer chemistry.Then the four pairs of isomers were differentiated by APCI-MS/MS, as well as thecharacterization of known and unknown compounds. The assumption was confirmed by HPLC-MS/MS. Among them the possible structures of four unknown saponinswas presented. The second part was discovery and synthesis of a new type of Pd pincer catalystby MS and tandem MS. The coupling reaction catalyzed by Pd is the most effectivemethod in C-C formation in organic synthesis. Apart from that, thiourea is type ofcompounds that are stable to atmosphere and moisture. Hence we designed a series ofPd thiourea catalysts. Some of them show the excellent catalyst activity. The abnormalparent ion [M.H]+ was founded in positive ESI mode when we conduct some massspectrometry experiments on the bicyclical thiourea Pd complex. The structure wasproposed by mass and tandem mass spectrometry. Because it was a new type of pincer,we want to test its catalyst activity. So the Pd pincer was synthesized and the detailstructure was obtained by x-ray experiment. It shows the more fitness in catalysis ofSuzuki reaction by comparison with the analogue. The third chapter dwells on the design and development of automatic tandemmass spectrometry analysis software. Inspired by the former two chapters, theAuMass (version 1.0) was developed. Its algorithm is: first check the diagnostic ion,diagnostic neutral loss or diagnostic ions mass intervals in database to find out whatthe analyst’s skeleton belongs to, then identify the peripheral functional group by thecorresponding analysis flowchart. The chemical constituents of Paeonia lactiflorawere identified rapidly by using AuMass. To increase the analysis ability, the othertypes of compounds from Chinese herbs was concluded. Actually, the software isproven to have the much valuable application. The last chapter presented the review on the some kinds of fission technique ofmass spectrometry. It involves the collision induced dissociation (CID), laser induceddissociation (LID), electron capture dissociation/electron transfer dissociation(ECD/ETD), infrared multiple photons dissiociation, black body irraditiondissociation and PQD fission technique from Finnigan.

Double ionization of helium in collision with 20-500-keV/amu Cq+ and Oq+ (q=1-3) ions

Target ionization and projectile charge changing were investigated for 20-500 keV/u Cq+, Oq++He (q=1-3) collisions. Double- to single-ionization ratios R-21 of helium associated with no projectile charge change (direct ionization), single-electron capture, and single-electron loss were measured. The cross-section ratio R-21 depends strongly on the collision velocity v, the projectile charge state q, and the outgoing reaction channel. Meanwhile, a model extended from our previous work [J. X. Shao, X. M. Chen, and B. W. Ding, Phys. Rev. A 75, 012701 (2007)] is presented to interpret the above-mentioned dependences. Good agreement is found between the model and the experimental data.

Quantum-mechanical calculations of vibrationally resolved cross sections for non-dissociative charge transfer of O3+ with H-2

Charge transfer due to collisions of ground state O3+ (2s(2)2p P-2) ions with molecular hydrogen is investigated using the quantum-mechanical molecular-orbital close-coupling (MOCC) method, and electronic and vibrational state-selective cross sections along with the corresponding differential cross sections are calculated for projectile energies of 100, 500, 1000 and 5000 eV/u at the orientation angles of 25 degrees,45 degrees and 89 degrees. The adiabatic potentials and radial coupling matrix elements utilized in the QMOCC calculations were obtained with the spin-coupled valence-bond approach. The infinite order sudden approximation (IOSA) and the vibrational sudden approximation (VSA) are utilized to deal with the rotation of H-2 and the coupling between the electron and the vibration of H-2. It is found that the distribution of vibrationally resolved cross sections with the vibrational quantum number upsilon' of H-2(+) (upsilon') varies with the increment of the projectile energy; and the electronic and vibrational stateselective differential cross sections show similar behaviors: there is a highest platform within a very small scattering angle, beyond which the differential cross sections decrease as the scattering angle increases and lots of oscillating structures appear, where the scattering angle of the first structure decreases as E-P(-1/2) with the increment of the projectile energy E-P; and the structure and amplitude of the differential cross sections are sensitive to the orientation of molecule H-2, which provides a possibility to identify the orientations of molecule H-2 by the vibrational state-selective differential scattering processes.