高电荷态氩离子与原子碰撞中的多电子转移过程研究

本工作建立起了符合关联测量实验装置，包括反冲离子飞行时间谱仪、散射离子位置灵敏探测器、差分拉瓦型气体喷嘴、基于微机的多参数数据获取系统以及数据分析和处理程序。在入射离子能量在80KeV～240KeV范围内，利用该装置系统研究了Arq++He，Arq++Ne和Arq++Ar（q=8，9，11，12）碰撞体系中的多电子转移规律，实验鉴别了反应中发生的各种多电子转移过程，测量了反应截面，获得了一批新的实验数据。 对于Arq++He碰撞体系，本工作主要研究了He原子的转移电离相对截面与入射离子能量和电荷态的规律，发现相对截面在所研究能区基本与入射离子能量无关，并利用核间势垒和复合分子的经典图象，描述了此碰撞体系转移电离过程发生的两种可能途径，估计了相对截面的经典上限，发现在此碰撞体系中，转移电离过程中电子关联作用起着重要的作用。 本工作系统研究了Arq++He和Arq++Ar碰撞体系中多电子转移反应截面与入射离子能量、电荷态和反冲离子电荷态的变化规律，以及反冲离子电荷态分布。研究发现，在低能高电荷态离子与多电子靶原子碰撞反应中，碰撞系统的相对运动动能对碰撞体系中的电子转移过程基本没有贡献；系统所具有的势能是碰撞体系中电子转移和靶原子电离的主要因素；在相同的入射离子条件下，靶原子电离能对电子转移有重要影响；碰撞反应中单电子过程占主要地位，而在多电子转移过程中，转移电离过程发生的几率一般大于纯的多电子俘获几率；入射离子单电子俘获截面、总电荷交换截面与入射离子电荷态成正比关系；入射离子电荷交换截面随离子俘获电子数目的增加而单调减小；入射离子俘获一个电子时，转移电离截面随反冲离子电荷态的升高而单调下降，而入射离子俘获电子数多于一个时，转移电离截面存在极大值分布现象，而且分布宽度随入射离子电荷态的升高具有增加的趋势。 本工作在分析实验现象和分子经典库仑过垒模型MCBM的基础上，提出基于MCBM描述，把高电荷态离子与原子碰撞反应中的电子转移过程分为四阶段描述的新想法，即：入射过程中的分子化→复合分子形成→复合分子解离和中间态离子的形成→多电子激发态散射离子和靶离子向末态的自电离衰变。并依据能量守恒原理，规范了处理多电子激发态离子发生自电离衰变的规则。在此基础上，对Arq++He和Arq++Ar碰撞体系中的电子转移截面进行了理论计算，通过与实验结果的对比研究发现，对在中间态形成的多电子激发态散射离子，根据这些规则进行自电离衰变修正后计算得到的结果与实验符合很好，因此，对多电子激发态离子的自电离修正是合理的，而且多电子激发态离子的自电离衰变是低能高电荷态离子与原子碰撞反应中转移电离过程发生的主要因素。

Characterization of saccharides and phenolic acids in the Chinese herb Tanshen by ESI-FT-ICR-MS and HPLC

This study sought to determine the main components (saccharides and phenolic acids) in crude extract of the Chinese herb Tanshen by electrospray ionization Fourier transform ion cyclotron resonant mass spectrometry (ESI-FT-ICR-MS) in negative-ion mode. Eleven compounds were identified as phenolic acids by exact mass measurement and further confirmed by sustained off-resonance irradiation (SORI) CID data. In addition, monosaccharicles and oligosaccharides (n = 2 similar to 5) and a serial of corresponding anionic adducts of saccharide were observed without adding any anions additionally to the extract solution, and the anionic components were unambiguously identified as H2O, HCl, HCOOH, HNO3, C3H6O2, H2SO4 and C5H7NO3 according to the exact mass measurement results.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry.

Surface plasmon resonance and electrochemistry characterization of layer-by-layer self-assembled DNA and Zr4+ thin films, and their interaction with cytochrome c

Through electrostatic layer-by-layer (LbL) assembly, negatively charged calf thymus double stranded DNA (CTds-DNA), and positively charged Zr4+ ions were alternately deposited on gold substrate modified with chemisorbed cysteamine. Thus-prepared three-dimensional DNA networks were characterized by surface plasmon resonance (SPR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS). SPR spectroscopy indicates that the effective thickness of DNA monolayer in the (DNA/Zr4+), bilayer was 1.5 +/- 0.1 nm, which corresponds to the surface coverage of 79% of its full packed monolayer. At the same time, a linear increase of film thickness with increasing number of layers was also confirmed by SPR characterizations. The data of XPS and IR-RAS show that Zr4+ ions interact with both the phosphate groups and nitrogenous bases of DNA and load into the framework of DNA. Furthermore, the interactions between this composite film and heme protein cytochrome c (Cyt c) were investigated by SPR spectroscopy and electrochemistry. Compared with the adsorption of Cyt c on DNA monolayer, this composite multilayer film can obviously enhance the amount of immobilized Cyt c confirmed by SPR reflectivity-incident angle (R-theta) curves.

Two- and three-dimensional Au nanoparticle/CoTMPyP self-assembled nanotructured materials: Film structure, tunable electrocatalytic activity, and plasmonic properties

Two- and three-dimensional Au nanoparticle/[tetrakis(N-methylpyridyl)porphyrinato]cobalt (CoTMPyP) nanostructured materials were prepared by "bottom-up" self-assembly. The electrocatalytic and plasmonic properties of the Au nanoparticle/CoTMPyP self-assembled nanostructured materials (abbreviated as Au/CoTMPyP SANMs) are tunable by controlled self-assembly of the An nanoparticles and CoTMPyP on indium tin oxide (ITO) electrode. The electrocatalytic activity of the Au/CoTMPyP SANMs can be tuned in two ways. One way is that citrate-stabilized An nanoparticles are positioned first on ITO surface with tunable number density, and then positively charged CoTMPyP ions are planted selectively on these gold sites. The other way is that An nanoparticles and CoTMPyP are deposited by virtue of layer-by-layer assembly, which can also tune the amount of the as-deposited electrocatalysts. FE-SEM studies showed that three-dimensional SANMs grow in the lateral expansion mode, and thermal annealing resulted in both surface diffusion of nanoparticles and atomic rearrangement to generate larger gold nanostructures with predominant (I 11) facets.

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.

Covariance analysis of the Coulomb explosion of ammonia induced by intense nanosecond laser at 532 nm

The Coulomb explosion of ammonia clusters induced by nanosecond laser at 532 not with an intensity of similar to 10(12) Wcm(-2) has been studied by time of flight mass spectrometry. The dominant multiply charged ions are N3+ and N2+ with kinetic energies of 110 and 50 eV respectively. The electrons generated from the multiphoton ionization are heated through inverse bremsstrahlung by the laser field when colliding with neutral or ionic particles. When their energies surpass the corresponding ionization potentials of the molecules or ions, the subsequent electron impact ionization may take place thus resulting in multi-charged nitrogen ions. Covariance analysis is made to study the possible pathways of the Coulomb explosion.

Dissociative electron attachment to HCCCN

Dissociative electron attachment to cyanoacetylene (propiolonitrile) HCCCN has been observed in the electron energy range 0-12 eV. Negative ions are formed in two main bands with maxima at similar to 1.6 eV (CCCN-) and similar to 5.3 eV (CCCN-, CN-, HCC- and CC-). There are also weaker resonances which lead to dissociative electron attachment to form CN-, HCC- and CC- with a maximum intensity at similar to 8.1 eV and CCCN-, CN- and CC- at similar to 11.2 eV. A trace of CCN- is observed at similar to 9.1 eV. The positions of the main dissociative attachment bands observed are close to positions of pi* resonances recently calculated by Sommerfeld and Knecht. Calculations have also been performed in this work, which confirm the position of the p* orbitals. The electron affinity of the CCCN radical is determined as 4.59 +/- 0.25 eV from the threshold for CCCN- formation at 1.32 +/- 0.15 eV. Dissociative electron attachment to this molecule will act as a source of negative ions in extraterrestrial environments where electrons are present with more than 1.3 eV energy.

Large molecules in the envelope surrounding IRC+10216

A new chemical model of the circumstellar envelope surrounding the carbon-rich star IRC+10216 is developed that includes carbon-containing molecules with up to 23 carbon atoms. The model consists of 3851 reactions involving 407 gas-phase species. Sizeable abundances of a variety of large molecules - including carbon clusters, unsaturated hydrocarbons and cyanopolyynes - have been calculated. Negative molecular ions of chemical formulae C-n(-) and CnH- (7 less than or equal to n less than or equal to 23) exist in considerable abundance, with peak concentrations at distances from the central star somewhat greater than their neutral counterparts. The negative ions might be detected in radio emission, or even in the optical absorption of background field stars. The calculated radial distributions of the carbon-chain CnH radicals are looked at carefully and compared with interferometric observations.

EXPERIMENTAL EVIDENCE FOR RADIATIVE ATTACHMENT IN ASTROCHEMISTRY FROM ELECTRON ATTACHMENT TO NCCCCN

Electron attachment to NCCCCN, dicyanoacetylene (2-butynedinitrile), has been observed. Metastable parent anions, NCCCCN-*, with microsecond or longer lifetimes are formed close to 0 eV electron energy with a cross section of >= 0.25 angstrom(2). The stability of NCCCCN suggests that radiative attachment to NCCCCN and similar linear carbon chain molecules may be an important mechanism for the formation of negatively charged molecular ions in astrophysical environments. CCCN- and CN- fragment anions are formed at similar to 3 and similar to 6 eV.

Electron attachment to 2-nitro-m-xylene

Electron attachment to nitroaromatic compound 2-nitro-m-xylene in gas phase has been performed utilizing a double focusing two sector mass spectrometer with high mass resolution (m/Delta m approximate to 2500). At low energy (below 20 eV), electron interactions with the neutral 2-nitro-m-xylene molecule reveal a very rich fragmentation pattern. A total of 60 fragment anions have been detected and the ion yield for all observed negative ions has been recorded as a function of the incident electron energy, among them a long lived (metastable) non-dissociated parent anion which is formed at energies near zero eV, and some ions observed at the mass numbers 26,42 and 121. Comparison of calculated isotopic patterns with measured ion yields for these fragment anions and their successors in the mass spectrum, allows the assignment of the chemical composition of these fragments as CN- (26 Da), CNO- (42 Da) and C8H9O- (121 Da). Electron attachment to 2-nitro-m-xylene leads to anion formation at four energy ranges. Between 0 eV and 2 eV only few product ions are formed. Between 4.6 eV and 6.1 eV all fragment anions are formed and for most of them the anion yield reaches its maximum value in this range. NO2- which is the most abundant product [M-H](-) and O- are the only fragments that exhibit a feature at 7.4eV, 8.1 eV and 7.9eV, respectively. About half of the fragment anions exhibit a broad, mostly low-intensity resonance between 9 eV and 10 eV. (C) 2009 Elsevier B.V. All rights reserved.

Asymptotic layer-type model of high pressure direct current glow discharge in electronegative gases

Here a self-consistent one-dimensional continuum model is presented for a narrow gap plane-parallel dc glow discharge. The governing equations consist of continuity and momentum equations for positive and negative ions and electrons coupled with Poisson's equation. A singular perturbation method is developed for the analysis of high pressure dc glow discharge. The kinetic processes of the ionization, electron attachment, and ion-ion recombination are included in the model. Explicit results are obtained for the asymptotic limits: delta=(r(D)/L)(2)--> 0, omega=(r(S)/L)(2)--> 0, where r(D) is the Debye radius, r(S) is recombination length, and L is the gap length. The discharge gap divides naturally into four layers with multiple space scales: anode fall region, positive column, transitional region, cathode fall region and diffusion layer adjacent to the cathode surface, its formation is discussed. The effects of the gas pressure, gap spacing and dc voltage on the electrical properties of the layers and its dimension are investigated. (C) 2000 American Institute of Physics. [S0021-8979(00)00813-6].

CROSS-SECTIONS FOR RESONANT TRANSFER AND EXCITATION IN FEQ++H-2 COLLISIONS

Resonant transfer and excitation (RTE) is investigated for Fe(q+) ions (q=23, 24, and 25) colliding with H2. For each charge state, cross sections for RTE were obtained from measurements of K x rays, emitted from the doubly excited intermediate state, coincident with single-electron capture by the incident ion. Additionally, for Fe25+ cross sections were obtained from measurements of coincidences between the two K x rays emitted from the intermediate state. These latter measurements Provide information on the lifetimes of intermediate metastable states formed in the RTE process. In all cases, measured cross sections are in good agreement with calculations based on theoretical cross sections for dielectronic recombination (DR). Since RTE closely approximates DR, the results indicate that dielectronic-recombination cross sections involving K-shell excitation can be accurately predicted for highly charged iron ions. The results for Fe25+ show that metastable states are sufficiently short lived to be observable in the RTE (or DR) process for these hydrogenlike ions.