环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

空气放电非平衡等离子体的模拟计算

 基于空气放电非平衡等离子体动力学,对空气放电进行了数值计算,分析了放电后等离子体中的主要粒子（N₂(v6),N₂(A3),O₂(a1),O和O₃）数密度随起始温度、电子数密度和约化场强的变化趋势。计算结果表明,随着初始温度的升高,空气放电产生的粒子数密度增加。温度为300 K时,放电产生的O原子数密度最大值约为4.90×⁷ cm^-3,而当温度升高到400 K和500 K时,O原子数密度的最大值则相应地增加到5.2×10¹⁰ cm^-3和5.51×10¹⁰ cm^-3。约化场强的影响与温度类似,其中氮气的振动激发态N₂(v6)数密度随约化场强的变化幅度不明显。电子数密度增加,粒子数密度大幅增加,氮分子的激发态N₂(A3)粒子数密度与电子数密度保持严格的线性关系。     

锰氧化物团簇正离子与硫化氢反应的实验与理论研究 (cited: 2)

采用激光溅射法制备了同位素标记的氧化锰团簇正离子Mn_m¹⁸O_n⁺,并研究了其在快速流动反应管中与硫化氢在热碰撞条件下的反应,氧化锰团簇正离子与硫化氢反应前后的质量分布与强度变化由飞行时间质谱仪检测．实验表明,绝大多数氧化锰团簇正离子可与硫化氢发生氧-硫交换反应产生水分子,反应通式为：Mn_m¹⁸O_n⁺+H₂S→Mn_m¹⁸O_n-1S⁺+H₂¹⁸O．通过密度泛函理论计算了氧化锰团簇正离Mn₂O₂⁺、Mn₂O₃⁺和Mn₂O₄⁺与H₂S反应的机理,结果显示,在这些反应体系中氧-硫交换反应通道同时具有热力学和动力学优势,印证了实验中观察到的现象．气相团簇研究发现的氧-硫交换反应与相关凝聚相体系反应结果一致     

AsO+同位素离子X2∑+和A2∏电子态的多参考组态相互作用方法研究

采用包含Davidson修正多参考组态相互作用(MRCI)方法结合价态范围内的最大相关一致基As/aug-cc-pV5Z和O/aug-cc-pV6Z, 计算了AsO⁺ (X²∑⁺)和AsO⁺(A²∏)的势能曲线. 利用AsO⁺离子的势能曲线在同位素质量修正的基础上, 拟合出了同位素离子⁷⁵As¹⁶O⁺和⁷⁵As¹⁸O⁺的两个电子态光谱常数. 对于X²∑⁺态的主要同位素离子⁷⁵As¹⁶O⁺, 其光谱常数R_e, ω_e, ω_ex_e, B_e和α_e分别为 0.15770 nm, 1091.07 cm^-1, 5.02017 cm^-1, 0.514826 cm^-1和0.003123 cm^-1; 对于A²∏态的主要同位素离子⁷⁵As¹⁶O⁺, 其T_e, R_e, ω_e, ω_ex_e, B_e和α_e分别为5.248 eV, 0.16982 nm, 776.848 cm^-1, 6.71941 cm^-1, 0.443385 cm^-1和0.003948 cm^-1. 这些数据与已有的实验结果均符合很好. 通过求解核运动的径向薛定谔方程, 找到了J=0时AsO⁺(X²∑⁺)和AsO⁺(A²∏)的前20个振动态. 对于每一振动态, 还分别计算了它的振动能级、转动惯量及离心畸变常数, 并进行了同位素质量修正, 得到各同位素离子的分子常数. 这些结果与已有的实验值非常一致. 本文对于同位素离子⁷⁵As¹⁶O⁺(X¹∑⁺), ⁷⁵As¹⁸O⁺(X¹∑⁺), ⁷⁵As¹⁶O⁺(A¹∏)和⁷⁵As¹⁶O⁺(A¹∏)的光谱常数和分子常数属首次报导.     

胸腺嘧啶低能量VUV光解离路径的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算研究了胸腺嘧啶的光解离反应路径, 通过改变光子能量得到不同的质谱信号, 光子能量在12.0 eV时主要的碎片有m/z=98 (C₄H₆N₂₄O⁺)、97 (C₄H₅N₂O⁺)、84 (C₃H₄N₂O⁺或C<     

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   

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.     

异戊二烯解离光电离理论研究

利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺的C₂H₃⁺的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from Ethylene by Stoichiometric Zirconium Oxide Clusters

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阳离子团簇Zr_xO_y⁺和乙烯的反应. 在这个反应中,发现了产物(ZrO₂)_xH⁺ (x=1～4). 使用密度泛函理论研究了乙烯在Zr₂O₄⁺上的反应通道,发现除了通常的氧转移反应外,乙烯脱氢反应也可以发生,从而支持观察到的产物(ZrO_{2相似文献}   

极板电压与间距对大气压射频氩等离子体放电参数的影响

 基于1维流体力学模型,对大气压射频裸露金属电极氩气放电过程进行了研究。模型中考虑了氩等离子体放电过程中主要发生的激发和电离等7个反应过程,对等离子体反应产生的主要粒子,包括电子、氩原子离子Ar⁺、氩分子离子Ar2⁺和氩激发态Ar^*等,建立连续性方程、动量方程和电流平衡方程。分析了极板电压、极板间距对上述粒子数密度分布的影响。给出了电子,Ar⁺,Ar^*和Ar₂⁺密度随极板电压及间距变化的时空演化过程。得出极板电压或极板间距的改变会使放电空间的电场发生改变,对应一定的极板间距,极板电压有一个最佳值,极板电压和间距的变化会使对应的极板间有一个最佳电场值,而对应最佳电场有一个等离子体气体间最佳反应系数,从而使放电空间粒子数密度发生改变。     

Excited-state photoelectron spectra of the one-photon forbidden C3IIg rydberg state of molecular oxygen

The Rydberg C³II_g, state of molecular oxygen, which is one-photon forbidden from the ground electronic state, has been studied by means of (2 + 1) multiphoton ionization (MPI) ion-current and photoelectron spectroscopic techniques in the laser wavelength region 287–289 nm. Excitedstate photoelectron spectra have been observed at different rotational levels of the C³Π_gv' = 2 state of O₂, and show marked deviation from the Franck-Condon distribution generally expected in ionization of Rydberg electrons. Namely, in addition to main photoelectron peaks due to Δv = 0 transitions, other vibrational peaks are also observed with considerable intensities. The v⁺= 2 photoelectron peak shows different angular dependence from the other vibrational peaks. The rotational structure in the MPI ion-current spectrum of O₂ is well interpreted in terms of the rotational constants of the X²Π_g ground electronic state of O₂⁺.     

Jets physics in comet P/Halley

Summary CCD images of comet P/Halley taken from Catania Observatory in April 1986 with IHW filters are analysed. On scale distances up to and larger than 200·10³ km these images show the presence of jets in the Cont 6850, H₂O⁺ and C₂ filters. The jet maximum intensity is at <1000 km from the nucleus for dust, at (20÷30)·10³km for H₂O⁺ and at (60÷90)·10³km for C₂, implying 2·10⁴s or 10⁵s formation time for the last two molecules. Comparison of various images shows that H₂O⁺ and C₂ jets are in very different directions, the first one coinciding with the main dust jet, the second one appearing as a continuation in space of a very short dust jet. It is speculated that dust grains have very different sizes and chemical composition from the moment they leave the cometary nucleus, and that grains in the small dust jet undergo fragmentation and chemical reactions to produce C₂ jets.     

A photoelectron-ion-ion triple coincidence technique for the study of double photoionization and its consequences

A new technique in which two photoions are detected in coincidence with a photoelectron is described, and its advantages in the study of double ionization are explored. The power of the technique to distinguish decay routes is demonstrated by proof that the equal mass fragmentation of SO₂²⁺produces predominantly O₂⁺ + S⁺and not O⁺ + O⁺. The dissociation of CH₃I²⁺ following He(II) ionization is shown to involve at least twelve distinct pathways, instead of the six previously known.A major potential of the new technique is to elucidate the dynamics of three-fragment decays: it is shown that the formation of C⁺ + S⁺ from CS₂²⁺ can be modelled as a sequential, rather than a simultaneous explosion. The new technique gives the first demonstration, in the case of NO₂, of angular anisotropy in the electrons ejected in double photoionization. The counting statistics of the new method are shown to allow absolute calibration of the detection efficiencies for both electrons and ions. Finally, the technique offers a new method for the detection and investigation of slowly dissociating doubly-charged ions.     

DC discharge experiment in an Ar/N2/CO2 ternary mixture: A laboratory simulation of the Martian ionosphere's plasma environment

A low-pressure DC plasma discharge sustained in a 1.6%Ar–2.7%N₂–95.3%CO₂ ternary mixture is studied. This plasma was generated in a total pressure range from 1.0 to 4.0 Torr, a power of 6.3 W and a 12 l/min flow rate of gases. The electron temperature was found to be 8.41 eV and the ion density, in the order of 10⁹ cm⁻³. The species observed in the plasma mixture were CO₂, CO₂⁺, CN, CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺. At the pressure range in the present study, the species observed do not change their intensity due to an increase in the pressure and they separate in two groups according to their emission intensity: the band of the first group (CO₂, CO₂⁺ and CN) is approximately a factor of 3 more intense than that of the second group (CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺). The behavior of the emission intensities may be correlated to the constant ion density and electron temperature measured. Also, we observed the same constant behavior in the ratios of the neutral and positive species intensities to that of the N₂ intensity, as a function of pressure. This may suggest that the different rate coefficients and cross sections of elastic collision, excitation and de-excitation of electronic or vibrational levels, inelastic and superelastic collisions of electrons with the gas phase and products, neutral–neutral interactions, resonant charged transfer processes, recombination, to mention some, to produce these species change in the same proportion, as a function of the pressure to keep the relative ratios of the species almost constant.     

Field ionization of ozone

Experimental results on the field ionization of ozone at an iridium surface using a magnetic sector atom-probe FIM show that at the lowest field of ~1.5 V/Å only 25% of all ions produced are O⁺₃, while O⁺₂ and a small percentage of O⁺ indicate field induced dissociation of ozone and recombination of atomic oxygen into O₂. At high fields and free space ionization, O⁺₂ is predominant, while the atomic oxygen as a dissociation product escapes without being ionized and cannot be detected. Using pure oxygen as an imaging gas in the FIM, O⁺₂ ions do not dissociate under the same conditions.     

Point defects related to 260 K thermostimulated luminescence in α-Al2O3

Abstract

Thermo- and photostimulated processes are studied in reduced hydrogen containing α-Al₂O₃ excited by UV light. It is found that UV excitation in F absorption band at 90 K results in a ionization of the F-centers and capture of released electrons at defects thus producing an anisotropy absorption band at 4.2 eV and the dominant thermoluminescence (TL) peak at 260 K. The 260 K TSL peak is accompanied by complete bleaching of the 4.2 eV absorption band and vice versa—by light stimulation in the region of the 4.2 eV band the 260 K TSL peak disappear and released electrons recombine with F⁺-centers. Both the effect of the preliminary high-temperature thermal treatment of samples on formation of 4.2 eV-centers and the observed dichroism characteristics allows to conclude that corresponding complex defect contains hydrogen and can involve vacancy pair.     

Electronic structure of F,-center in MgO

The embedded-cluster numerical variational method has been developed to calculate the electronic structure of perfect MgO, F and F⁺-centers in MgO. The energy band, bulk density of states has been calculated by cluster Mg₁₄O₁₃, Mg₁₄O₁₂F⁺ and Mg₁₄O₁₂F. The calculated absorption energy for F⁺ and F centers is in good agreement with experimental data. In our calculated defect energy levels, that the first excited state of F⁺-center is at CB-3.46 eV, indicates the necessity of a large photoelectron yielding energy. We also calculate the radius of color center electron, and plot the map of charge-density distribution of valence electrons in which the structure of the color center is shown directly. Received 22 May 1998     

Collisionless multiphoton ionization of water molecules by a TEACO2 laser

Collisionless ionization of water molecules into fragments of H⁺, H₂⁺, O⁺, OH⁺, H₂O⁺ were observed using a high power TEACO₂ laser. The mechanism could be related to that of selective dissociation of complex molecules by the same laser.     

大气等离子体中氮氧化物粒子行为的数值模拟

利用一个空间零维大气等离子体模型对其中的氮氧化物在不同电离度情况下的变化规律进行了数值模拟,得到了放电后不同初始电子密度下的氮氧化物(包括NO,NO⁺,NO₂,NO₂⁺,N₂O,N₂O⁺,NO₃和N₂O₅)及影响其产消的主要反应物N和O₃的密度随时间的演化规律.结果表明,电子初始密度n_e0=10⁹ cm^-3时,NO和NO₂的去除率较高,氮氧化物总密度较小,最适合消除氮氧化物污染.同时,还对N和O₃随电离度变化的行为进行了分析. 关键词： 大气等离子体 氮氧化物 电离度 数值模拟     

Hard X-ray emission by clusters in an intense femtosecond laser field during collective recombination

We consider the new mechanism of X-ray generation by clusters under irradiation by femtosecond laser pulses, the so-called collective photorecombination. We develop the theory of the photo-recombination of electrons that pass from atomic clusters at the outer ionization to the ground level of a homogeneously charged cluster. Such a cluster is considered to be a quantum potential well. The dipole approximation is inapplicable for this process. We conclude that X-ray photons in collective photorecombination on a charged cluster as a whole have an energy that is much larger than that for photorecombination on separate atomic ions inside the cluster. For a typical cluster of 2.25 × 10⁶ electrons, with a radius R = 300 Å, and a number density of plasma electrons n _e = 2 × 10²² cm^?3, we find that at a 5% outer ionization of this cluster, the energy of hard X-ray photons is 7.2 keV.