ESD and IID study of CO on nickel

Electron and ion induced desorption has been used to study release of ionic species from CO on nickel. O⁺, CO⁺, and O^? are found to be released by electron impact. Thermal desorption spectra indicate the presence of two binding states. The O⁺ species is observed to be released from state 1, the state of higher binding energy, while state 2, a more loosely bound state is the source of CO⁺. O^? species appear to be released from both states. The cluster ions NiCO⁺ and Ni₂CO⁺ released by argon ion impact were observed to originate from state 2.     

Dissociative photoionization of l-menthone: An experimental and theoretical study

The dissociative photoionization mechanism of l-menthone has been investigated with photoionization mass spectrometry using synchrotron radiation. The adiabatic ionization energy (IE) of l-menthone and the appearance energies (AE) of its major fragment ions C₉H₁₅O⁺, C₉H₁₇⁺, C₈H₁₆⁺, C₇H₁₁O⁺, C₆H₁₀O⁺, C₆H₉O⁺, C₅H₈O⁺, C₅H₁₀⁺, C₄H₆O⁺, C₅H₉⁺, C₄H₈⁺, C₄H₇⁺, C₃H₇⁺, C₃H₆⁺, C₂H₂O⁺, and CH₃⁺ are determined with their photoionization efficiency (PIE) spectra in the photon energy region of ∼8−15.5 eV. Breakdown diagrams identifying the major products are presented. Dissociative photoionization channels for formation of these fragment ions are proposed based on comparison of determined experimental appearance energies and energies predicted with the DFT calculations. According to our results, the experimental dissociation energies are in fair agreement with the theoretical values of the possible photodissociation channels of C₁₀H₁₈O.     

On the dissociation of the ozone dication

A mechanism for the dissociation of the ozone dication formed by double ionisation of neutral O₃ is determined by ab initio calculations. The dication ground singlet state is found to have a linear equilibrium geometry that is stable with respect to dissociation to O⁺ and O₂⁺. However, at the Franck-Condon zone for formation of O₃²⁺ from the neutral molecule the singlet potential energy surface intersects with a dissociative triplet state. We propose that crossing to this dissociative triplet state can account for the absence of any long-lived O₃²⁺ ions in the electron-impact mass spectrum of ozone. Further calculations of the kinetic energy release for the fragmentation of O₃²⁺ to O⁺+O₂⁺ indicate that considerable vibrational excitation may be present in the O₂⁺ ion.     

Kinetic energy release for the collision-induced dissociation of CO<Superscript>+</Superscript>

The kinetic energy release distributions (KERDs) of C⁺ and O⁺ fragments arising from 5 keV collision-induced dissociation (CID) of CO⁺ ions with helium have been measured. The KERDs of C⁺ and O⁺ exhibit different features corresponding to the states that participate in CID processes. We have identified groups of dissociative and predissociative states, and compare them with theoretical and experimental values.     

1,4-二氧六环的真空紫外同步辐射光解离电离研究

The photoionization and photodissociation of 1,4-dioxane have been investigated with a reflectron time-of-flight photoionization mass spectrometry and a tunable vacuum ultraviolet synchrotron radiation in the energy region of 8.0-15.5 eV. Parent ion and fragment ions at m/z 88, 87, 58, 57, 45, 44, 43, 41, 31, 30, 29, 28 and 15 are detected under supersonic conditions. The ionization energy of DX as well as the appearance energies of its fragment ions C₄H₇O₂⁺, C₃H₆O⁺, C₃H₅O⁺, C₂H₅O⁺, C₂H₄O⁺, C₂H₃O⁺, C₃H₅⁺, CH₃O⁺, C₂H₆⁺, C₂H₅⁺/CHO⁺, C₂H₄⁺ and CH₃⁺ was determined from their photoionization efficiency curves. The optimized structures for the neutrals, cations, transition states and intermediates related to photodissociation of DX are characterized at the B3LYP/6-31+G(d,p) level and their energies are obtained by G3B3 method. Possible dissociative channels of the DX are proposed based on comparison of experimental AE values and theoretical predicted ones. Intramolecular hydrogen migrations are found to be the dominant processes in most of the fragmentation pathways of 1,4-dioxane.     

电子束引起的残余含氧气体在镍(001)面上的吸附

当一束具有一定能量和强度的电子束轰击超高真空系统中残余的水汽、一氧化碳和二氧化碳时,将导致这些气体分子通过如下反应:H₂O→O_ad+H₂,CO₂→O_ad+CO,CO→O_ad+C_ad分解并共吸于镍表面。碳和氧的原子各自占据镍(001)面部份四重吸附位置,形成结构为p(2×2)或c(2×2)的许多独立的吸附畴,电子束轰击促进畴的成核、长大、连结和有序化。当氧和碳的原子占据了镍(001)面约一半的四重吸附位后,上述吸附反应将与导致氧和碳的脱附反应:C^*+O_ad→CO,O^*+C_ad→CO平衡,氧化镍与碳化镍开始成核。由于残余含氧气体中氧的含量超过碳,氧化镍成核占优势,使碳的吸附被排斥,已吸附的碳被排挤,形成电子束斑内氧高碳低、束斑外碳高氧低的“互补”分布。电子束轰击过程中碳的俄歇峰形的变化反映着碳原子与基底原子的不同结合状态。电子束的解离效应在吸附的初始阶段起重要作用,而其热效应对氧化镍的长大起重要作用。 关键词：     

II. Electron-impact dissociative excitation of C<Subscript>2</Subscript>H<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and C<Subscript>2</Subscript>D<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections for electron-impact dissociative ionization of C₂ H₂⁺ and C₂ D₂⁺ to CH⁺, C⁺, C₂⁺ , H⁺, CH₂⁺ and C₂D⁺ fragments are determined for electron energies ranging from the corresponding threshold to 2.5 keV. Results obtained in a crossed beams experiment are analyzed to estimate the contribution of dissociative ionization to each fragment formation. The dissociative ionization cross sections are seen to decrease for more than an order of magnitude, from CH⁺ (5.37±0.10) × 10^-17 cm² over C⁺ (4.19± 0.16) × 10^-17 cm², C₂D⁺ (3.94±0.38) × 10^-17 cm², C₂⁺ (3.82±0.15) × 10^-17 cm² and H⁺ (3.37±0.21) × 10^-17 cm² to CH₂⁺ (2.66±0.14) × 10^-18 cm². Kinetic energy release distributions of fragment ions are also determined from the analysis of the product velocity distribution. Cross section values, threshold energies and kinetic energies are compared with the data available from the literature. Conforming to the scheme used in the study of the dissociative excitation of C₂H₂⁺ ( C₂ D₂⁺ )\left( {\rm C}_2 {\rm D}_2^+ \right), the cross-sections are presented in a format suitable for their implementation in plasma simulation codes.     

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.     

Elektronenlawinen in elektronegativen Gasen

It is possible to determine the coefficients of ionisation (α) and attachment (η) and the drift velocities of the positive and negative ions formed by these processes by analysing the current pulses of avalanches (started by c. 10³ electrons) under homogeneous field conditions with wide band oscillographic techniques. Measurements were made with some electronegative gases such as CO₂, Freon 12, SO₂, SF₆, and O₂. In CO₂ and Freon 12 negative ions are formed by dissociative attachment only, while in SO₂ additional negative ions are formed in a three body process. At higher pressures in Freon 12 clustering of negative ions becomes apparent, as the existence of two different mobilities was confirmed. For O₂ a detachment process of negative ions must be taken into account. The same seems to apply, to a lesser extent, to SF₆.     

Positive and negative ionic desorption from condensed formic acid photoexcited around the O 1s-edge: Relevance to cometary and planetary surfaces

Photon stimulated ion desorption (PSID) studies have been performed in condensed formic acid using oxygen 1s-edge synchrotron radiation from the Brazilian synchrotron light source (LNLS), operating in a single-bunch mode. Ion formation was discussed in terms of the Auger stimulated ion desorption (ASID) and X-ray induced electron stimulated desorption (XESD) mechanisms. It is found that O 1s(C-OH) → π*(CO) and O 1s(CO) → 3s/σ*(HCO) transitions favored the production of C⁺, CH⁺, O⁺, O⁻ and H⁻ ions. The hydroxyl anion has not been observed while the hydroxyl cation showed low intensity or was absent. Some anion formation routes from dissociative reactions are suggested taking into account the positive ion yields.     

Dissociative charge exchange in collisions of 10keV H 2 + ions on H2, He,and Ar targets

The velocity distributions of H-H fragment pairs arising from dissociative collisions of 10keV H ₂ ⁺ ions incident on H₂, He, and Ar were measured using a flight-time-difference method. The H ₂ ⁺ ions were produced in an electron impact ion source at two different electron energies, at 100eV and 18eV. The influence of the electron energy on the fragment velocity distributions is studied. Conclusions are drawn on the processes which lead to the formation of neutral fragment pairs. Electron capture into the repulsive b³ Σ _u ⁺ state of H₂ plays a dominant role.     

Equilibrium charge state distributions of beam foil excited molecular fragments exiting carbon foils

Summary Equilibrium charge state distributions of ions emerging from solids have been measured. As incident particles were used both atomic (C⁺, N⁺, O⁺) and molecular (N ₂ ⁺ , CO⁺) projectile ions (0.025<E/M<0.108 MeV/u). The data of atomic projectile ions agree well with the data of other authors in a range in which they overlap. Charge state fractions of emerging molecular-fragment ions behind a carbon foil are strongly influenced by the Coulomb explosion and possibly by the wake potential. Supported by BMFT/Bonn.     

甲烷分子电子碰撞电离和解离的实验研究

本文利用反应显微成像技术(reaction microscope)研究了54 eV电子入射甲烷分子导致的电离解离过程,详细分析了电离解离产生的CH⁺₂,CH⁺,C⁺离子碎片的动能分布情况.实验结果表明,该入射能量下产生CH⁺₂,CH⁺,C⁺离子碎片主要贡献来自2a₁内价轨道电子的直接电离过程产生的离子态(2a< 关键词： 反应显微成像谱仪 电离解离 能量沉积 动能分布     

Electron stimulated desorption of CO from

The electron impact behavior of CO adsorbed on was investigated. The desorption products observed were neutral CO, CO⁺, and O⁺. After massive electron impact residual carbon, C/W = 0.15, but not oxygen was also found, suggesting that energetic neutral O, not detected in a mass analyzer must also have been formed. Formation of β-CO, i.e., dissociated CO with C and O on the surface was not seen. The total disappearance cross section varies only slightly with coverage, ranging from 9 × 10 ⁻¹⁸ cm² at low to 5 × 10⁻¹⁸ cm² at saturation (CO/W = 0.75). The cross section for CO⁺ formation varies from 4 × 10⁻²² cm² at satura to 2 × 10⁻²¹ cm² at low coverage. That for O⁺ formation is 1.4 × 10⁻²² cm² at saturation and 2 × 10⁻²¹ cm² Threshold energies are similar to those found previously [J.C. Lin and R. Gomer, Surf. Sci. 218 (1989) 406] for and CO/Cu₁/W(110) which suggests similar mechanisms for product formation, with the exception of β-CO on clean W(110). It is argued that the absence or presence of β-CO in ESD hinges on its formation or absence in thermal desorption, since electron impact is likely to present the surface with vibrationally and rotationally activated CO in all cases; β-CO formation only occurs on surfaces which can dissociate such CO. It was also found that ESD of CO led to a work function increase of the remaining Pd₁/W(110) surface of 500 meV, which could be annealed out only at 900 K. This is attributed to surface roughness, caused by recoil momentum of energetic desorbing entities.     

Ionization of nitrogen,oxygen, water,and carbon dioxide molecules by near-threshold electron impact

An experimental technique for measuring the cross sections of direct and dissociative ionization of N₂, O₂, H₂O, and CO₂ molecules by electron impact in the near-threshold energy range is described. The setup used in the experiments allows mass separation of ions with a monopole mass spectrometer. It is shown that such a setup can be used to advantage in separation experiments. For incident electron energies between 7 and 35 eV, the energy dependences of the cross sections of generation of parent ions and ion fragments due to parent molecule dissociation are obtained.     

Primary ion state conservation in electron capture from Li(2s) by singly charged ions

Conservation of the initial electronic configuration of singly charged ions in state-selective single electron capture from Li(2s) has been investigated. For impact of O⁺, N⁺ and C⁺ (2–20 keV) it could be demonstrated within the experimental errors, that “core conservation” holds for population of the most probable final states.     

On the bound states in the muonic molecular ions

Absolute cross sections for electron impact ionization and dissociation of OH⁺ and OD⁺ leading to the formation of the OH²⁺, O⁺, O²⁺, O³⁺ and D⁺ ions have been measured by applying the animated electron-ion beam method in the energy range from the respective reaction thresholds up to 2.5 keV. The maximum of the single ionization cross section is found to be (0.95? ± ?0.02) × 10^?19 cm² at 155 eV. The maximum total cross sections for O⁺ and D⁺ fragments production are observed to be (15.7? ± ?0.2) × 10^?17 cm² at 95 eV and (10.8? ± ?0.5) × 10^?17 cm² at 95 eV, respectively. The cross sections for O²⁺ and O³⁺ are much smaller, (5.37? ± ?0.04) × 10^-18 cm² at 135 eV and (7.95? ± ? 0.23) × 10^-20 cm² at 315 eV, respectively. The collected data are analyzed in details in order to determine separately the contributions of dissociative excitation and of dissociative ionization to the O⁺ and D⁺ fragments production.     

Electron-impact ionization and dissociation of C<Subscript>2</Subscript>D<Superscript>+</Superscript>

Absolute cross sections for electron-impact single ionization, dissociative excitation and dissociative ionization of the ethynyl radical ion (C₂D⁺)^+) have been measured for electron energies ranging from the corresponding reaction thresholds to 2.5 keV. The animated crossed electron-ion beam experiment is used and results have been obtained for the production of C₂D²⁺, C²⁺, C₂⁺_2^+ , CD⁺, C⁺ and D⁺. The maximum of the cross section for single ionization is found to be (2.01 ± 0.02) × 10^-17 cm², at the incident electron energy of 105 eV. Absolute total cross sections for the various singly charged fragments production are observed to decrease by a factor of almost three, from the largest cross-section measured for C⁺, over C₂⁺_2^+ and CD⁺ down to that of D⁺. The maxima of the cross sections are obtained to be (14.5 ± 0.5) × 10^-17 cm² for C₂⁺_2^+, (12.1 ± 0.1) × 10^-17 cm² for CD⁺, (27.7 ± 0.2) × 10^-17 cm² for C⁺ and (11.1 ± 0.8) × 10^-17 cm² for D⁺. The smallest cross section is measured to be (1.50 ± 0.04) × 10^-18 cm² for the production of the doubly charged ion C²⁺. Individual contributions for dissociative excitation and dissociative ionization are determined for each singly-charged product. The cross sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. Kinetic energy release distributions of dissociation fragments are seen to extend from 0 to 6 eV for the heaviest fragment C₂⁺_2^+, up to 11.0 eV for CD⁺, 14.2 eV for C⁺ and 11.2 eV for D⁺ products.     

Ionization and dissociative ionization of methane molecules

A technique for mass-spectrometric investigation of the yield of positive ions produced by direct and electron-impact dissociative ionization of methane molecules is described, and respective experimental data are presented. Doubly charged C ₂ ⁺ , CH ₃ ²⁺ , and CH ₄ ²⁺ ions, as well as singly charged D ₂ ⁺ , CD ₃ ⁺ , and CD ₄ ⁺ ions, are detected in the mass spectrum of a methane molecule at electron energy U _e = 90 eV for the first time. From ionization efficiency curves, the ionization energy of the parent molecule and the appearance energy of fragment ions are determined. The ionization energy of the CH₄ molecule is found to be 12.62 ± 0.20 eV. Electron-molecular reactions that may take place when a low-energy electron beam interacts with a methane molecule are analyzed. The ionization process and the formation of methane molecule fragments are studied.     

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.