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.     

Fragmentation of adenine and uracyl molecules through electron captures in collisions with ions

The time-of-flight mass spectrometry method is used to study processes occurring when 36-keV multiply charged Ar ions (Ar⁶⁺) capture electrons from adenine and uracyl molecules. Adenine and uracyl constitute one of two base pairs entering into the RNA composition. The fragmentation scheme of resulting molecular ions is derived by analyzing correlations between the detection times of all fragment ions. Fragmentation patterns for molecular ions resulting from molecule ionization by photons, electrons, protons, and multiply charged ions are compared.     

Dissociative ionization of the H2O molecule bombarded by swift singly charged and slow highly charged ions

Fragment ion energy spectra of the water molecule have been measured in conventional crossed-beam experiments by the impact of 46 keV/u energy, singly charged ions (SCIs) and 4.3 keV/u energy, highly charged ions (HCIs). Double differential cross sections have been determined and a comparative analysis has been performed. We found that the fragmentation spectra for SCIs and HCIs are very similar, indicating that both collisions lead to the same fragmentation channels. This suggests that the Coulomb explosion of the water molecule is dominantly determined by the charge state of the transient molecular ions, and it is almost independent from the primary ionization mechanism. Differences were observed not only between the SCI and HCI impact-induced fragmentation cross sections, but between those obtained by the 60 keV N⁶⁺ and 70 keV O⁷⁺ projectiles. The differences were attributed to the selectivity of the electron capture process for HCIs. Multiple target ionization cross sections have been deduced from the fragment ion spectra. We found contributions of up to fivefold ionization for SCIs and up to sixfold ionization for HCIs.     

Single and multiple ionization of N2 molecules by intense light fields of femtosecond duration

We report studies on the multiple ionization of the N₂ molecule using intense, femtosecond laser pulses. We present details of the experimental characterisation of the light pulses and analysis and detection of the ions produced. Precautions to be taken in intense field ionization experiments are discussed. We illustrate the retrieval of information about different aspects of the ionization process (such as, kinetic energies of the fragments produced, dissociation bond lengths and information on the precursors to fragmentation) using coincidence techniques. We report results of the first measurements of the angular distribution of a highly charged fragment, N³⁺.     

Observation of high-energy electrons from a metal target irradiated by protons with a mean energy of 25 keV

Electrons with abnormally high energies of up to 16 keV are detected from an iron target irradiated by ions (H⁺, Fe⁺, Fe²⁺, Fe³⁺) with energies ranging from 20 to 100 keV from the plasma of a high-power femtosecond laser pulse with an intensity of 10¹⁶ J/(s cm²). These electrons indicate that the energy of an incident ion is almost completely transferred to an electron knocked out of the target. In a range of 6–16 keV, the spectrum of electrons knocked out of the K shell of iron atoms by protons with an energy of 22 ± 2 keV is quasi-exponential with an exponent of 4 keV. For 8-keV electrons, the double differential cross section for ionization by such protons is estimated as 10^?7 b/(eV sr).     

Multiple ionization and fragmentation of negatively charged fullerene ions by electron impact

Cross sections for the electron-impact multiple ionization and fragmentation of negatively charged fullerene ions C(-)(n) ( n = 60, 70) to C(q+)(n-m) ( q = 1,2,3 and m = 0,2,4) have been measured for electron energies up to 1 keV. In the case of pure ionization all threshold energies are about 10 eV higher than the values expected. This shift, however, is not observed for the fragment ions. The experimental data indicate that there is no strong electron-electron interaction between the incident electron and the attached electron. A novel ionization mechanism is proposed which can be expected to be valid for all negatively charged molecular or cluster ions which are able to shield the attached electron from the incident electron.     

Decay reactions of rare gas cluster ions: Kinetic energy release distributions and binding energies

We have carried out measurements on metastable fragmentation of mass selected argon cluster ions which are produced by electron impact ionization of a neutral argon cluster beam. From the shape of the fragment ion peaks (MIKE scan technique) one can deduce information about the distribution of kinetic energy that is released in the decay reaction. In this study, for Ar ₅ ⁺ to Ar ₁₅ ⁺, it is Gaussian and thus we can calculate from the peak width the mean kinetic energy release 〈KER〉 of the corresponding decay reactions. Using finite heat bath theory we calculate from these data the binding energies of the decaying cluster ions. Received 20 November 2000     

Elementary processes during collisions of ions with tryptophan molecules

The relative cross sections of elementary processes occurring in single collisions of tryptophan molecules in the gaseous phase with He²⁺ ions with energy 4 keV/u are measured using time-of-flight mass spectrometry for studying the mechanism of radiation damage of amino acid molecules. The fragmentation channels for intermediate singly and doubly charged tryptophan molecular ions formed during one-electron capture, two-electron capture, and electron capture with ionization are investigated. Significant difference is observed in the mass spectra of fragmentation of intermediate doubly charged ions formed during the capture with ionization and double capture, which is associated with different energies of excitation of {C₁₁H₁₂N₂O₂}²⁺* ions.     

Capture of an electron by ions in methionine and norleucine molecules

The relative cross sections of processes taking place when H⁺ and He²⁺ ions with an energy of 6z keV (z is the ionic charge) capture an electron from molecules of C₅H₁₁NO₂S methionine (proteogenic amino acid) and C₆H₁₃NO₂ norleucine (nonproteogenic amino acid) are measured by time-of-flight mass spectrometry (a methionine molecule transforms into a norleucine molecule by substituting the CH₂ group for the S heteroatom). The fragmentation pattern of resulting molecular ions is established from correlation analysis of the detection times of all fragment ions. The results are compared with experimental data for fragmentation of the same molecules ionized by electrons and photons. In these amino acids, the pattern of molecular ion fragmentation is found to depend on the type of molecule ionization. However, the detachment cross section of the COOH neutral group or residue (neutral or charged) R of a side chain of the amino acid is invariably among the largest. The relative cross sections of capture with single and double ionization of molecules are measured.     

Recent results on multiple ionization and fragmentation of negatively charged fullerene ions by electron impact

Employing the dynamic crossed-beams technique, the absolute cross sections of the electron-impact multiple ionization and fragmentation of mass-selected negatively charged fullerene ions C _m ^? → C _m?n ²⁺ (m=60, 70, 84; q=1, 2, 3; n=0, 2, 4) were measured. The electron energy varied from the respective threshold up to 1 keV. A scaling law was observed for the cross-section magnitude as a function of the fullerene size m and the charge state q of product ions. The data indicate that different mechanisms account for the detachment of an extra electron from the negatively charged fullerene and the formation of a positively charged ion, respectively. Moreover, the multiple ionization of a fullerene anion is found to be a sequential process. A novel ionization mechanism is proposed which might be expected to be valid for all negatively charged molecular or cluster ions able to shield the attached electron from the incident electron.     

Processes involving a change in the charge states during interactions of He2+ ions with fullerenes

The cross sections for the elementary processes involving a change of the charge states of both particles during the interaction of He²⁺ ions with fullerene molecules are for the first time measured over a broad energy range of electron-volt energies. It is found that processes involving the capture of one or two electrons by the He²⁺ ions are accompanied by additional ionization of the fullerene and that the collisional contribution of the transfer-ionization processes increases with increasing velocity. Single-electron capture is rarely accompanied by fragmentation of the fullerene. Double-electron capture leads, with a higher probability, to fragmentation with the formation of several light charged fragments and, with a smaller probability, to fragmentation with the formation of a heavy charged fragment containing an even number of carbon atoms and light fragments in an uncharged state. Zh. Tekh. Fiz. 68, 12–14 (April 1998)     

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     

Charge driven fragmentation of nucleobases

We studied multiple ionization of single nucleobases by means of slow highly charged ions (Xe(q+), q=5-25). The products of the subsequent fragmentation were studied using high resolution coincidence time-of-flight spectrometry. We observed a strong dependence of the fragment kinetic energies on the initial charge state of the intermediate parent ions as well as on the initial chemical environment of the respective fragment ions within the parent molecule. The data allow us to shed light on the charge distribution within the molecule as well as on the fragmentation dynamics of these intermediate size systems.     

Electron-impact ionization and dissociative ionization of sulfur in the gas phase

We describe the methods and the results of investigation of the yield of positive ions formed as a result of electron-impact ionization of sulfur. The ionization energy for the basic molecule and the energies corresponding to the emergence of fragment ions are obtained from the ionization efficiency curves. The dynamics of formation of molecular sulfur ions in the temperature range 320–700 K is investigated. The energy dependences of efficiency S _n of the ion formation for n = 1–6 are analyzed, and their appearance energies are determined. The total cross section of sulfur ionization by a monochromatic electron beam is also investigated. Using the linear approximation method, we marked out features on the ionization function curve, which correspond to the ionization and excitation energies for multiply charged ions. The total cross section of the formation of negative sulfur ions is measured in the energy range 0–9 eV.     

Examination of a molecular se beam by mass spectrometry with electron ionization

The methodology and results of mass-spectrometric studies of producing positive ions as a result of the dissociative ionization of a molecular selenium beam by electron impact are discussed. The appearance energies of fragment ions were determined from the ionization efficiency curves. The dynamics of production of molecular selenium ions in the temperature range of 420–500 K was also examined. The energy dependences of efficiency of production of singly charged Se _n ⁺ ions for n = 1–4 and the doubly charged selenium ion in the interval from the threshold to 36 eV were studied for the first time. The observed specific features of effective ionization cross sections were analyzed.     

Effect of electrons of the multiply charged ion core on single-electron capture

The population of various electronic states of particles that arise during the capture of a single electron in hydrogen and helium atoms, as well as hydrogen molecules, by Ar³⁺ and Ne³⁺ ions with an energy of several kiloelectronvolts was studied by collision spectroscopy, viz., precision analysis of kinetic energy variation for ions formed as a result of interaction between ions and atoms. It is shown that single-electron capture in many cases is a multielectron process accompanied by the rearrangement of a multiply charged ion core. It is found that the triply charged Ne³⁺ ions formed as a result of ionization of Ne atoms by electron impacts are formed mainly in metastable states. The population of excited states of particles during their multiple ionization should be taken into account in determining the characteristics of various particles by the appearance potential method. Collision spectroscopy can be used for analyzing the metastable ion impurities in ionic beams.     

Ionization of iridium ions in the Dresden EBIT studied by X-ray spectroscopy of direct excitation and radiative recombination processes

Ir^q+ ( 41≤q≤64) ions with open-shell configurations have been produced in the electron beam of the room-temperature Dresden Electron Beam Ion Trap (Dresden EBIT) at electron excitation energies from 2 keV to 13 keV. X-ray emission from direct excitation processes and radiative capture in krypton-like to aluminium-like iridium ions is measured with an energy dispersive Si(Li) detector. The detected X-ray lines are analyzed and compared with results from multiconfigurational Dirac-Fock (MCDF) atomic structure calculations. This allows to determine dominant produced ion charge states at different electron energies. The analysis shows that at the realized working gas pressure of 5×10^-9mbar for higher charged ions the maximum ion charge state is not preferently determined by the chosen electron beam energy needed for ionization of certain atomic substates, but by the balance between ionization and charge state reducing processes as charge exchange and radiative recombination. This behaviour is also discussed on the basis of model calculations for the resulting ion charge state distribution. Received 12 July 2001 and Received in final form 10 September 2001     

Experiments on clusters

In this contribution we discuss four different types of experiments that have been conducted at molecular beams of neutral clusters. The size of particularly stable sodium chloride clusters and their corresponding geometrical structure is inferred from intensity anomalies in mass spectra. This information is obtained either for charged or for neutral clusters depending on whether the clusters are ionized by electron impact or by multiphoton absorption. The important role of fragmentation in mass spectrometry of xenon clusters is revealed by multiphoton ionization; dissociative reactions occurring on the time scale of 10⁻⁷ s with respect to the ionizing event can be analyzed. The solvation energy of negatively charged carbon dioxide clusters as a function of cluster size is obtained from electron attachment spectra. A resonance in the ion yield close to zero eV electron energy signifies that all clusters except for the monomer feature a positive electron affinity. An analysis of the kinetic energy of fragment ions, originating from delayed dissociation of triply charged carbon dioxide clusters, reveals that the size distribution of their fission fragments is extremely symmetric.     

高电荷态离子与Si(110)晶面碰撞的沟道效应研究

不同电荷态低速离子(Ar^q+,Pb^q+)轰击Si(110)晶面,测量不同入射角情况下的次级粒子的产额. 通过比较溅射产额与入射角的关系,证实沟道效应的存在. 高电荷态离子与Si相互作用产生的沟道效应说明溅射产额主要是由动能碰撞引起的. 在小角入射条件下,高电荷态离子能够增大溅射产额. 当高电荷态离子以40°—50°入射时,存在势能越高溅射产额越大的势能效应. 关键词： 高电荷态离子 溅射 沟道效应     

Fragmentation of polyatomic ions produced by electron-loss collisions of butane and isobutane molecules with ions of kiloelectronvolt energy

Fragmentation accompanying the loss of electrons by butane and isobutane (C₄H₁₀) molecules in collisions with energy H⁺, He²⁺, and Ar⁶⁺ ions of kiloelectronvolt energies is studied. The electron density functional technique is applied to C _n H_2n+2 alkane molecules and their respective C _n H _2n+2 ⁺ ions to carry out quantum-chemical calculations of the atomic spacing, electron total energy for the initial configuration of the ionizing molecules and ions in the ground state, and atomic bond breaking energy necessary to produce different ion fragments. The fragmentation energy is correlated with the fragmentation probability. It is shown that the relative cross sections of ion fragmentation depend primarily on the related energy consumption. However, the process cross section is also strongly affected by the initial configuration of C₄H₁₀ isomer molecules, as well as by the amount of dangling and arising atomic bonds involved in the formation of each ion fragment.