Electron Impact Dissociative Ionization Research Articles

Astronomical CH3+ rovibrational assignments

Context. The methyl cation (CH3+) has recently been discovered in the interstellar medium through the detection of 7 μm (1400 cm−1) features toward the d203-506 protoplanetary disk by the JWST. Line-by-line spectroscopic assignments of these features, however, were unsuccessful due to complex intramolecular perturbations preventing a determination of the excitation and abundance of the species in that source. Aims. Comprehensive rovibrational assignments guided by theoretical and experimental laboratory techniques provide insight into the excitation mechanisms and chemistry of CH3+ in d203-506. Methods. The rovibrational structure of CH3+ was studied theoretically by a combination of coupled-cluster electronic structure theory and (quasi-)variational nuclear motion calculations. Two experimental techniques were used to confirm the rovibrational structure of CH3+:(1) infrared leak-out spectroscopy of the methyl cation, and (2) rotationally resolved photoelectron spectroscopy of the methyl radical (CH3). In (1), CH3+ ions, produced by the electron impact dissociative ionization of methane, were injected into a 22-pole ion trap where they were probed by the pulses of infrared radiation from the FELIX free electron laser. In (2), neutral CH3, produced by CH3NO2 pyrolysis in a molecular beam, was probed by pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy. Results. The quantum chemical calculations performed in this study have enabled a comprehensive spectroscopic assignment of the v2+ and v4+ bands of CH3+ detected by the JWST. The resulting spectroscopic constants and derived Einstein A coefficients fully reproduce both the infrared and photoelectron spectra and permit the rotational temperature of CH3+ (T = 660 ± 80 K) in d203-506 to be derived. A beam-averaged column density of CH3+ in this protoplanetary disk is also estimated.

Dehydrogenation in Electron-Induced Dissociative Ionization of Pyridine Molecule

"The electron-impact dissociative ionization of pyridine has been investigated using mass spectrometry. Thirty-two well-resolved mass peaks have been identified in the cation mass spectra and assigned to the most likely ionic molecular fragments. The new sixteen ionic fragments' appearance energies have been determined, and sixteen others remeasured. The total cross-section for electron-impact ionization of pyridine has been measured at 100 eV. Thorough analysis indicates that at least three peaks' groups in the mass spectra occur via the shake-off dehydrogenation mechanism, i.e., by sequential hydrogen atoms elimination from the pyridine parent cation or its fragmentation products. The nature of this process is deciphered. "

Electron scattering with ethane adsorbed on rare gas multilayers: Hole transfer, coulomb decay, and ion dissociation.

Positive ion desorption following electron impact dissociative ionization of ethane adsorbed on Ar, Kr, and Xe multilayers has been studied as a function of incident electron energy from threshold to 100eV. Based on the dependence of ion yields on the identity of the rare gas, it is likely that the majority of ethane molecules undergo indirect ionization following hole transfer from the ionized underlying rare gas. This has also been corroborated by density of states calculations showing the energetic alignment of the outer valence states of ethane and the condensed rare gas ionization energies. Due to the near-resonant nature of charge transfer for single-hole states, the ethane molecular ion is excited to different final ionic states on different rare gases, which leads to differences in ion desorption yields and branching ratios. The quantitative yields increase with increasing ionization energy gap between the rare gas and ethane, in the order Ar > Kr > Xe. The large increase in yields from 25eV onwards for all rare gases is likely due to the formation and decay of two-hole states on neighboring rare gas and ethane molecules due to interatomic and intermolecular Coulomb decay (ICD) and not electron transfer mediated decay (ETMD). The ICD and ETMD pathways become accessible when the incoming electron has sufficient energy to excite the inner valence ns level of the rare gas to a Rydberg state or ionize it. The experimental findings are supported by calculations of thresholds, density of states for the final configurations of these processes, and coupling strengths for hole transfer between ethane and rare gases. The fragment ion branching ratios vary with energy from threshold to about 35eV, showing the fragmentation pattern changes with the mode of hole transfer and availability of excess energy. Sigma C-C bonds are more likely to break than C-H bonds in the mid-20eV range, and this effect is most pronounced for Xe, followed by Kr, and then Ar.

The Binary-Encounter-Bethe Model for Computation of Singly Differential Cross Sections Due to Electron-Impact Ionization

In the present work, we assess the effectiveness of singly differential cross sections (SDCS) due to electron-impact ionization by invoking the binary-encounter-Bethe (BEB) model on various atomic and molecular targets. The computed results were compared with the experimental and theoretical data. A good agreement was observed between the present and the available results. This agreement improves as the incident energy of the projectile increases. The model can be applied to compute the SDCS for the ions produced due to the electron-impact dissociative ionization process and the average energy due to the secondary electrons. Both these quantities are of interest in plasma processing and radiation physics.

Symmetry breaking in electron-impact dissociative ionization of linear symmetric molecules

The authors report experimental measurements on electron-impact ionization of CO${}_{2}$ using the angle- and energy-resolved electron-ion-coincidence technique. The results provide experimental evidence of symmetry breaking in electron-impact dissociative ionization of symmetric molecules.

Ab initio study of energy characteristics of small polyatomic molecules in threshold electron-impact dissociative ionization processes

SynopsisA joint theoretical study of electron-impact dissociative ionization (DI) processes of small polyatomic molecules is presented. Different organic (CH4 and C2H6) and inorganic (SF6 and Sn, n = 2-8) target molecules were examined. The investigated dissociative ionization processes take place at threshold energies, so our main focus is to study the appearance energies (E ap) of different ion fragments as well as to analyse the corresponding DI reaction pathways.

Ion energy distributions in highly transient EUV induced plasma in hydrogen

This work reports on the measurements of ion flux composition and ion energy distribution functions (IEDFs) at surfaces in contact with hydrogen plasmas induced by extreme ultraviolet (EUV) radiation. This special type of plasma is gaining interest from industries because of its appearance in extreme ultraviolet lithography tools, where it affects exposed surfaces. The studied plasma is induced in 5 Pa hydrogen gas by irradiating the gas with short (30 ns) pulses of EUV radiation (λ= 10–20 nm). Due to the low duty cycle (10–4), the plasma is highly transient. The composition and IEDF are measured using an energy resolved ion mass spectrometer. The total ion flux consists of H+, H2+, and H3+. H3+ is the dominant ion as a result of the efficient conversion of H2+ to H3+ upon collision with background hydrogen molecules. The IEDFs of H2+ and H3+ appear similar, showing a broad distribution with a cut-off energy at approximately 8 eV. In contrast, the IEDF of H+ shows an energetic tail up to 18 eV. Most probably, the ions in this tail gain their energy during their creation process by photoionization and dissociative electron impact ionization.

Ionization of glycerin molecule by electron impact

The methods and results of studying the yield of positive ions produced due to direct and dissociative electron impact ionization of the glycerin molecule are described. The experiment is carried out using two independent setups, namely, a setup with a monopole mass spectrometer employing the method of crossing electron and molecular beams and a setup with a hypocycloidal electron spectrometer with the gas-filled cell. The mass spectra of the glycerin molecule are studied in the range of mass numbers of 10–95 amu at various temperatures. The energy dependences of the effective cross sections of the glycerin molecular ions produced by a monoenergetic electron beam are obtained and analyzed; using these dependences, the appearance energies of fragment ions are determined. The dynamics of the glycerin molecule fragment ions formation is investigated in the temperature range of 300–340 K.

Ion appearance energies at electron-impact dissociative ionization of sulfur hexafluoride molecule and its fragments

Theoretical analysis of appearance energies for SF + (k = 0−n) ion fragments of SF6 molecule as well as F+ and F 2 + ions at electron-impact dissociative ionization of SF n (n = 1−6) molecules is presented. Theoretical methods of GAMESS software package were used to calculate the total energies of neutral and charged molecular and atomic fragments. The dissociative ionization process is concluded to occur via repulsive highly-excited electronic states of the SF6 molecule and its fragments, due to which the observed appearance energies exceed the theoretical values. The electron binding energies on the molecular orbitals in the SF6 molecule are compared with the ion fragment appearance energies.

Ionization of the glycerin molecule by the electron impact

The paper describes experimental method for and presents the results of studying positive ion yields produced due to direct and dissociative electron-impact ionization of the glycerin molecule. The mass spectra of the glycerin molecule are studied in the range of mass numbers of 10–95 amu at different temperatures. The energy dependences of the ionization efficiency cross sections of the glycerin molecule ions produced by a monoenergetic electron beam are analyzed; using these dependences, the appearance energies of fragment ions are determined. The dynamics of fragment ion formation is investigated in the temperature range of 300–340 K.

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.

Effect of Addition of Nitrogen to a Capacitively Radio-Frequency Hydrogen Discharge

A hybrid PIC/MC model is developed in this work for H2-xN2 capacitively coupled radio-frequency (CCRF) discharges in which we take into account 43 kinds of collisions reaction processes between charged particles (e−, H+3, H+2, H+, N+2, N+) and ground-state molecules (H2, N2). In addition, the mean energies and densities of electrons and ions (H+3, H+2, H+), and electric field distributions in the H2-N2 CCRF discharge are simulated by this model. Furthermore, the effects of addition of a variable percentage of nitrogen (0–30%) into the H2 discharge on the plasma processes and discharge characteristics are studied. It is shown that by increasing the percentage of nitrogen added to the system, the RF sheath thickness will narrow, the sheath electric field will be enhanced, and the mean energy of hydrogen ions impacting the electrodes will be increased. Because the electron impact ionization and dissociative ionization rates increase when N2 is added to the system, the electron mean density will increase while the electron mean energy and hydrogen ion density near the electrodes will decrease. This work aims to provide a theoretical basis for experimental studies and technological developments with regard to H2-N2 CCRF plasmas.

Mass-spectrometric study of the electron-impact-induced fragmentation of the tryptophan molecule

The formation of ion products upon single and dissociative electron-impact ionization of the tryptophan (C11H12N2O2) molecule has been studied using mass-spectrometric techniques. The mass-spectrum of tryptophan has been obtained and interpreted, and the near-threshold ion yields from the initial molecule and the main products of its electron-impact ionization have been measured. The absolute values of ionization energy of the initial tryptophan molecule and the appearance potentials of its main fragment ions have been determined. The influence of exposure to a high-energy beam of accelerated electrons on the resulting mass spectra of initial molecule has been studied.

Electron-impact ionization of sulfur in the gas phase

The procedure and results of studying the yield of positive ions formed via electron-impact dissociative ionization of sulfur are described. The ionization energy of the ground molecule and appearance energies of fragmentary ions are derived from the ionization efficiency curves. The dynamics of formation of molecular sulfur ions in the temperature range of 300–670 K are studied. The energy dependences of the efficiency of formation of ions Sn for n = 1–6 are analyzed, and the appearance energies are determined. The total ionization cross section of sulfur is determined using a monoenergetic electron beam.

Electron-impact dissociation of HeH+: absolute cross sections for the production of Heq+ (q = 1–2) fragments

Absolute cross sections have been measured for electron-impact dissociative excitation and ionization of the helium-hydride ion (HeH+) leading to the formation of helium ions Heq+ (q = 1–2). Measurements have been performed for electron energies ranging from the respective thresholds up to 2.5 keV. For He+ production, the maximum absolute cross section for dissociative excitation is found to be (2.5 ± 0.2) ×10−17 cm2 (around 40 eV), while for dissociative ionization, it is found to be (2.1 ± 0.1) ×10−17 cm2 (around 135 eV). For He2+ production, only the inclusive absolute cross section is presented, without attempting to isolate any distinct contribution, and it is measured to be (2.6 ± 0.2) ×10−19 cm2 (around the maximum, 195 eV). Appearance energies for He+ and He2+ are determined to be (11.2 ± 0.5) eV and (66.5 ± 1.0) eV, respectively. Kinetic energy release and angular distributions are obtained, at specific incident electron energies.

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 C2+, CH32+, and CH42+ ions, as well as singly charged D2+, CD3+, and CD4+ ions, are detected in the mass spectrum of a methane molecule at electron energy Ue = 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.

A Combined Experimental and Theoretical Study on the Gas‐Phase Synthesis of Toluene under Single Collision Conditions

physical-organic chemistry communities. Toluene portrays the simplest representative of an alkyl-substituted benzene molecule with the methyl group enhancing the reactivity toward radical and electrophile aromatic substitution compared to benzene. It is further considered as a crucial building block to form methyl-substituted polycyclic aromatic hydrocarbons (PAHs) such as 1and 2-methylnaphthalene. In combustion flames, the formation of phenylacetylene 2, styrene 3, and biphenyl 4 (Scheme 1) can be rationalized through phenyl addition. Atomic hydrogen is eliminated upon reaction of the phenyl radical with acetylene (C2H2), [14] ethylene (C2H4), [15] and benzene (C6H6). [16] The analogous reaction of the phenyl radical with methane (CH4) does not lead to toluene, but solely to benzene plus a methyl radical (CH3) through hydrogen abstraction. [17] Consequently, the formation routes of toluene in combustion flames and in the interstellar medium have not been unraveled to date. Here, we show that the reaction of the ethynyl radical (CCH; C2H) with isoprene (2-methyl-1,3-butadiene; C5H8) presents a facile, barrierless route to the toluene molecule in a single collision event in the gas phase through the reaction of two acyclic precursor molecules. This reaction is also of interest to the physical-organic chemistry community since it represents a benchmark system to untangle the formation of a methylsubstituted aromatic molecule through radical substitution reactions involving successive isomerizations through cyclization and hydrogen shifts. Reactive scattering signal from the reaction of [D1]ethynyl radical C2D(X S) with isoprene (C5H8; X A’) was monitored at mass-to-charge ratios (m/z) of 93 (C7H7D ), 92 (C7H6D /C7H8 ), and 91 (C7H5D /C7H7 ). The signal atm/ z= 93 originates from the C7H7D product(s) formed through atomic hydrogen loss, whereas ion counts at m/z= 92 could have two contributions: an atomic deuterium loss connected to the formation of C7H8 products or dissociative ionization of C7H7D products in the electron impact ionizer of the detector. The signal at m/z= 91 may depict two contributions from dissociative electron impact ionization of C7H7D and/or C7H6D product molecules. However, all data could be fit with the product mass combinations of 93 amu (C7H7D) plus 1 amu (H). This finding suggests the existence of a [D1]ethynyl (C2D, 26 amu) versus atomic hydrogen replacement channel and the gas-phase synthesis of a molecule with the molecular formula C7H7D (Figure 1). Considering that the [D1]ethynyl reactant does not have a hydrogen atom, the hydrogen atom is emitted from the isoprene molecule. The laboratory angular distribution (Figure 2) extends at least 408 within the scattering plane and peaks close to the center-of-mass angle at 41.1 1.28. These results suggest indirect scattering dynamics through C7H8D complex(es). Scheme 1. Toluene 1, phenylacetylene 2, styrene 3, and biphenyl 4.

Energy distributions of neutrals and charged species in hollow cathode H2 discharges: a study of fast H atoms

A joint study of atomic and molecular emission spectroscopy, ion mass spectrometry and Langmuir probes is presented for a hollow cathode H2 discharge at pressures 0.7–20 Pa, rendering energy distributions of the different groups of particles that span five orders of magnitude. The H Balmer line profiles can be decomposed into three contributions (‘narrow peak’, ‘plateau’ and ‘far wings’) with very different widths. The narrow peak and the plateau are largely attributed to electron impact dissociative excitation and ionization of H2, and display Doppler temperatures of ∼0.3 eV and ∼6 eV, respectively. The energy-resolved mass spectra of H+ confirm the assignment of the plateau region. The far wings give rise to emissions extending to Doppler shifts of 0.5 nm, which correspond to translational energies of ∼300 eV. The dependence of the relative intensities of these components on pressure is studied. With a grounded grid before the observation window, a structure is induced in the blue-shifted wing. Assuming that the structure is solely caused by dissociative excitation of H2 upon collisions with the plasma ions (H+, and ), their relative concentrations can be estimated. These estimations are in very good agreement with the values derived from independent mass spectrometric measurements.

Specific features of the dissociative ionization of methane molecules

Experimental techniques and results of a mass-spectrometric investigation of the yield of positive ions formed as a result of the dissociative electron-impact ionization of methane molecules. It is established that the ionization energy of CH4 molecule is 12.62 ± 0.25 eV. Possible electron-molecular reactions involved in the interaction of an electron beam with methane molecules are analyzed.

ELECTRON IMPACT DISSOCIATIVE IONIZATION OF NITROSYL CHLORIDE

Electron impact dissociative ionization of nitrosyl chloride ( ClNO ) has been studied at the electron beam energy of 200 eV. The dissociation channels of up to triply ionized ClNO are investigated by two- and three-dimensional covariance mapping methods. The absolute cross-sections for the different dissociation channels are measured. No stable ClNO + or ClNO 2+ ions are observed in the mass spectrum. The most possible pathway for the dissociation of ClNO + is ClNO + → NO + + Cl . The total double ionization cross-section of ClNO is found to be 6.3% compared to the total single ionization cross-section. The main ion-pair dissociation channels for ClNO 2+ are ClNO 2+ → N + + O ++ Cl and ClNO 2+ → NO + + Cl +. The ClNO trications dissociate into either an ion pair or an ion triple, with comparable probabilities.