Ionization Efficiency Curves Research Articles

Mixed Cluster Ions of Magnesium and C60.

Magnesium clusters exhibit a pronounced nonmetal-to-metal transition, and the neutral dimer is exceptionally weakly bound. In the present study, we formed pristine Mgnz+ (n = 1-100, z = 1-3) clusters and mixed (C60)mMgnz+ clusters (m = 1-7, z = 1, 2) upon electron irradiation of neutral helium nanodroplets doped with magnesium or a combination of C60 and magnesium. The mass spectra obtained for pristine magnesium cluster ions exhibit anomalies, consistent with previous reports in the literature. The anomalies observed for C60Mgn+ strongly suggest that Mg atoms tend to wet the surface of the single fullerene positioning itself above the center of a pentagonal or hexagonal face, while, for (C60)mMgnz+, the preference for Mg to position itself within the dimples formed by fullerene cages becomes apparent. Besides doubly charged cluster ions, with the smallest member Mg22+, we also observed the formation of triply charged ions Mgn3+ with n > 24. The ion efficiency curves of singly and multiply charged ions exhibit pronounced differences compared to singly charged ions at higher electron energies. These findings indicate that sequential Penning ionization is essential in the formation of doubly and triply charged ions inside doped helium nanodroplets.

Thermodynamic properties of indoline and benzoxazine based spiropyrans studied by Knudsen effusion mass spectrometry

An approach including thermal analysis and Knudsen effusion mass spectrometry was used to investigate the thermal stability range and the thermodynamic properties of sublimation for four indoline and benzoxazine based spiropyrans: 1,3,3-trimethyl-6′- (tert-butyl) −8′-formyl-spiro [indoline-2,2′-2H-chromene] (1), 1,3,3,8′-tetramethyl-6′-formyl-spiro [indoline-2,2′-2H-chromene] (4), 1,3,3-trimethyl-8′-methoxy-6′-formyl-spiro [indoline-2,2′-2H-chromene] (7), and 3-methyl-6′-methoxy-8′-formyl-spiro [1,3-benzoxazin-4-one-2,2′-2H-chromene] (9). The melting and decomposition temperatures as well as the melting enthalpies were obtained by thermal analysis. The electron ionization mass spectra as well as the ionization efficiency curves were measured. Schemes of the formation of the main ions in the mass spectra were suggested. The temperature dependencies of vapor pressures were used to obtain the sublimation enthalpies. All data were obtained for the first time.

Ionization of aluminum clusters

Near-threshold photoionization cross sections for several aluminum clusters have been estimated from the ionization efficiency curves. Their magnitude raises the possibility that the edge of a collective electron resonance (surface plasmon) may contribute to the photoemission channel. On the other hand, electron impact ionization efficiently produces multiply charged metal cluster ions and is unaccompanied by noticeable fragmentation. Consequently it does not appear to involve collective excitations.

Pathway exploration in low-temperature oxidation of a new-generation bio-hybrid fuel 1,3-dioxane

The joint and flexible utilization of renewable electricity, ligno-cellulosic biomass, and/or CO2 point sources to produce so-called bio-hybrid fuels is a promising solution to achieve carbon neutrality while still meeting the energy demand of the transportation sector. One of the new-generation bio-hybrid fuels is 1,3-dioxane. It has a special chemical structure with two oxygen atoms in a six-membered ring. In this work, the low-temperature oxidation of 1,3-dioxane was studied theoretically and experimentally. Potential energy surfaces of the products of the O2 recombination with the three radicals formed from the H-atom abstraction of 1,3-dioxane were calculated at the DLPNO-CCSD(T)/CBS//B2PLYP-D3/cc-pVTZ level. The reaction rate coefficients were calculated with the RRKM/master equation method (T = 500–2000 K, p = 0.01–100 atm). To validate the proposed pathways, low-temperature oxidation experiments of 1,3-dioxane were performed in a jet stirred reactor (JSR) coupled with a synchrotron photon ionization time of flight molecular beam mass spectrometer (T = 590 K, p = 1 bar). Key intermediates in the investigated pathways were captured and identified by the combination of measured photon ionization efficiency curves and calculated ionization energies. Compared to cyclohexane, which has no oxygen in the six-membered ring, 1,3-dioxane has much weaker C-H bonds for the carbon between the two oxygen atoms, thus enabling faster internal H-atom migration from ROO to QOOH. Furthermore, oxidation of 1,3-dioxane tends to favor cyclic ethers + OH (chain propagation) instead of alkenes + HO2 (chain termination), explaining its high reactivity in the low-temperature regime.

Stabilization of benzene radical anion in ammonia clusters.

We investigate electron attachment to large ammonia clusters doped with a single benzene (Bz) molecule (NH3)N·Bz, N̄ ≈ 320. Negatively charged clusters are probed by mass spectrometry, and the energy-dependent ion yields are derived from mass spectra measured at different electron energies. The ion efficiency curves of pure ammonia clusters exhibit two maxima. At around 6 eV, (NH3)n-1NH2- ions are produced via dissociative electron attachment (DEA) to NH3 molecules. (NH3)n- ions produced at this energy are formed by DEA followed by fragment caging. At low energies around 1.3 eV, only (NH3)n- ions are formed for cluster sizes n ≥ 35 that correspond to solvated electrons in ammonia clusters. The doped (NH3)n·Bz- cluster ions exhibit essentially the same energy dependence. The (NH3)n·Bz- ions are metastable and evaporate NH3 molecule(s), while pure (NH3)n- ions are stable. The lifetime for NH3 molecule evaporation from the Bz-doped clusters was estimated as τ ≈ 18 μs. We interpret the metastability of the doped clusters by the charge localization on a Bz- ion solvated in the ammonia, which is accompanied by an energy release leading to the evaporation of NH3 molecule(s).

Electron Ionization of Size-Selected Positively and Negatively Charged Helium Droplets

A beam of size-selected charged helium droplets was crossed with an electron beam, and the ion efficiency curves for the product droplets in all different charge states were recorded. We estimate that the selected helium droplets on their passage through the electron beam are hit by several hundred electrons which can interact with the individual He atoms of the droplets. Reaction channels corresponding to the removal or capture of up to eight electrons were identified, and in all cases, inelastic scattering and the formation of metastable helium played a significant role.

Electron Driven Reactions in Tetrafluoroethane: Positive and Negative Ion Formation

In the search for alternatives to chlorine-containing gases, tetrafluoroethane, CF3CH2F (R134a), a widely used refrigerant gas, has been recognized as a promising substitute for dichlorodifluoromethane, CCl2F2 (R12). When R12 is replaced by R134a, the global warming potential drops from 8100 to 1430, the ozone depletion potential changes from 1 to 0, and the atmospheric lifetime decreases from 100 to 14 years. Electron interactions in the gas phase play a fundamental role in the atmospheric sciences. Here, we present a detailed study on electron-driven fragmentation pathways of CF3CH2F, in which we have investigated processes induced by both electron ionization and electron attachment. The measurements allow us to report the ion efficiency curves for ion formation in the energy range of 0 up to 25 eV. For positive ion formation, R134a dissociates into a wide assortment of ions, in which CF3+ is observed as the most abundant out of seven ions with a relative intensity above 2%. The results are supported by quantum chemical calculations based on bound state techniques, electron-impact ionization models, and electron-molecule scattering simulations, showing a good agreement. Moreover, the experimental first ionization potential was found at 13.10 ± 0.17 eV and the second at around 14.25 eV. For negative ion formation, C2F3- was detected as the only anion formed, above 8.3 eV. This study demonstrates the role of electrons in the dissociation of R134a, which is relevant for an improvement of the refrigeration processes as well as in atmospheric chemistry and plasma sciences.

Electron ionization and photoionization of cyclopropylamine

We present an experimental and theoretical study of electron ionization (EI) of Cyclopropylamine (CPA) molecule, using crossed electron – molecular beam technique with mass spectrometric detection of the ions. We have obtained energy resolved mass spectra, and electron energy dependent ion efficiency curves for ions of particular mass charge ratios (m/z). Except the ionization energy of the CPA molecule (8.46 ± 0.20 eV) we have evaluated the appearance energies of most of the ions in the mass spectrum formed via dissociative ionization (DI) processes. In addition we have carried out He∗ photoelectron spectrometry (PES) and determined the vertical ionization energy (VIE) of 9.47 ± 0.1 eV and detected the excited states of CPA. PES study was supported by outer valence green function (OVGF) calculation of the vertical ionization energy (9.55 eV). We have carried out quantum-chemical calculations of the neutral molecule, of the molecular ions, the neutral and ionic fragments and the reaction enthalpies for the DI processes were calculated. The theoretical DI values were applied for identification of the DI reactions and fragment ions in experiment.

Thermochemical activation of hydrogen in the process of desorption from metal hydride

The results of mass spectrometric studies of the energy state of hydrogen molecules with the usage of the electron impact ionization efficiency curves measurement method, both during desorption and in the mode of hydrogen flowing through the metal hydride layer, are presented. The dependences of the breakdown voltage on the pressure in the gas-discharge chamber for an electric discharge in activated hydrogen are obtained. Those dependencies indicate a significant decrease in the ionization potential of hydrogen under the electric current influence. Within the framework of the presented material, the results of hydrogen emission from hydride-forming materials based on LaNi5 are presented and an assessment of its thermodynamic state is given, which made it possible to study the energy-physical characteristics of gas-discharge processes. The possibility of practical use of metal hydride activation to increase the energy and operational efficiency of electric-discharge hydrogen systems is shown.

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 Sen+ 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.

Electron-Induced Fragmentation of Methylated Formamides

At an electron ionization of 70eV, all cationic fragments for N,N-dimethylformamide (DMF) and N-methylformamide (NMF) were detected with a quadrupole mass spectrometer and confirmed using isotopically-labelled molecules. Ion efficiency curves near the threshold region (5–20eV) for all of the major cationic fragments were measured and fit with a Wannier-type function to determine their appearance energies (AEs). Possible reaction pathways for the formation of each observed cation were proposed, and the corresponding enthalpies (ΔH⁰s) of reaction were evaluated from quantum chemical calculations using the Gaussian09 computational quantum chemistry package. Our results suggest that hydrogen loss for both molecules occurs primarily from the carbonyl carbon. We confirm that hydrogen transfer from the carbonyl site to the nitrogen site occurs during amide bond cleavage. The resultant cations, C2H6N+ and CH4N+, and their further fragments, formed by losing an H atom, H2, or C2H2, were first identified in mass spectra and were further probed by comparing the AEs with calculated ΔH⁰s of all possible formation pathways. Additionally, we suggest that hydrogen transfer also occurs when the N-CH3 bond breaks in DMF. This detailed study of the simplest molecule with the peptide linkage contributes to our understanding of electron impact on peptide-like molecules.

Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization.

Electron ionization of neat tungsten hexacarbonyl (W(CO)6) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)6 clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)n (+) (0 ≤ n ≤ 6) and W2(CO)n (+) (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)n (+) (0 ≤ n ≤ 3) and W2C(CO)n (+) (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.

Insights in m-xylene decomposition under fuel-rich conditions by imaging photoelectron photoion coincidence spectroscopy

A fuel-rich (Φ=1.79) m-xylene flame (7.3% m-C8H10, 42.7% O2, 50.0% Ar) at low-pressure (40mbar) was investigated with focus on the reactive fuel radicals (C8H9) and the first decomposition steps leading to C8H8 isomers. The results show that an isomerization of the m-xylyl radical to o- and p-xylyl must take place to explain the observed intermediates in agreement with pyrolysis experiments. Important higher polycyclic aromatic hydrocarbons (PAHs) relevant to soot formation were also identified. All Measurements were performed with a molecular-beam mass spectrometry (MBMS) setup at the Swiss Light Source (SLS), where single-photon ionization with VUV radiation offers soft ionization of the sampled species. Isomer-selective detection with unprecedented resolution is achieved by a combination of time-of-flight mass spectrometry and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. In principle, species can be identified by comparison of measured ionization efficiency (PIE) curves with known or calculated ionization energies of expected species. For convoluted signals of several species, this procedure works well for the isomer with the lowest ionization energy. Changes in the slopes of the ionization efficiency curve do not necessarily correlate with ionization thresholds of other isomers and the assignment of higher thresholds can become difficult. PEPICO spectrometry, which detects the electrons that are produced in the ionization process in coincidence with the ions, enables the measurement of mass-selected threshold photoelectron spectra (ms-TPES). These spectra improve the detection capability of isomers because vibrational transitions from the neutral into ionic states can be observed and used as a fingerprint of a specific molecule. The obtained ms-TPES are compared with reference spectra from the literature or Franck–Condon simulations. Quantification of the major species as well as several intermediate species for this fuel-rich m-xylene flame yields a data set for model validation and experimental results are compared with five kinetic reaction models from the literature.

An electron-impact ionization study of molecular selenium beams

We describe the method and presents results of a mass-spectrometric investigation of the yield of positive ions formed as a result of the dissociative ionization of a molecular selenium beam by electron impact. Appearance energies of fragment ions have been determined from the ionization efficiency curves. The dynamics of formation of the molecular ions of selenium in a temperature interval of 420–495 K has been studied. The energy dependences of the efficiency of formation of singly charged Sen+ (n = 1–3) and doubly charged Se++ ions are analyzed.

Ion formation upon electron collisions with valine embedded in helium nanodroplets

We report here experimental results for the electron ionization of large superfluid helium nanodroplets with sizes of about 105 atoms that are doped with valine and clusters of valine. Spectra of both cations and anions were monitored with high-resolution time-of-flight mass spectrometry (mass resolution >4000). Clear series of peaks with valine cluster sizes up to at least 40 and spaced by the mass of a valine molecule are visible in both the cation and anion spectra. Ion efficiency curves are presented for selected cations and anions at electron energies up to about 40 eV and these provide insight into the mode of ion formation. The measured onset of 24.59 eV for cations is indicative of valine ionization by He+ whereas broad resonances at 2, 10 and 22 eV (and beyond) in the formation of anions speak to the occurrence of various modes of dissociative electron attachment by collisions with electrons or He*− and the influence of droplet size on the relative importance of these processes. Comparisons are also made with gas phase results and these provide insight into a matrix effect within the superfluid helium nanodroplet.

Vapor phase composition as an indicator of thermal stability of the Sm, Eu, and Yb chlorides

The Sm, Eu, and Yb tri- and dichlorides were investigated by Knudsen effusion mass spectrometry. It was found out by the analysis of mass spectra and ionization efficiency curves that the vapor composition is complex due to the partial high temperature decomposition/disproportionation of the samples. Up to five vapor species were identified for both LnCl3 (LnCl3, LnCl2, Ln2Cl4, Ln2Cl5, and Ln2Cl6) and LnCl2 (LnCl3, LnCl2, LnCl, Ln, and Ln2Cl4). The quantitative evaluation of vapor composition was made. It indicates that the disproportionation of SmCl2 and EuCl2 is negligible in the temperature range studied whereas that of YbCl2 and the decomposition of SmCl3 and YbCl3 cannot be neglected.

Dissociative electron attachment to the gas-phase nucleobase hypoxanthine.

We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C5H4N4O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp - H) anion (C5H3N4O(-)) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp - NH)(-), C4H3N4 (-)/C4HN3O(-), C4H2N3 (-), C3NO(-)/HC(HCN)CN(-), OCN(-), CN(-), and O(-). Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

Electron ionization of the nucleobases adenine and hypoxanthine near the threshold: a combined experimental and theoretical study.

Electron ionization of the DNA nucleobase, adenine, and the tRNA nucleobase, hypoxanthine, was investigated near the threshold region (∼5-20 eV) using a high-resolution hemispherical electron monochromator and a quadrupole mass spectrometer. Ion efficiency curves of the threshold regions and the corresponding appearance energies (AEs) are presented for the parent cations and the five most abundant fragment cations of each molecule. The experimental ionization energies (IEs) of adenine and hypoxanthine were determined to be 8.70 ± 0.3 eV and 8.88 ± 0.5 eV, respectively. Quantum chemical calculations (B3LYP/6-311+G(2d,p)) yielded a vertical IE of 8.08 eV and an adiabatic IE of 8.07 eV for adenine and a vertical IE of 8.51 eV and an adiabatic IE of 8.36 eV for hypoxanthine, and the lowest energy optimized structures of the fragment cations and their respective neutral species were calculated. The enthalpies of the possible reactions from the adenine and hypoxanthine cations were also obtained computationally, which assisted in determining the most likely electron ionization pathways leading to the major fragment cations. Our results suggest that the imidazole ring is more stable than the pyrimidine ring in several of the fragmentation reactions from both adenine and hypoxanthine. This electron ionization study contributes to the understanding of the biological effects of electrons on nucleobases and to the database of the electronic properties of biomolecules, which is necessary for modeling the damage of DNA in living cells that is induced by ionizing radiation.

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.

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.