Scattering of low energy He2+ ions by Ne,Ar, and Kr atoms

Experimental studies of collisions of He²⁺ ions with Ne, Ar, and Kr atoms have been carried out at laboratory kinetic energies in the range 8 ? E₁ ? 10 eV. For each collision pair, relative differential cross sections for elastic scattering, and for the formation of He⁺ by single charge transfer [e.g., He²⁺ + R = He⁺ + (R⁺)^*] were measured. Information concerning the initial states of the charge transfer products was also obtained, from measurements of the kinetic energy distributions of the He⁺ + He = Ne⁺(2s 2p⁶²S) ± He⁺(²S), whereas for the other systems, transfer proceeds via a number of channels. The He⁺-ion kinetic energy measurements indicated that for He²⁺. Ar both Ar⁺ both Ar⁺ and Ar²⁺ are formed in transfer, and that for He²⁺, Kr only Kr²⁺ (and no Kr⁺) was formed.The differential elastic scattering patterns were analyzed by means of cross section calculations based on an approximate form of the optical model. These calculations indicated that the pronounced shoulders observed in the σ_el(θ) versus θ curves arose from scattering from an attractive potential well, in the presence of concurrent inelastic scattering. Using parametrized Morse potentials to represent the ground electronic states of (HeNe)²⁺, (HeAr)²⁺, and (HeKr)²⁺, the corresponding well-depth are estimated to be, respectively: 1.0 eV, 2.1 eV and 2.6 eV.     

Two-photon ionization of Li2: isotopic separation and determination of IP(Li2) and De(Li+2)

Complete isotope separation is achieved by two-photon ionization of Li₂ by a single mode Ar⁺ laser. With the use of two Ar⁺ lasers, the ionization potential of Li₂ is found to be 5.174 ± 0.013 eV, and the dissociation energy D_e(Li⁺₂) to be 1.274 ± 0.019 eV.     

Dissociation cross sections of silane and disilane by electron impact

The total dissociation cross sections for silane and disilane are reported for electron energies above their ionization thresholds up to 110 eV. The measurements are derived from a kinetic analysis of silane and disilane dissociation in a constant-flow multipole dc plasma reactor. The methane dissociation cross section was also measured and found in agreement with published data. Maxima for silane and disilane, occurring around 60 eV, are respectively (1.2±3)×10^?15 cm² and (2.6±0.6)× 10^?15 cm². Total ionization cross sections are also measured and above 50 eV the ratios of dissociative ionization to dissociation cross sections are 0.5±0.1 and 0.25±0.10 respectively for silane and disilane. The probability for silane elimination in the disilane fragmentation reaches a maximum of 0.8 at 19 eV and decreases down to 0.5 at 100 eV. Dissociation processes of silane and disilane are discussed in comparison with methane and ethane     

Photoionization of the Ar2 dimer

The relative photoionization cross section for Ar₂ was measured in the wavelength region 820–860 Å. The spectrum shows detailed autoionization structure throughout this region with no contribution from direct ionization. The appearance potential of Ar⁺₂ corresponds to 856.5 ± 1.5 Å.     

Total ionization and electron attachment cross sections of CCl2F2 by electron impact

The absolute total ionization cross sections from threshold to 250 eV and dissociative attachment cross sections from zero to 10 eV have been measured for the CCl₂F₂ (dichloro-difluoro-methane) molecule by using a parallel plate condenser type ionization chamber. The maximum of the ionization cross-section curve was found to be at an energy of about 90 eV with a cross section of 1.44 × 10^?19 m². The attachment cross-section curve shows three peaks, the most intense being at zero electron energy with a cross-section value of 1.80 × 10^?20 m², and the other two at energies of 0.6 eV and 3.5 eV, respectively. The maximal relative error in cross-section values is 0.08, for electron energies larger than 0.4 eV.     

Electron impact and single photon ionization cross sections of neutral silver clusters

Neutral silver atoms and small clusters Ag _n (n=1...4) were generated by sputtering, i.e. by bombarding a polycrystalline silver surface with Ar⁺ ions of 5 keV. The sputtered particles were ionized by a crossed electron beam and subsequently detected by a quadrupole mass spectrometer. In alternative to the electron impact ionization, the same neutral species were also ionized by single photon absorption from a pulsed VUV laser (photon energy 7.9 eV), and the photoionization cross sections were evaluated from the laser intensity dependence of the measured signals. By in situ combining both ionization mechanisms, absolute values of the ratio σ _e (Ag _n )/σ _e (Ag) between the electron impact ionization cross sections of silver clusters and atoms could be determined for a fixed electron energy of 46 eV. These values can then be used to calibrate previously measured relative ionization functions. By calibrating the results using literature data measured for silver atoms, we present absolute cross sections for electron impact ionization of neutral Ag₂, Ag₃ and Ag₄ as a function of the electron energy between threshold and 125 eV.     

Electron-impact excitation of the 3s'3P° and 2s2p53P° autoionizing states of atomic oxygen

The excitation of the 3s''³P° and 2s2p⁵³P° autoionizing states of OI by electron impact on atomic oxygen has been studied. Absolute cross section values from threshold to 300 eV have been obtained for the 3s''³P° state. Limited emission cross section data for the 2s2p⁵³P° and other partially radiating autoionizing states were also obtained at an impact energy of 100 eV. These results suggest that the excitation of the OI autoionizing states account for ≈33% of the total O⁺ total ionization cross section at 40 eV under optically thin conditions and that the cross section ratio, σ(⁴S)/σ(²D + ²P), has been underestimated substantially in earlier theoretical work. Electron-impact excitation of the 3s''³P° and 2s2p⁵³P° states in an optically thick medium enhances the effective total ionization cross section for atomic oxygen by ≈15% and increases the specific O⁺(⁴S) production rate by ≈25% with important implications for O⁺ ion chemistry in gaseous discharges and planetary ionospheres.     

Absolute partial and total electron impact ionization cross sections for C3H8 from threshold up to 950 eV

Electron impact ionization of propane (C₃H₈) was studied using the ion beam deflection technique and a double focussing mass spectrometer in conjunction with a recently developed correction procedure that accounts for discrimination due to the initial kinetic energy of fragment ions. The relative corrected partial ionization cross sections for the production of C₃H ₈ ⁺ , C₃H ₇ ⁺ , C₃H ₆ ⁺ , C₃H ₅ ⁺ , C₃H ₄ ⁺ , C₃H ₃ ⁺ , C₃H ₂ ⁺ , C₃H⁺, C ₃ ⁺ ; C₂H ₅ ⁺ , C₂H ₄ ⁺ , C₂H ₃ ⁺ , C₂H ₂ ⁺ , C₂H⁺, C ₂ ⁺ ; CH ₃ ⁺ , CH ₂ ⁺ , CH⁺, C⁺; C₃H ₅ ²⁺ , C₃H ₄ ²⁺ , C₃H ₃ ²⁺ and C₃H ₂ ²⁺ were determined from threshold up to 950 eV. Absolute partial ionization cross sections were obtained by charge weighted summing of all the observed partial ionization cross sections and by normalizing to a recent accurate determination of the total ionization cross section at 100 eV by Djuric et al. 1991. The absolute total ionization cross section curve obtained is in excellent agreement in shape and magnitude with the low energy data (<200 ev)=" of=" djuric=" et=" al.=" 1991=" and=" the=" high=" energy=" data=" points=" of=" schram=" et=" al.=">     

Electron impact ionization of small silver and copper clusters

Using a quadrupole mass spectrometer, relative cross sections for electron impact ionization of neutral Ag _n and Cu _n clusters withn=1 ... 4 have been measured for electron energies between threshold and 125 eV. From the results, the following ionization energies were obtained: Ag₂: 7.26±0.1 eV, Ag₃: 6.19±0.2 eV, Ag₄: 6.33±0.3 eV, Cu₂: 7.46±0.15 eV, Cu₃: 6.14±1.0 eV, Cu₄: 7.00±0.6 eV. With only two exceptions, these values agree with other data published for Ag₂, Cu₂, Cu₃ and Cu₄.     

Energy and substituent effects on gaseous ionic decompositions: Electron and charge exchange ionization of benzophenones and benzils

The correlation with substituent constants reported previously for [YØCO]⁺/[ØCO]⁺ ratios in the electron ionization mass spectra of substituted benzophenones and acetophenones has also been observed in the electron ionization spectra of substituted benzils. The [YØCO]⁺/[ØCO]⁺ ratio for the substituted benzils varied with energy of the ionizing electrons according to predictions from a simple kinetic and thermochemical analysis. [YØCO]⁺/[ØCO]⁺ ratios in the charge exchange spectra of benzophenones obtained with Xe, Kr, CO, N₂ and Ar gave good correlations with sub-stituent constants in agreement with the same analysis. Good correlations were also noted for [YØCO]⁺/[ØCO]⁺ ratios with substituent constants for [M]⁺ ions of the benzophenones of the same excess energy (5.5 eV). [YØCO]⁺/[ØCO]⁺ ratios for benzils obtained by charge exchange with [CO]⁺ also showed good correlations with substituent constant. It is suggested that [Ø]⁺ and [YØ]⁺ ions from the benzophenones may be formed primarily by one step decompositions of the molecular ions, but that the [Ø]⁺ and [YØ]⁺ ions from the benzils are formed primarily by decomposition of [ØCO]⁺ and [YØCO]⁺ ions.     

Symmetric resonance charge transfer of Ar2+ IN Ar

Merging beams are used to measure cross sections for the reaction Ar²⁺ + Ar → Ar + Ar²⁺ at relative energies from 2 to 1000 eV. The results are in fair agreement with the theory of Fetisov and Firsov.     

Study of small chlorine‐doped potassium clusters by thermal ionization mass spectrometry

The theoretical calculations have predicted that nonmetal‐doped potassium clusters can be used in the synthesis of a new class of charge‐transfer salts which can be considered as potential building blocks for the assembly of novel nanostructured material. In this work, K_nCl (n = 2–6) and K_nCl_n?1 (n = 3 and 4) clusters were produced by vaporization of a solid potassium chloride salt in a thermal ionization mass spectrometry. The ionization energies (IEs) were measured, and found to be 3.64 ± 0.20 eV for K₂Cl, 3.67 ± 0.20 eV for K₃Cl, 3.62 ± 0.20 eV for K₄Cl, 3.57 ± 0.20 eV for K₅Cl, 3.69 ± 0.20 eV for K₆Cl, 3.71 ± 0.20 eV for K₃Cl₂ and 3.72 ± 0.20 eV for K₄Cl₃. The K_nCl⁺ (n = 3–6) clusters were detected for the first time in a cluster beam generated by the thermal ionization source of modified design. Also, this work is the first to report experimentally obtained values of IEs for K_nCl⁺ (n = 3–6) and K_nCl_n?1⁺ (n = 3 and 4) clusters. The ionization energies for K_nCl⁺ and K_nCl_n?1⁺ clusters are much lower than the 4.34 eV of the potassium atom; hence, these clusters should be classified as ‘superalkali’ species. Copyright © 2012 John Wiley & Sons, Ltd.     

Absolute cross sections for electron impact ionization of Ag2

The previously measured relative cross section function for electron impact ionization (EII) of neutral Ag₂ has now been calibrated quantitatively by combining the electron impact ionization with in situ non resonant two photon ionization (NR2PI). By comparing the NR2PI saturation intensities measured for Ag ₂ ⁺ and Ag⁺ with the corresponding EII intensities, the ratio between the electron impact ionization cross sections (EIICS) of neutral Ag₂ and Ag was determined to be σ_Ag2/σ_Ag=1.53 for an electron energy of 46 eV. This result agrees well with the geometricn ^2/3-rule \((\sigma X_n \sim n^{2/3} )\) commonly proposed for the dependence of the EIICS of clustersX _n on the cluster sizen.     

Fission neutron spectrum averaged cross sections for threshold reactions on arsenic

Summary We have measured the cross sections, averaged over a ²³⁵U fission neutron spectrum, for the two high threshold reactions: ⁷⁵As(n,p)^75mGe and ⁷⁵As(n,2n)⁷⁴As. The measured averaged cross sections are 0.292±0.022 mb, referred to the 3.95±0.20 mb standard for the ²⁷Al(n,p)²⁷Mg averaged cross section, and 0.371±0.032 mb referred to the 111±3 mb standard for the ⁵⁸Ni(n,p)^58m+gCo averaged cross section, respectively. The measured averaged cross sections were also evaluated semi-empirically by numerically integrating experimental differential cross section data extracted for both reactions from the current literature. The calculations were performed for four different representations of the thermal-neutron-induced ²³⁵U fission neutron spectrum. The calculated cross sections, though depending on analytical representation of the flux, agree with the measured values within the estimated uncertainties.     

Electron ionization of acetylene

Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H+2, C2+, C+/C2+ 2, CH+/C2H+2, CH+2, C+2, and C2H+ relative to the formation of C2H+2, as a function of ionizing electron energy from 30-200 eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50 eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100 eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H2+2 dissociates predominantly on the ground triplet potential energy surface (3Sigma*g) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (1Delta g). Measurements of the kinetic energy released in the fragmentation reactions of C2H2+2 have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.     

Determination of elemental compositions by gas chromatography/time‐of‐flight mass spectrometry using chemical and electron ionization

Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under standard 70 eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam‐steering voltage of the ion source, the relative abundances of molecular ions at 70 eV EI were increased up to ten‐fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2‐fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high‐mass tuning. Thirty‐three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([M+H]⁺, [M–CH₃]⁺ for CI and [M]^{+ .} , [M–CH₃]^{+ .} for EI). On average, CI yielded 8‐fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8 ± 1.6 mm/z units and isotope ratio errors of 2.3 ± 2.0% (A+1/A ratio) and 1.7 ± 1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top‐3 hits in 80% of the cases. Copyright © 2010 John Wiley & Sons, Ltd.     

Absolute partial and total electron ionization cross sections for CCl4 from threshold up to 180 eV

Electron impact ionization of carbon tetrachloride was studied as a function of electron energy from threshold up to 180 eV. A double-focusing mass spectrometer system in combination with an improved electron impact ion source was used, alleviating the problems of ion extraction from the source and the transmission of the extracted ions through the mass spectrometer system. Absolute partial ionization cross sections for the occurrence of CCl ₃ ⁺ , CCl ₂ ⁺ , CCl⁺, Cl ₂ ⁺ , Cl⁺, C⁺, CCl ₃ ²⁺ , and CCl ₂ ²⁺ have been determined. In addition, the total ionization cross-section function of CCl₄ is reported and compared with theoretical predictions based on a classical binary encounter approximation. Using nth root extrapolation the following ionization energies of the doubly ionized fragment ions have been derived: AE(CCl ₃ ²⁺ )=30.4±0.3 eV; and AE (CCl ₂ ²⁺ )=31.8±0.3 eV. In accordance with theoretical predictions and previous results, no stable CCl ₄ ⁺ has been detected, however, metastable dissociation processes CCl ₄ ⁺ CCl ₃ ⁺ have been observed.     

Indirect processes in the electron-impact ionization of Li-like ions

Detailed measurements of electron-impact ionization cross sections have been made in the vicinity of the excitation-autoionization thresholds of Li-like B²⁺, C³⁺, N⁴⁺, O⁵⁺ and F⁶⁺ ions. With an energy spread of 0.4 to 1% of the electron energy and statistical uncertainties as low as 0.1% we could clearly resolve thresholds for excitation of individual terms in 1s2s2l configurations. Numerous resonance features were found which are due to dielectronic capture of the incident electron with subsequent two-electron emission. In particular, dielectronic capture processes involving Δn=2 excitations of a 1s electron provide the dominant resonance contributions to the measured cross sections. Rydberg series 1s2snln′l′ of resonances withn=3 (Δn=2) andn=4 (Δn=3) are resolved up to principle quantum numbersn′ equal to 6 or 7.     

Dissociation energy and ionization potential of the molecule CF

The gaseous equilibrium S + CF₂ = SF + CF was studied over the temperature range 1851 to 2232 K by mass spectrometry, and the derived enthalpy change was used to evaluate the heat of formation of CF ΔH₂₉₈ = 58.0 ± 2.4 kcal/mol (2.52 ± 0.10 eV), and the dissociation energy D₀⁰ (CF) = 130.8 ± 2.4 kcal/mol (5.67 ± 0.10 eV). The new thermochemical data indicate a slightly higher stability for CF than earlier determinations. Direct measurement by electron impact yielded a value of 9.17 ± 0.10 eV for the vertical ionization potential of CF, in agreement with an indirect result obtained from the photodissociative ionization of C₂F₄.     

Total one-electron capture cross sections for Ar q+ and I q+ ions in slow collisions on H2 and He

Argon and iodine recoil ions were produced by a 2 GeV U⁷⁵⁺ beam and total one electron capture cross sections are measured for 198 eV/q Ar ^q+ (4≦q≦15) and I ^q+ (5≦q≦27 on He andH ₂. The cross section can be approximately reproduced by 1/2 πR ² according to the classical barrier model. Theq-dependences exhibit significant fluctuations even for high charge states.