Absolute electron-impact total ionization cross sections of chlorofluoromethanes

An experimental study is reported on the electron-impact total ionization cross sections (TICSs) of CCl4, CCl3F, CCl2F2, and CClF3 molecules. The kinetic energy of the colliding electrons was in the 10-85 eV range. TICSs were obtained as the sum of the partial ionization cross sections of all fragment ions, measured and identified in a linear double focusing time-of-flight mass spectrometer. The resulting TICS profiles--as a function of the electron-impact energy--have been compared both with those computed by ab initio and (semi)empirical methods and with the available experimental data. The computational methods used include the binary-encounter-Bethe (BEB) modified to include atoms with principal quantum numbers n> or =3, the Deutsch and M?rk (DM) formalism, and the modified additivity rule (MAR). It is concluded that both modified BEB and DM methods fit the experimental TICS for (CF4), CClF3, CCl2F2, CCl3F, and CCl4 to a high accuracy, in contrast with the poor accord of the MAR method. A discussion on the factors influencing the discrepancies of the fittings is presented.     

Gas-phase positive ion chemistry of 1-bromo-1-chloro-2,2,2-trifluoroethane (halothane) upon electron ionization within an ion trap mass spectrometer

The positive ion chemistry occurring within an ion trap mass spectrometer upon electron ionization of 1-bromo-1-chloro-2,2,2-trifluoroethane, the important anaesthetic halothane, has been mapped by means of collision-induced decomposition and ion/molecule self-reaction experiments. Ionized halothane (M+*) reacts with neutral halothane to form the ionized olefin [ClBrC=CF2]+*. via HF elimination. Among the ionic fragments, [M-Br]+ and [M-F]+ react with halothane via chloride abstraction while [M-Cl]+ is unreactive under the same experimental conditions. Substituted methyl cations CHFX+ and CF2X+ (X = F, Cl, Br) undergo halide transfer processes, their reactivity being highest for X = F. Ionized carbenes CXY+ (X,Y = F,F; H,Br; H,Cl; H,F) react with halothane to form CClXY+ and CBrXY+, whereas CF+ inserts into the C-Cl bond to form CF3+ and CClF2+. Finally, Br+ and Cl+ react with halothane by charge transfer. Collision-induced dissociation experiments disclosed interesting rearrangements involved in the dissociations of +CHX-CF3 ions (X = Br, Cl), which undergo fluorine migration and elimination of CF2, as already observed for +CCl2-CF3 in a previous investigation.     

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): a comparison with CCl4

The kinetics of decomposition and subsequent chemistry of adsorbed CF(2)Cl(2), activated by low-energy electron irradiation, have been examined and compared with CCl(4). These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF(2)Cl(2) and CCl(4) dissociation increase in an H(2)O (D(2)O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H(2)O, using 180 eV incident electrons, are measured (using TPD) to be 1.0+/-0.2 x 10(-15) cm(2) for CF(2)Cl(2) and 2.5+/-0.2 x 10(-15) cm(2) for CCl(4). RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl(-) and F(-) anions in the halocarbon/water films and production of H(3)O(+), CO(2), and intermediate compounds COF(2) (for CF(2)Cl(2)) and COCl(2), C(2)Cl(4) (for CCl(4)) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.     

Electron transfer and bond-forming reactions following collisions of Cl2+ and HCl2+ with CO

Collisions between Cl(2+) and CO have been investigated using time-of-flight mass spectrometry over a collision energy range between 2.2 eV and 7.1 eV in the centre-of-mass frame. The formation of Cl(+), CO(+) and C(+) in electron transfer reactions has been detected and an unusual bond-forming reaction which generates CCl(2+) has also been observed. The reactive cross-sections, in arbitrary units, for the electron transfer reactions have been evaluated. To extract these cross sections we employ a new method of analysing mass spectral intensities for crossed-beam experiments, an algorithm which allows inter-comparison of the fluxes of all the ionic products from the electron transfer reactions. The observed electron transfer reactivity has been rationalized by calculations based on Landau-Zener theory. To account for the observation of CCl(2+), we have calculated the relevant energetics showing that the lowest lying doublet state of this dication is bound and is energetically accessible at our collision energies. These energetic arguments indicate that electron transfer in the exit channel between the separating CCl(2+) and O atom probably forms C(+) ions via the dissociation of CCl(+). Additionally, collisions between HCl(2+) and CO have been studied at collision energies from 2.2 to 7.0 eV in the centre-of-mass frame. In this collision system, proton transfer to form HCO(+) is observed to compete efficiently with dissociative and non-dissociative electron transfer.     

Electron ionization of methane: the dissociation of the methane monocation and dication

Time-of-flight mass spectrometry and two-dimensional coincidence techniques have been used to determine, for the first time, the relative precursor-specific partial ionization cross sections following electron-methane collisions. Precursor-specific partial ionization cross sections quantify the contribution of single, double, and higher levels of ionization to the partial ionization cross section for forming a specific ion (e.g. CH(+)) following electron ionization of methane. Cross sections are presented for the formation of H(+), H(2)(+), C(+), CH(+), CH(2)(+), and CH(3)(+), relative to CH(4)(+), at ionizing electron energies from 30 to 200 eV. We can also reduce our dataset to derive the relative partial ionization cross sections for the electron ionization of methane, for comparison with earlier measurements. These relative partial ionization cross sections are in good agreement with recent determinations. However, we find that there is significant disagreement between our partial ionization cross sections and those derived from earlier studies. Inspection of the values of our precursor-specific partial ionization cross sections shows that this disagreement is due to the inefficient collection of energetic fragment ions in the earlier work. Our coincidence experiments also show that the lower energy electronic states of CH(4)(2+) populated by electron double ionization of CH(4) at 55 eV are the same (ground (3)T(1), first excited (1)E(1)) as those populated by 40.8 eV photoionization. The (3)T(1) state dissociating to form CH(3)(+) + H(+) and CH(2)(+) + H(2)(+) and the (1)E(1) to form CH(2)(+) + H(+) and CH(+) + H(+). At this electron energy, we also observe population of the first excited triplet state of CH(4)(2+) ((3)T(2)) which dissociates to both CH(2)(+) + H(+) + H and CH(+) + H(+) + H(2).     

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.     

Electron-impact ionization of silicon tetrachloride (SiCl4)

We measured absolute partial cross sections for the formation of various singly charged and doubly charged positive ions produced by electron impact on silicon tetrachloride (SiCl4) using two different experimental techniques, a time-of-flight mass spectrometer (TOF-MS) and a fast-neutral-beam apparatus. The energy range covered was from the threshold to 900 eV in the TOF-MS and to 200 eV in the fast-neutral-beam apparatus. The results obtained by the two different experimental techniques were found to agree very well (better than their combined margins of error). The SiCl3(+) fragment ion has the largest partial ionization cross section with a maximum value of slightly above 6x10(-20) m2 at about 100 eV. The cross sections for the formation of SiCl4(+), SiCl+, and Cl+ have maximum values around 4x10(-20) m2. Some of the cross-section curves exhibit an unusual energy dependence with a pronounced low-energy maximum at an energy around 30 eV followed by a broad second maximum at around 100 eV. This is similar to what has been observed by us earlier for another Cl-containing molecule, TiCl4 [R. Basner, M. Schmidt, V. Tamovsky, H. Deutsch, and K. Becker, Thin Solid Films 374 291 (2000)]. The maximum cross-section values for the formation of the doubly charged ions, with the exception of SiCl3(++), are 0.05x10(-20) m2 or less. The experimentally determined total single ionization cross section of SiCl4 is compared with the results of semiempirical calculations.     

Low energy (0-10 eV) electron driven reactions in the halogenated organic acids CCl3COOH, CClF2COOH, and CF3CHNH2COOH (trifluoroalanine)

Negative ion formation following resonant electron attachment to the three title molecules is studied by means of a beam experiment with mass spectrometric detection of the anions. All three molecules exhibit a pronounced resonance in the energy range around 1 eV which decomposes by the loss of a neutral hydrogen atom thereby generating the closed shell anion (M-H)(-) (or RCOO(-)), a reaction which is also a common feature in the non-substituted organic acids. The two chlorine containing molecules CCl(3)COOH and CClF(2)COOH exhibit an additional strong and narrow resonance at very low energy (close to 0 eV) which decomposes by the cleavage of the C-Cl bond with the excess charge finally localised on either of the two fragments Cl(-) and (M-Cl)(-). This reaction is by two to three orders of magnitude more effective than hydrogen loss. Apart from these direct bond cleavages (C-Cl, O-H) resonant attachment of subexcitation electrons trigger additional remarkably complex unimolecular decompositions leading, e.g., to the formation of the bihalide ions ClHCl(-) and ClHF(-) from CCl(3)COOH and CClF(2)COOH, respectively, or the loss of a neutral CF(2) unit from trifluoroalanine thereby generating the fluoroglycine radical anion. These reactions require substantial rearrangement in the transitory negative ion, i.e., the cleavage of different bonds and formation of new bonds. F(-) from both chlorodifluoroacetic acid and trifluoroalanine is formed at comparatively low intensity (more than three orders of magnitude less than Cl(-) from the chlorine containing molecules) and predominantly within a broad resonant feature around 7-8 eV characterised as core excited resonance.     

Isomeric effects in the gas-phase reactions of dichloroethene, C2H2CL2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH(4)(+), H(3)O(+), SF(3)(+), CF(3)(+), CF(+), SF(5)(+), SF(2)(+), SF(+), CF(2)(+), SF(4)(+), O(2)(+), Xe(+), N(2)O(+), CO(2)(+), Kr(+), CO(+), N(+), N(2)(+), Ar(+), F(+), and Ne(+)) with the three structural isomers of dichloroethene, i.e., 1,1-C(2)H(2)Cl(2), cis-1,2-C(2)H(2)Cl(2), and trans-1,2-C(2)H(2)Cl(2) is reported. The recombination energy (RE) of these ions spans the range of 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube (SIFT). Collisional rate coefficients are calculated by modified average dipole orientation (MADO) theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C(2)H(2)Cl(2) with photon energies in the range of 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H(3)O(+), CF(3)(+), and CF(+). For 1,1-C(2)H(2)Cl(2) the reaction with H(3)O(+) proceeds at the collisional rate with the only ionic product being 1,1-C(2)H(2)Cl(2)H(+). However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C(2)H(2)Cl(2), but only proceeds with 14% and 18% efficiency, respectively. The CF(3)(+) reaction proceeds with 56-80% efficiency, the only ionic product for 1,1-C(2)H(2)Cl(2) being C(2)H(2)Cl(+) formed via Cl(-) abstraction, whereas the only ionic product for both 1,2-isomers is CHCl(2)(+) corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C(2)H(2)Cl(2) isomers, have been found in the reactions of SF(+), CO(2)(+), CO(+), N(2)(+), and Ar(+). Although these five ions have REs above the ionization energy (IE) of any of the C(2)H(2)Cl(2) isomers, and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C(2)H(2)Cl(2) is responsible for the observed effects.     

Differential elastic electron scattering cross sections for CCl4 by 1.5-100 eV energy electron impact

We report absolute elastic differential, integral and momentum transfer cross sections for electron interactions with CCl(4). The incident electron energy range is 1.5-100 eV, and the scattered electron angular range for the differential measurements varies from 15°-130°. The absolute scale of the differential cross section was set using the relative flow technique with helium as the reference species. Comparison with previous total cross sections shows good agreement. Atomic-like behaviour in this scattering system is shown here for the first time, and is further investigated by comparing the CCl(4) elastic cross sections to recent results on the halomethanes and atomic chlorine at higher impact energies [H. Kato, T. Asahina, H. Masui, M. Hoshino, H. Tanaka, H. Cho, O. Ingólfsson, F. Blanco, G. Garcia, S. J. Buckman, and M. J. Brunger, J. Chem. Phys. 132, 074309 (2010)].     

A guided-ion beam study of the reactions of Xe(+) and Xe(2+) with NH(3) at hyperthermal collision energies

We have measured the absolute cross sections for reactions of Xe(+) and Xe(2+) with NH(3) at collision energies in the range from near-thermal to ～34 and ～69?eV, respectively. For Xe(+), the cross section for charge transfer, the only exothermic channel, decreases from ～200A?(2) below 0.1 eV to ～12A?(2) at the highest energies studied. The production of NH(3) (+) is the only channel observed below 5 eV, above which a small amount of NH(2) (+) is also formed. In Xe(2+) reactions, the main products observed are NH(3) (+) and NH(2) (+). The charge transfer cross section decreases monotonically from ～80 to ～6A?(2) over the studied energy range. The NH(2) (+) cross section is similar to the charge transfer cross section at the lowest energies, and exhibits a second component above 0.4 eV, with a maximum of 65A?(2) at 0.7 eV, above which the cross section decreases to ～30A?(2) at the highest energies studied. At energies above 10 eV, a small amount of NH(+) is also observed in Xe(2+) collisions. Product recoil velocity distributions were determined at selected collision energies, using guided-ion beam time-of-flight methods.     

ClO radical yields in the reaction of O(1D) with Cl2, HCl, chloromethanes, and chlorofluoromethanes

Absolute ClO radical product yields in the gas-phase reactions of O((1)D) with Cl(2), HCl, CCl(4), CHCl(3), CH(2)Cl(2), CH(3)Cl, CFCl(3), CF(2)Cl(2), CF(3)Cl, CHFCl(2), and CHF(2)Cl are reported. Product yields were measured using pulsed-laser photolysis of O(3) to produce O((1)D) in the presence of excess reactant combined with dual wavelength differential cavity ring-down spectroscopic detection of the ClO radical. ClO radical absorption cross sections for the A(2)Π(v = 10) ← X(2)Π(v = 0) transition band head near 280 nm were determined between 200 and 296 K as part of this work. The ClO product yields obtained at room temperature were Cl(2) (0.77 ± 0.10), HCl (0.20 ± 0.04), CCl(4) (0.79 ± 0.04), CHCl(3) (0.77 ± 0.04), CH(2)Cl(2) (0.73 ± 0.04), CH(3)Cl (0.46 ± 0.06), CFCl(3) (0.79 ± 0.04), CF(2)Cl(2) (0.76 ± 0.06), CF(3)Cl (0.82 ± 0.06), CHFCl(2) (0.73 ± 0.05), and CHF(2)Cl (0.56 ± 0.03), where the quoted error limits are 2σ of the measurement precision. ClO product yields in the O((1)D) + Cl(2) and CFCl(3) reactions were found to be independent of temperature between 200 and 296 K, within the precision of the measurements. The absolute ClO yields obtained in this study are compared with previously reported values determined using relative and indirect methods.     

4d-->4f dipole resonance of the metal atom encapsulated in a fullerene cage: Ce@C82

The yield curves for photoions from Ce@C(82) are measured by using synchrotron radiation in the photon energy range from 90 to 160 eV. Parent Ce@C(82) (z+) and fragment ions C(60) (z+) and C(70) (z+) are observed in a mass spectrum (z=1 and 2). The yield curves for doubly charged ionic species exhibit broad resonance in the photon energy region of from 120 to 140 eV which is ascribed to the 4d-->4f giant dipole resonance of the encapsulated Ce atom. The total photoabsorption cross section of Ce@C(82) was determined from partial photoionization cross sections for formation of the parent and fragment ions to be 5.3(-1.1) (+1.8) and 19.6(-3.9) (+6.5) Mb at photon energies of 110 and 130 eV, respectively.     

Products, rate constants and mechanisms of gas-phase reactions of CX(3)(+), CX(2)(+), CX(+) (X = F and/or Cl) and Cl(+) with 1,1,1- and 1,1,2-trichlorotrifluoroethane.

The gas-phase ion chemistry of 1,1,1- and 1,1,2-trichlorotrifluoroethane was investigated with an ion trap mass spectrometer. Following electron ionization both compounds (M) fragment to [M - Cl](+), CX(3)(+), CX(2)(+), CX(+) (X = F and/or Cl) and Cl(+). The reactivity of each of these fragments towards their neutral precursors was studied to obtain product and kinetic data. Whereas [M - Cl](+), CCl(3)(+) and CCl(2)F(+) cations are unreactive under the experimental conditions used, all other species react via halide abstraction to give [M - Cl](+) and, to a far lesser extent, [M - F](+). In addition, CX(2)(+) ions form CClX(2)(+) in a process which formally amounts to chlorine atom abstraction, but more likely involves chloride ion abstraction followed by charge transfer. CX(+) ions also form minor amounts of CX(3)(+) product ions, possibly via chloride abstraction followed by or concerted with dihalocarbene elimination from the (incipient) [M - Cl](+) ion. Trivalent carbenium ions are less reactive than divalent species, which in turn are less reactive than the monovalent ions (reaction efficiencies are given in parentheses): CF(3)(+)(0.70) < CF(2)(+)(0.78) < CF(+)(0.96). More interestingly, within each family of ions reactivity increases with the number of fluorine substituents (e.g. CF(2)(+) > CFCl(+) > CCl(2)(+) and CF(+) > CCl(+)), i.e. reactivity increases with the ion thermochemical stability, as measured by available standard free enthalpies of formation. Evaluation of the energetics involved shows that reactions are largely driven by the stability of the neutrals more than of the ions. Finally, the products observed in the reaction of Cl(+) are attributed to ionization of the neutral via charge transfer and fragmentation.     

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.     

Bond-forming reactions of dications with molecules: a computational and experimental study of the mechanisms for the formation of HCF2+ from CF3(2+) and H2

The QCISD and QCISD(T) quantum chemical methods have been used to characterize the energetics of various possible mechanisms for the formation of HCF2+ from the bond-forming reaction of CF3(2+) with H2. The stationary points on four different pathways leading to the product combinations HCF2+ + H+ + F and HCF2+ + HF+ have been calculated. All four pathways begin with the formation of a collision complex [H2-CF3]2+, followed by an internal hydrogen atom migration to give HC(FH)F2(2+). In two of the mechanisms, immediate charge separation of HC(FH)F2(2+) via loss of either HF+ or a proton, followed by loss of an F atom, yields the experimentally observed bond-forming product HCF2+. For the other two mechanisms, internal hydrogen rearrangement of HC(FH)F2(2+) to give C(FH)2F(2+), followed by charge separation, yields the product CF2H+. This product can then overcome a 2.04 eV barrier to rearrange to the HCF2+ isomer, which is 1.80 eV more stable. All four calculated mechanisms are in agreement with the isotope effects and collision energy dependencies of the product ion cross sections that have been previously observed experimentally following collisions between CF3(2+) and H2/D2. We find that in this open-shell system, CCSD(T) and QCISD(T) T1-diagnostic values of up to 0.04 are acceptable. A series of angularly resolved crossed-beam scattering experiments on collisions of CF3(2+) with D2 have also been performed. These experiments show two distinct channels leading to the formation of DCF2+. One channel appears to correspond to the pathway leading to the ground state 1DCF2+ + D+ + F product asymptote and the other to the 3DCF2+ + D+ + F product asymptote, which is 5.76 eV higher in energy. The experimental kinetic energy releases for these channels, 7.55 and 1.55 eV respectively, have been determined from the velocities of the DCF2+ product ion and are in agreement with the reaction mechanisms calculated quantum chemically. We suggest that both of these observed experimental channels are governed by the reaction mechanism we calculate in which charge separation occurs first by loss of a proton, without further hydrogen atom rearrangement, followed by loss of an F atom to give the final products 1DCF2+ + D+ + F or 3DCF2+ + D+ + F.     

Absolute partial cross sections and kinetic energy analysis for the electron impact ionization of ethylene

We present absolute partial electron impact ionization cross sections for ethylene in the electron energy range between threshold and 1000 eV measured with a two sector field double focusing mass spectrometer. Ion kinetic energy distribution functions have been measured at all electron energies by applying a deflection field method. Multiplication of the measured relative cross sections by the appropriately determined discrimination factors lead to accurate relative partial cross sections. Normalization of the sum of the relative partial cross sections to an absolute total cross section gives absolute partial cross section values. The initial kinetic energy distributions of several fragment ions show the presence of two or more contributions that exhibit different electron energy dependencies. Differential cross sections with respect to the initial kinetic energy of the ions are provided and are related to specific ion production channels. The electron threshold energies for the direct and numerous other dissociative ionization channels are determined by quantum chemical calculation and these allow the determination of the total kinetic energy release and the electron energy loss for the most prominent dissociative ionization channels.     

Formation of doubly positively charged diatomic ions of Mo2(2+) produced by Ar+ sputtering of an Mo metal surface

Long-lived metastable doubly positively charged diatomic ions of Mo2(2+) have been produced by Ar+ bombardment of a molybdenum metal surface. These exotic molecular dications, such as for example 92,95Mo2(2+) at m/z 93.5, could be observed in positive ion mass spectra for ion flight times of approximately 17 micros in a Cameca IMS-3f secondary ion mass spectrometer, when the ion extraction field was adjusted for detection of ions that are formed in the gas phase several micrometers in front of the sputtered surface. Mo2(2+) was observed at high primary current densities for projectile ions of Ar+, but could not be detected under very similar bombarding conditions for projectile ions of Xe+. Such a dependence of ion production by inert gas sputtering on the primary ion species [ionization energies: IP1(Ar) = 15.76 eV and IP1(Xe) = 12.13 eV] is unusual. It is shown that formation of Mo2(2+) dications takes place by resonant charge transfer in grazing gas-phase collisions between incoming projectile ions of Ar+ and sputtered molecular ions of Mo2+. The efficiency for such a resonant electron capture (Mo2+ + Ar+ --> Mo2(2+) + Ar) is of the order of 10(-5) for the bombarding conditions in our mass spectrometer and corresponds to a cross section of a few 10(-15) cm2.     

Penning ionization of N2O molecules by He*(2(3,1)S) and Ne*(3P2,0) metastable atoms: a crossed beam study

The energetics of [Rg... N2O]* autoionizing collision complexes (where Rg=He or Ne) and their dynamical evolution have been studied in a crossed beam apparatus, respectively, by Penning ionization electron spectroscopy (PIES) and by mass spectrometry (MS) techniques in the thermal energy range. The PIES spectra, detected by an electron energy analyzer, were recorded for both complexes at four different collision energies. Such spectra allowed the determination of the energy shifts for Penning electron energy distributions, and the branching ratios for the population of different electronic states and for the vibrational population in the molecular nascent ions. For the [Ne...N2O]* collision complex it was found, by MS, that the autoionization leads to the formation of N2O+, NO+, O+, and NeN2O+ product ions whose total and partial cross sections were measured in the collision energy range between 0.03 and 0.2 eV. The results are analyzed exploiting current models for the Penning ionization process: the observed collision energy dependence in the PIES spectra as well as in the cross sections are correlated with the nature of the N2O molecule orbitals involved in the ionization and are discussed in term of the Rg-N2O interaction potentials, which are estimated by using a semiempirical method developed in our laboratory.