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.     

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.     

The anomalous shape of the cross section for the formation of SF3+ fragment ions produced by electron impact on SF6 revisited

The partial ionization cross section for the formation of SF(3) (+) fragment ions following electron impact on SF(6) is known to have a pronounced structure in the cross section curve slightly above 40 eV. We used the mass-analyzed ion kinetic energy (MIKE) scan technique to demonstrate the presence of a channel contributing to the SF(3) (+) partial ionization cross section that we attribute to the Coulomb explosion of doubly charged metastable SF(4) (2+) ions into two singly charged ions SF(3) (+) and F(+), with a threshold energy of about 45.5 eV. Thus the observed unusual shape of the SF(3) (+) partial ionization cross section is the result of two contributions, (i) the direct formation of SF(3) (+) fragment ions via dissociative ionization of SF(6) with a threshold energy of 22 eV and (ii) the Coulomb explosion of metastable SF(4) (2+) ions with a threshold energy of about 45.5 eV. A detailed analysis of the MIKE spectrum reveals an average kinetic energy release of about 5 eV in the Coulomb explosion of the SF(4) (2+) ions with evidence of a second channel corresponding to an average kinetic energy release of about 1.1 eV.     

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).     

Differential, partial and total electron impact ionization cross sections for SF(6)

Single and double differential ionization cross sections for the production of ions resulting from dissociative, single and double ionization of SF(6) by electron impact have been calculated using a semiempirical formulation based on the Jain-Khare approach. In addition, triple differential cross sections have been obtained for some of the doubly charged fragment ions at an incident electron energy of 100, 150, and 200 eV, respectively, and a fixed scattering angle of 30 degrees. As no previous data seem to exist for differential cross sections we have derived from these differential cross sections corresponding partial and total ionization cross sections from threshold up to 900 eV and compared those with the available theoretical and experimental data.     

Dissociative electron attachment resonances in ammonia: a velocity slice imaging based study

Negative ion resonance states of ammonia are accessed upon capture of electrons with energy 5.5 eV and 10.5 eV, respectively. These resonance states dissociate to produce H(-) and NH(2)(-) fragment anions via different fragmentation channels. Using the velocity slice imaging technique, we measured the angular and kinetic energy distribution of the fragment H(-) and NH(2)(-) anions with full 0-2π angular coverage across the two resonances. The scattered H(-) ions at both resonances show variation in their angular distribution as a function of the kinetic energy indicating geometric rearrangement of NH(3)(-*) ion due to internal excitations and differ from the equilibrium geometry of the neutral molecule. The second resonance at 10.5 eV shows strong forward-backward asymmetry in the scattering of H(-) and NH(2)(-) fragment ions. Based on the angular distributions of the H(-) ions, the symmetry of the resonances at 5.5 eV and 10 .5 eV are determined to be A(1) and E, respectively, within C(3v) geometry.     

Electron-impact ionization of CCl4 and CCl2F2

Absolute partial and total cross sections for electron-impact ionization of CCl4 and CCl2F2 are reported for electron energies from threshold to 1000 eV. The product ions are mass analyzed using a time-of-flight mass spectrometer and detected with a position-sensitive detector whose output demonstrates that all product ion species are collected with equal efficiency irrespective of their initial kinetic energies. Data are presented for production of CCl3(+), CCl2(+), CCl+, C+, Cl2(+), and CCl3(2+) from CCl4; and for production of CCl(2)F+, CClF2(+), CClF(+), (CCl+ + CF2(+)), Cl+, CF+, F+, and C+ from CCl2F2. Data are also reported for formation of (CCl2(+),Cl+) and (CCl+, Cl+) ion pairs from CCl4. The total cross section for each target is obtained as the sum of the partial cross sections. The overall uncertainty in the absolute cross sections for most of the singly charged ions is +/- 5-7 %. The present partial cross sections for lighter fragment ions are found to be considerably greater than had been previously reported but the most recent total cross section measurements agree well with those reported here. Neither the binary-encounter-Bethe theory nor the Deutsch-Mark theory reproduces the experimental cross sections correctly for both targets.     

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.     

Reactions of O+ with CnH2n+2, n=2-4: a guided-ion beam study

We have measured absolute reaction cross sections for the interaction of O(+) with ethane, propane, and n-butane at collision energies in the range from near thermal to approximately 20 eV, using the guided-ion beam (GIB) technique. We have also measured product recoil velocity distributions using the GIB time-of-flight (TOF) technique for several product ions at a series of collision energies. The total cross sections for each alkane are in excess of 100 A(2) at energies below approximately 2 eV, and in each case several ionic products arise. The large cross sections suggest reactions that are dominated by large impact parameter collisions, as is consistent with a scenario in which the many products derive from a near-resonant, dissociative charge-transfer process that leads to several fragmentation pathways. The recoil velocities, which indicate product ions with largely thermal velocity distributions, support this picture. Several product ions, most notably the C(2)H(3) (+) fragment for each of the alkanes, exhibit enhanced reaction efficiency as collision energy increases, which can be largely attributed to endothermic channels within the dissociative charge-transfer mechanism.     

Dissociative ionization of O2 and N2 by electron impact — N+ and O+ kinetic energies and angular distributions

An apparatus containing cross molecular and pulsed electron beams has been used to obtain distributions in kinetic energy and angle of fast (? 0.5 eV) positive ions produced through dissociative ionization of N₂ and O₂ by impact of 50 to 2000 eV electrons. Four main O⁺ ion groups are observed with peak energies of 0.8, 2.0, 3.0, and 5.0 eV. Two main N⁺ groups peaking at 2.0 and 3.0 eV are seen. Angular distributions of both N⁺ and O⁺ ions are essentially isotropic for electron-beam-ion detection angles from 30° to 110°.     

Dissociative scattering of hyperthermal energy CF3+ ions from modified surfaces

Dissociative scattering of CF3+ ions in collision with a self-assembled monolayer surface of fluorinated alkyl thiol on a gold 111 crystal has been studied at low ion kinetic energies (from 29 to 159 eV) using a custom built tandem mass spectrometer with a rotatable second stage energy analyzer and mass spectrometer detectors. Energy and intensity distributions of the scattered fragment ions were measured as a function of the fragment ion mass and scattering angle. Inelastically scattered CF3+ ions were not observed even at the lowest energy studied here. All fragment ions, CF2+, CF+, F+, and C+, were observed at all energies studied with the relative intensity of the highest energy pathway, C+, increasing and that of the lowest energy pathway, CF2+, decreasing with collision energy. Also, the dissociation efficiency of CF3+ decreased significantly as the collision energy was increased to 159 eV. Energy distributions of all fragment ions from the alkyl thiol surface showed two distinct components, one corresponding to the loss of nearly all of the kinetic energy and scattered over a broad angular range while the other corresponding to smaller kinetic energy losses and scattered closer to the surface parallel. The latter process is due to delayed dissociation of collisionally excited ions after they have passed the collision region as excited parent ions. A similar study performed at 74 eV using a LiF coated surface on a titanium substrate resulted only in one process for all fragment ions; corresponding to the delayed dissociation process. The intensity maxima for these fragmentation processes were shifted farther away from the surface parallel compared to the thiol surface. A new mechanism is proposed for the delayed dissociation process as proceeding via projectile ions' neutralization to long-lived highly excited Rydberg state(s), reionization by the potential field between the collision region and entrance to the energy analyzer, and subsequent dissociation several microseconds after collisional excitation. A kinematic analysis of experimental data plotted as velocity Newton diagrams demonstrates that the delayed dissociation process results from the collisions of the ion with the bulk surface; i.e., the self-assembled monolayer surface acts as a bulk surface. A similar analysis for the highly inelastic collision processes shows that these are due to stronger collisions with a fraction of the thiol molecular chain, varying in length (mass) with the ion energy.     

High resolution dissociative electron attachment to gas phase adenine

The dissociative electron attachment to the gas phase nucleobase adenine is studied using two different experiments. A double focusing sector field mass spectrometer is utilized for measurements requiring high mass resolution, high sensitivity, and relative ion yields for all the fragment anions and a hemispherical electron monochromator instrument for high electron energy resolution. The negative ion mass spectra are discussed at two different electron energies of 2 and 6 eV. In contrast to previous gas phase studies a number of new negative ions are discovered in the mass spectra. The ion efficiency curves for the negative ions of adenine are measured for the electron energy range from about 0 to 15 eV with an electron energy resolution of about 100 meV. The total anion yield derived via the summation of all measured fragment anions is compared with the total cross section for negative ion formation measured recently without mass spectrometry. For adenine the shape of the two cross section curves agrees well, taking into account the different electron energy resolutions; however, for thymine some peculiar differences are observed.     

Electron ionization of SiCl4

Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV).     

13C labelling study of the interconversion of ethylbenzene, 7-methylcycloheptatriene and p-xylene ions

The isomerization of the molecular ions of ethylbenzene, 7-methylcycloheptatriene and p-xylene by skeletal rearrangement prior to the formation of [C₇H₇]⁺ ions has been investigated by using ¹³C labelled compounds. The results obtained for ions generated by 70 eV and 12 eV electron impact, and fragmenting in the ion source, the 1st field free region and the 2nd field free region, respectively, are compared with those obtained from D labelled derivatives. It is shown that at long reaction times metastable p-xylene ions lose a methyl radical after scrambling of all C atoms and H atoms, while the unstable molecular ions in the ion source react by specific loss of one of the methyl substituents. Both unstable and metastable ethylbenzene ions fragment by two competing mechanisms, one corresponding to specific loss of the terminal methyl group, and the other involving scrambling of all C and H atoms. These results are discussed by use of a dynamic model developed for the mutual interconversion and fragmentation of the molecular ions of ethylbenzene, methylcyclo-heptatriene and p-xylene. The experimental results can be explained by an equilibrium between metastable methylcycloheptatriene ions and p-xylene ions with sufficient energy for skeletal rearrangement, while about 40% of the metastable ethylbenzene ions fragment after rearrangement to methylcycloheptatriene ions and about 60% of the ethylbenzene ions rearrange further to xylene ions before fragmentation. Metastable methylcycloheptatriene ions, mainly lose a methyl group without a skeletal rearrangement, however, because the rearranged ions are kinetically trapped as ‘stable’ xylene ions or ethylbenzene ions.     

Electron and positron scattering from 1,1-C2H2F2

1,1-difluoroethylene (1,1-C2H2F2) molecules have been studied for the first time experimentally and theoretically by electron and positron impact. 0.4-1000 eV electron and 0.2-1000 eV positron impact total cross sections (TCSs) were measured using a retarding potential time-of-flight apparatus. In order to probe the resonances observed in the electron TCSs, a crossed-beam method was used to investigate vibrational excitation cross sections over the energy range of 1.3-49 eV and scattering angles 90 degrees and 120 degrees for the two loss energies 0.115 and 0.381 eV corresponding to the dominant C-H (nu2 and nu9) stretching and the combined C-F (nu3) stretching and CH2 (nu11) rocking vibrations, respectively. Electron impact elastic integral cross sections are also reported for calculations carried out using the Schwinger multichannel method with pseudopotentials for the energy range from 0.5 to 50 eV in the static-exchange approximation and from 0.5 to 20 eV in the static-exchange plus polarization approximation. Resonance peaks observed centered at about 2.3, 6.5, and 16 eV in the TCSs have been shown to be mainly due to the vibrational and elastic channels, and assigned to the B2, B1, and A1 symmetries, respectively. The pi* resonance peak at 1.8 eV in C2H4 is observed shifted to 2.3 eV in 1,1-C2H2F2 and to 2.5 eV in C2F4; a phenomenon attributed to the decreasing C=C bond length from C2H4 to C2F4. For positron impact a conspicuous peak is observed below the positronium formation threshold at about 1 eV, and other less pronounced ones centered at about 5 and 20 eV.     

Applications of collision dynamics in quadrupole mass spectrometry

Some applications of collision dynamics in the field of quadrupole mass spectrometry are presented. Previous data on the collision induced dissociation of ions in triple quadrupole mass spectrometers is reviewed. A new method to calculate the internal energy distribution of activated ions directly from the increase in the cross section for dissociation with center of mass energy is presented. This method, although approximate, demonstrates explicitly the high efficiency of transfer of translational to internal energy of organic ions. It is argued that at eV center of mass energies, collisions between protein ions and neutrals such as Ar are expected to be highly inelastic. The discovery and application of collisional cooling in radio frequency quadrupoles is reviewed. Some previously unpresented data on fragment ion energies in triple quadrupole tandem mass spectrometry are shown that demonstrate directly the loss of kinetic energy of fragment ions in the cooling process. The development of the energy loss method to measure collision cross sections of protein ions in triple quadrupole instruments is reviewed along with a new discussion of the effects of inelastic collisions in these experiments and related ion mobility experiments.     

Electron stimulated desorption: A critical review

A critical review of the literature in the field of electron stimulated desorption is presented. The material is covered through December 1976. The literature on electron-induced ion desorption using bombarding electrons with energy <200 eV has been reviewed in detail several times. This review, therefore, concentrates on electron-induced desorption of ground state and excited state neutrals and the effect of electron bombarding energy in the energy range above several hundred eV. There is general agreement that ESD involves the direct interaction of the bombarding electron with the adsorbed species. Electronic transitions to anti-bonding modes result in the desorption of neutrals, excited state and ionic species. The cross sections are atomic in nature and vary from 10^-15 cm² to <10^-20 cm². The interactions and cross sections are relatively independent of the substrate material. The largest cross sections occur for weakly bound molecular species. Although there is agreement on the qualitative character of the interaction, there is very poor agreement on the quantitative cross section values. Very little information exists at all on direct measurements of neutral desorption and the effect of bombarding electron energy in the energy range above 500 eV.The material on neutral desorption is divided into three parts, namely experiments involving total pressure measurements, partial pressure measurements, and detection of desorbing excited state neutrals. The following section considers high energy data, independent of type of desorbing particle. Finally, new data concerning ion angular distributions in ESD is discussed.     

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.     

Cleavage of the ether bond by electron impact: differences between linear ethers and tetrahydrofuran

Dissociative electron attachment (DEA) to diethyl ether yielded primarily the C(2)H(5)O(-) ion, with a strong Feshbach resonance band at 9.1 eV and a weaker shape resonance band at 3.89 eV. Very similar spectra were obtained for dibutyl ether, with C(4)H(9)O(-) bands at 8.0 and 3.6 eV. Some of these primary ions subsequently lost H(2) and yielded weaker signals of the C(2)H(3)O(-) and C(4)H(7)O(-) ions. In contrast, DEA to the cyclic ether tetrahydrofuran (THF) yielded mainly a fragment of mass 41, presumably deprotonated ketene, at 7.65 eV. The low-energy band was missing in THF. H(-) with two bands at 6.88 and 8.61 eV, and an ion of mass 43 (presumably deprotonated acetaldehyde) with two bands at 6.7 and 8.50 eV were also observed. We propose that in the primary DEA step the C-O bond is cleaved in both the open-chain and the cyclic ethers. In the open-chain ethers the excess energy is partitioned between the (internal and kinetic) energies of two fragments, resulting in an RO(-) ion cool enough to be observed. The CH(2)(CH(2))(3)O(-) ion resulting from cleavage of the C-O bond in THF contains the entire excess energy (more than 6 eV at an electron energy of 7.65 eV) and is too short-lived with respect to further dissociation and thermal autodetachment to be detected in a mass spectrometer. These findings imply that there could be a substantial difference between the fragmentation in the gas phase described here and fragmentation in the condensed phase where the initially formed fragments can be rapidly cooled by the environment.     

S(1S) production following electron impact on thiophosgene (Cl2CS)

A special xenon matrix detector has been used to study the production of S(1S) following controlled electron impact on thiophosgene (Cl2CS) targets over an electron energy range from threshold to 400 eV. Time-of-flight spectroscopy has been used to measure S(1S) fragment kinetic energies. Fragments with energies in excess of 1 eV have been observed. The absolute cross section for S(1S) production reaches a maximum of [1.05+/-0.35] x 10(-18) cm2 at approximately 125 eV impact energy. Two different fragmentation processes, involving triplet and singlet excited states of the parent Cl2CS molecule, have been identified.