Absolute electron impact ionization cross-sections for CF4: Three dimensional recoil-ion imaging combined with the relative flow technique.

Here we present measurements of dissociative and non-dissociative cross-sections for the electron impact of the CF4 molecule. The present experiments are based on a Recoil Ion Momentum Spectrometer (RIMS), a standard gas mixing setup for CF4, and a reference gas. The measurements were carried out at several electron energies up to 1 keV, covering the energy range of previous experiments. We apply the relative flow technique (RFT) to convert the relative cross-sections measured by the RIMS into absolute values. Using the combination of RIMS and RFT, ion collection and calibration errors were minimized. The results were compared with theoretical and experimental studies available in the literature. Previous electron impact experiments present relative cross-sections or use correction terms for the absolute cross-sections due to losses of energetic ions. We elucidate the differences between the new measurement method and the existing ones in the literature and explain why the present method can be considered reliable. Furthermore, we show how reducing correction terms affects the results.

Surface damage in cystine, an amino acid dimer, induced by keV ions.

We have studied the interaction of an ion beam (17.6 keV F-) with cystine, a dimer formed by the binding of two cysteine residues. Cystine can be considered as an ideal prototype for the study of the relevance of the disulfide (-S-S-) chemical bond in biomolecules. For the sake of comparison, the amino acid cysteine has also been subjected to the same experimental conditions. Characterization of the samples by XPS and NEXAFS shows that both pristine cystine and pristine cysteine are found as a dipolar ion (zwitterion). Following irradiation, the dimer and the amino acid show a tendency to change from the dipole ion form to the normal uncharged form. The largest spectral modification was observed in the high resolution XPS spectra obtained at around the N 1s core level for the two biomolecules. The 2p sulfur edge spectra of cysteine and cystine were much less sensitive to radiation effects. We suggest that the disulfide bond (-S-S-) remains stable before and after irradiation, contributing to the larger radiation stability of cystine as compared to the amino acid cysteine.

VUV and soft x-ray ionization of a plant volatile: Vanillin (C8H8O3).

Plant volatiles are emitted by plants in response to several forms of stress, including interaction with energetic photons. In the present work, we discuss the interaction of extreme UV and soft X-ray photons with a plant volatile, vanillin. The single and double (multiple) ionization of the vanillin molecule have been studied for the first time using time-of-flight mass spectrometry and VUV and soft X-ray photons (synchrotron radiation, at 12.0 eV, 21.2 eV, 130 eV, 310 eV, 531 eV, and 550 eV). At 12.0 and 21.2 eV, only singly charged species are observed and the parent ion, C8H8O3 (+), is the dominant species. Energy differences for some selected fragments were calculated theoretically in this energy region. At 130 eV, direct double and triple ionization of the valence electrons may occur. The fragmentation increases and CHO(+) becomes one of the main cations in the mass spectrum. The molecular ion is still the dominant species, but other fragments, such as C6H5O(+), begin to present similar intensities. At 310 eV, C 1s electrons may be ionized and Auger processes give rise to dissociative doubly ionized cations. Ionization around the O 1s edge has been studied both at the 531 eV resonance and above the ionization edge. Resonant and normal Auger processes play a significant role in each case and a large fragmentation of the molecule is observed at both photon energies, with intense fragments such as CHO(+) and CH3 (+) being clearly observed. A near edge X-ray absorption fine structure spectrum of the vanillin molecule was obtained around the O 1s ionization threshold. In addition, the fragmentation of vanillin has also been studied using a fast beam of electrons (800 eV), for the sake of comparison.

Application of a multivariate normal distribution methodology to the dissociation of doubly ionized molecules: The DMDS (CH3 -SS-CH3 ) case.

RATIONALE: The ion-ion-coincidence mass spectroscopy technique brings useful information about the fragmentation dynamics of doubly and multiply charged ionic species. We advocate the use of a matrix-parameter methodology in order to represent and interpret the entire ion-ion spectra associated with the ionic dissociation of doubly charged molecules. This method makes it possible, among other things, to infer fragmentation processes and to extract information about overlapped ion-ion coincidences. This important piece of information is difficult to obtain from other previously described methodologies. METHODS: A Wiley-McLaren time-of-flight mass spectrometer was used to discriminate the positively charged fragment ions resulting from the sample ionization by a pulsed 800 eV electron beam. We exemplify the application of this methodology by analyzing the fragmentation and ionic dissociation of the dimethyl disulfide (DMDS) molecule as induced by fast electrons. The doubly charged dissociation was analyzed using the Multivariate Normal Distribution. RESULTS: The ion-ion spectrum of the DMDS molecule was obtained at an incident electron energy of 800 eV and was matrix represented using the Multivariate Distribution theory. The proposed methodology allows us to distinguish information among [CHn SHn ]+ /[CH3 ]+ (n = 1-3) fragment ions in the ion-ion coincidence spectra using ion-ion coincidence data. Using the momenta balance methodology for the inferred parameters, a secondary decay mechanism is proposed for the [CHS]+ ion formation. As an additional check on the methodology, previously published data on the SiF4 molecule was re-analyzed with the present methodology and the results were shown to be statistically equivalent. CONCLUSIONS: The use of a Multivariate Normal Distribution allows for the representation of the whole ion-ion mass spectrum of doubly or multiply ionized molecules as a combination of parameters and the extraction of information among overlapped data. We have successfully applied this methodology to the analysis of the fragmentation of the DMDS molecule. Copyright © 2015 John Wiley & Sons, Ltd.

Single and double ionization of the camphor molecule excited around the C 1s edge.

RATIONALE: An interesting class of volatile compounds, the monoterpenes, is present in some plants although their functions are not yet fully understood. We have studied the interaction of the camphor molecule with monochromatic high-energy photons (synchrotron radiation) using time-of-flight mass spectrometry and coincidence techniques. METHODS: A commercial sample of S-camphor was admitted into the vacuum chamber, without purification, through an inlet system. Monochromatic light with energy around the C 1s edge was generated by the TGM beamline at the Brazilian Synchrotron Facility. A Wiley-McLaren mass spectrometer was used to characterize and detect the ions formed by the camphor photoionization. The data analysis was supported by energy calculations. RESULTS: Although the fragmentation patterns were basically the same at 270 eV and 330 eV, it was observed that above the C 1s edge the contribution to the spectrum from lower mass/charge fragment ions increased, pointing to a higher degree of dissociation of the molecule. Projections of the PEPIPICO spectra demonstrated the existence of unstable doubly charged species. The Gibbs free energy was calculated using the Møller-Plesset perturbation theory (MP2) for the neutral, singly and doubly excited camphor molecule. CONCLUSIONS: Our PEPIPICO spectrum clearly demonstrated the formation of doubly ionic dissociative species. From a slope analysis, we propose a secondary decay after a deferred charge separation mechanism in which, after a few steps, the camphor dication dissociates into C2 H3 (+) and C3 H5 (+) . This is the main relaxation route observed at 270 eV and 330 eV. The large energy difference between the mono and the dication (of the order of 258.2 kcal/mol) may explain the experimentally observed absence of stable dications in the spectra, because their formation is disadvantaged energetically.

Positive and negative ion formation in deep-core excited molecules: S 1s excitation in dimethyl sulfoxide.

The photo-fragmentation of the dimethyl sulfoxide (DMSO) molecule was studied using synchrotron radiation and a magnetic mass spectrometer. The total cationic yield spectrum was recorded in the photon energy region around the sulfur K edge. The sulfur composition of the highest occupied molecular orbital's and lowest unoccupied molecular orbital's in the DMSO molecule has been obtained using both ab initio and density functional theory methods. Partial cation and anion-yield measurements were obtained in the same energy range. An intense resonance is observed at 2475.4 eV. Sulfur atomic ions present a richer structure around this resonant feature, as compared to other fragment ions. The yield curves are similar for most of the other ionic species, which we interpret as due to cascade Auger processes leading to multiply charged species which then undergo Coulomb explosion. The anions S(-), C(-), and O(-) are observed for the first time in deep-core-level excitation of DMSO.

Core level (S 2p) excitation and fragmentation of the dimethyl sulfide and dimethyldisulfide molecules.

Electronic excitation and ionic dissociation of dimethylsulfide (DMS) and dimethyldisulfide (DMDS) have been studied around the S 2p edge using synchrotron radiation and time-of-flight mass spectrometry techniques. Mass spectra were obtained for both molecules, below, on and above the well defined resonances observed in the S 2p photoabsorption spectrum and centered at approximately 166 eV photon energy. Ab initio IS-CASSCF calculations were performed for a better understanding of the photoabsorption spectra. Similar calculations were also performed for the H(2)S molecule, in order to establish a bench mark. For both molecules, a higher fragmentation degree is observed with increasing photon energy. In the DMDS case, selective fragmentation was observed in the formation of the [CH(n)S](+) ions at the first S 2p resonance (corresponding to excitation to a σ*SS state) and in the formation of the [S(2)](+) and [S](+) ions at the third S 2p resonance (corresponding to excitation to a σ*CS state). Previously unreported doubly charged ([S](2+), [CH(3)](2+)) are observed for DMS and DMDS.

Dissociative photoionization of adenine following valence excitation.

We present results on the valence level excitation, ionization and dissociation of adenine, using time-of-flight mass spectrometry and synchrotron radiation, in the vacuum ultraviolet (VUV) range of 12-21 eV. The measurements were performed using a gas-phase (Ne) harmonics filter in order to eliminate contributions from higher-order harmonics. Mass spectra were obtained using the photoelectron-photoion coincidence technique (PEPICO). The relative abundances for each ionic fragment and their mean kinetic energy release have been determined from the analysis of the corresponding peak shapes in the mass spectra. Comparison with the available photoelectron spectra and previous measurements allowed the assignment of the main features in the spectra. A discussion on the dissociative photoionization channels of this molecule has also been included. Due to our harmonics-free incident photon beam we were able to propose new appearance energy (AE) for the most important ionic channels in this energy range. The precursor ion, C(5)H(5)N(5)+, is the most abundant species (40% at 15 eV and 20% at 20 eV), which confirms the high stability of adenine upon absorption of VUV photons. We have observed other intense fragment ions such as: C(4)H(4)N(4)+, C(3)H(3)N(3) (+), C(2)H(2)N(2)+ and HCNH+. The production of the neutral HCN fragment represents up to 40% of the dissociative channels for this molecule as induced by VUV photons.

Relativistic and interchannel coupling effects in photoionization angular distributions by synchrotron spectrocopy of laser cooled atoms.

We investigate the angular distribution of photoionization fragments at low photon energies (12-40 eV) in an open shell atom, by synchrotron radiation recoil ion momentum spectroscopy in a laser cooled and trapped sample. For cesium atoms, for which relativistic effects play an important role and the ion recoil is relatively small, we could determine large and rapid changes of the asymmetry parameter beta from two, observed for s electrons outside resonances and far from the Cooper minimum. They can be explained by relativistic effects and interchannel coupling arising from final state configuration mixing.