O_{2}

In CO_{2}-rich atmospheres that are always exposed to ionizing radiation (e.g., Venus and Mars), every fragmentation process can significantly impact the inventory of moieties present in these environments. Nevertheless, the production of O_{2}^{+} ions as a direct result of CO_{2} fragmentation has never been quantified so far. Since molecular oxygen is considered as a potential trace of living organisms, nonbiotic pathways for its production must be known. In this work, O_{2}^{+} coming from CO_{2} fragmentation by electron impact is unambiguously identified and measured in absolute scale.

Three-Body Fragmentation from Single Ionization of Water by Electron Impact: The Role of Satellite States.

Ionization of water with energy transfers close to the 2a1 inner valence orbital is accompanied by a fast electronic rearrangement driven by electron relaxation and electron-electron correlations. Quasi-degenerate single vacancy and satellites one-electron-two-vacancies excited states in outer shells are created and leave their fingerprints in the three-body fragmentation pattern. Single vacancy states have been associated with Auger decay and double ionization. Satellite excited states are here convincingly assigned to single ionization. We focus on the H0 + O+ + H0 fragmentation by electron impact taking advantage of the high sensitivity of the delayed extraction time-of-flight technique to uncover kinematic attributes of suprathermal O+ ions. It is found that the H0 ejections occur under a large angular rearrangement, in an approximate linear geometry, and leaving the O+ near at rest, with ∼50% of the O+ produced in water fragmentation by swift electrons presenting this feature.

A novel double-focusing time-of-flight mass spectrometer for absolute recoil ion cross sections measurements.

In this work, the inclusion of an Einzel-like lens inside the time-of-flight drift tube of a standard mass spectrometer coupled to a gas cell-to study ionization of atoms and molecules by electron impact-is described. Both this lens and a conical collimator are responsible for further focalization of the ions and charged molecular fragments inside the spectrometer, allowing a much better resolution at the time-of-flight spectra, leading to a separation of a single mass-to-charge unit up to 100 a.m.u. The procedure to obtain the overall absolute efficiency of the spectrometer and micro-channel plate detector is also discussed.

Kinetic Energy Release of the Singly and Doubly Charged Methylene Chloride Molecule: The Role of Fast Dissociation.

The center of mass kinetic energy release distribution (KERD) spectra of selected ionic fragments, formed through dissociative single and double photoionization of CH2Cl2 at photon energies around the Cl 2p edge, were extracted from the shape and width of the experimentally obtained time-of-flight (TOF) distributions. The KERD spectra exhibit either smooth profiles or structures, depending on the moiety and photon energy. In general, the heavier the ionic fragments, the lower their average KERDs are. In contrast, the light H(+) fragments are observed with kinetic energies centered around 4.5-5.5 eV, depending on the photon energy. It was observed that the change in the photon energy involves a change in the KERDs, indicating different processes or transitions taking place in the breakup process. In the particular case of double ionization with the ejection of two charged fragments, the KERDs present have characteristics compatible with the Coulombic fragmentation model. Intending to interpret the experimental data, singlet and triplet states at Cl 2p edge of the CH2Cl2 molecule, corresponding to the Cl (2p → 10a1*) and Cl (2p → 4b1*) transitions, were calculated at multiconfigurational self-consistent field (MCSCF) level and multireference configuration interaction (MRCI). These states were selected to form the spin-orbit coupling matrix elements, which after diagonalization result in a spin-orbit manifold. Minimum energy pathways for dissociation of the molecule were additionally calculated aiming to give support to the presence of the ultrafast dissociation mechanism in the molecular breakup.

Strong Electronic Selectivity in the Shallow Core Excitation of the CH2Cl2 Molecule.

The photoexcitation and multiphotoionization of the dichloromethane molecule have been studied for photons with energies from 100 eV to the Cl 2p edge, using the time-of-flight multicoincidence technique and synchrotron radiation. The electronic de-excitation gives rise to one to three electrons and an ionic molecule that decays onto smaller moieties through several fragmentation channels. To discern the channels, sets of fragments have been dispersed in time, measured in coincidence, and recorded as a function of incident photon energy. The chlorine ion, Cl(+), has the highest intensity around and above the Cl 2p edge, while the CHnCl(+) ion, corresponding to the loss of one neutral chlorine atom, dominates the mass spectra in the valence region. In addition, strong electronic selectivity has been observed for the core-excited molecule.

Absolute cross sections for O2 dication production by electron impact.

Direct detection of homonuclear diatomic dications using mass spectrometry has the intrinsic inability to distinguish between fragments with the same mass-to-charge ratio, as is the case of the oxygen molecule. In this work, absolute cross sections for the double ionization of the homoisotopic (16)O2 molecule by electron impact, in the 30-400 eV energy range, is reported for the first time, and show significant discrepancies with previous results, obtained with the heteroisotopic (16)O(17)O. The measurements suggest that O2 (++) is mainly produced through post-collisional Auger-like deexcitation.

Ionization and fragmentation of methane induced by 40 eV to 480 eV synchrotron radiation: from valence to beyond core electron ionization.

Photoionization and fragmentation of gaseous methane induced by tunable synchrotron radiation were investigated in a wide energy range, from 40 eV up to 480 eV. We report electron-ion coincidence experiments by measuring the relative partial-ion yields and precursor-specific relative yields for individual fragment ions and for ion fragment pairs as a function of photon energy. The fragmentation patterns are discussed with emphasis on the transition behavior of the bond breaking reactions and of the hydrogen rearrangements from valence to core electron ionization. Below the C 1s threshold, a comparison between photon induced dissociation and electron impact data showed that the ionic fragments formation depends for both projectiles on the same final electronic state reached upon ionization.