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See detailElectronic spectroscopy of nucleic acids in the gas phase
Gabelica, Valérie ULg; Rosu, Frédéric ULg; Joly, Laure ULg et al

Conference (2010)

DNA polyanions trapped in a mass spectrometer undergo electron detachment following UV irradiation. Photodetachment is a single-photon process. Its efficiency depends on the nature of the DNA bases, the ... [more ▼]

DNA polyanions trapped in a mass spectrometer undergo electron detachment following UV irradiation. Photodetachment is a single-photon process. Its efficiency depends on the nature of the DNA bases, the ion's charge, and the excitation wavelength. Photodetachment can therefore be used to perform ion spectroscopy experiments, which probe electronic excitation within the initial charge state of the nucleic acids. Ion spectroscopy experiments on trapped nucleic acid cations and anions were performed from 4 to 20 eV using an OPO laser or using synchrotron radiation. Photoelectron spectroscopy experiments were also performed on multiply charged anions to probe direct detachment cross sections and electronic excitations within the final charge. The electronic spectra obtained from photodetachment integral cross sections show several resonances, provided that the photon energy is larger than the electron binding energy. We will also discuss whether the electronic spectra obtained via photodetachment can be used to probe gas phase ion structure. [less ▲]

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See detailC 1s and N 1s core excitation of aniline: Experiment by electron impact and ab initio calculations
Duflot, D.; Flament, J. P.; Giuliani, Alexandre et al

in Physical Review A (2007), 75(5), 052719

Core shell excitation spectra of aniline at the carbon and nitrogen 1s edges have been obtained by inner-shell electron energy-loss spectroscopy recorded under scattering conditions where electric dipolar ... [more ▼]

Core shell excitation spectra of aniline at the carbon and nitrogen 1s edges have been obtained by inner-shell electron energy-loss spectroscopy recorded under scattering conditions where electric dipolar conditions dominate, with higher resolution than in the previous studies. They are interpreted with the aid of ab initio configuration interaction calculations. The spectrum at the C 1s edge is dominated by an intense pi(*) band. The calculated chemical shift due to the different chemical environment at the carbon 1s edge calculated is in agreement with the experimental observations within a few tenths of an eV. The transition energies of the most intense bands in the C 1s excitation spectrum are discussed at different levels of calculations. In the nitrogen 1s excitation spectrum the most intense bands are due to Rydberg-valence transitions involving the sigma(*)-type molecular orbitals, in agreement with the experiment. This assignment is different from that of extended Huckel molecular orbital calculations. The geometries of the core excited states have been calculated and compared to their equivalent core molecules and benzene. [less ▲]

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See detailFragmentation induced in atmospheric pressure photoionization of peptides
Debois, Delphine ULg; Giuliani, Alexandre; Laprévote, Olivier

in Journal of Mass Spectrometry [=JMS] (2006), 41(12), 1554-1560

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See detailStudy of a bisquaternary ammonium salt by atmospheric pressure photoionization mass spectrometry
Giuliani, Alexandre; Debois, Delphine ULg; Laprévote, Olivier

in European Journal of Mass Spectrometry (Chichester, England) (2006), 12(3), 189-197

A comprehensive atmospheric pressure photoionization (APPI) mass spectrometry investigation of hexamethonium bromide is reported. This bisquaternary ammonium salt is a model system for the investigation ... [more ▼]

A comprehensive atmospheric pressure photoionization (APPI) mass spectrometry investigation of hexamethonium bromide is reported. This bisquaternary ammonium salt is a model system for the investigation of multiply charged species and elucidation of ion formation processes. It has been used to elucidate the physico-chemical phenomenon occurring when photoionization is carried out at atmospheric pressure. First, the in-source fragmentations were studied for aqueous solutions of the salt with the photoionization lamp switched off, i.e. under thermospray conditions. It is shown that, in this mode of operation, fragmentations are minor and may be classified into two classes, namely dequaternization and charge separation, arising from the two precursors, M2+ and [M+Br]+. Second, the fragmentation patterns have been monitored in dopant-assisted APPI for different dopants (toluene, toluene-d8 anisole and hexafluorobenzene) at various amounts. At low dopant flow rates, the [M+Br]+ and M2+ ions are still observed. As the flow rate is increased, these precursor ions lose intensity and are finally suppressed for all three dopants. Comparison of toluene and toluene-d8 reveals that H atoms may be transferred from the dopant to the molecular ions, very likely mediated by the solvent. The role of the solvent (water) was also investigated by using heavy water. Apart from the thermospray fragmentations, which are also observed in APPI, several fragmentation pathways appear to be specific to the photoionization process. Photoionization efficiencies are measured by determination of the relative photoionization cross sections with respect to toluene. It is found that, when the ionization efficiencies are taken into account, the depletion of the precursors as a function of the dopant flow rates is the same for all three dopant molecules. This result shows that the precursor ions are depleted by reactions with the photoelectrons released from the dopant. Three additional mechanisms are proposed to account for this effect: electron transfer or H atom transfer from negatively charged water nanodroplets and H atom transfer from the dopant. [less ▲]

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