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Register a new userFragmentation branching ratios of highly excited hydrocarbon molecules CnH and their cations CnH+ (n<4)
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Added by
Karine Wohrer-Beroff
Publication date
2008
fields
Physics
and research's language is
English
Authors
T. Tuna
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We have measured fragmentation branching ratios of neutral CnH and CnH+ cations produced in high velocity (4.5 a.u) collisions between incident CnH+ cations and helium atoms. Electron capture gives rise to excited neutral species CnH and electronic excitation to excited cations CnH+. Thanks to a dedicated set-up, based on coincident detection of all fragments, the dissociation of the neutral and cationic parents were recorded separately and in a complete way. For the fragmentation of CnH, the H-loss channel is found to be dominant, as already observed by other authors. By contrast, the H-loss and C-loss channels equally dominate the two-fragment break up of CnH+ species. For these cations, we provide the first fragmentation data (n > 2). Results are also discussed in the context of astrochemistry.
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As a part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by the interaction with vacuum ultraviolet (VUV) photons that are emitted by hot young stars. This interaction leads to the emission of the well-known aromatic infrared bands but also of electrons, which can significantly contribute to the heating of the interstellar gas.Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs.Methods. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9 to 20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy.Photoionization is found to be predominant over dissociation at all energies, which differs from an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size.Large PAH cations could be efficiently ionized in H i regions and provide a contribution to the heating of the gas by photoelectric effect. Also, at the border of or in H ii regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points.
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