Photoprocessing of large PAH cations.

In cosmic environments, polycyclic aromatic hydrocarbons (PAHs) strongly interact with vacuum ultraviolet (VUV) photons emitted by young stars. Trapped PAH cations ranging in size from 30 to 48 carbon atoms were irradiated by tunable synchrotron light (DESIRS beamline at SOLEIL). Their ionization and dissociation cross sections were determined and compared with TD-DFT computed photoabsorption cross sections.

Investigating the importance of edge-structure in the loss of H/H of PAH cations: the case of dibenzopyrene isomers.

We present a detailed study of the main dehydrogenation processes of two dibenzopyrene cation (CH) isomers, namely dibenzo(a,e)pyrene (AE) and dibenzo(a,l)pyrene (AL). First, action spectroscopy under VUV photons was performed using synchrotron radiation in the 8-20 eV range. We observed lower dissociation thresholds for the non-planar molecule (AL) than for the planar one (AE) for the main dissociation pathways: H and 2H/H loss.

Unimolecular reaction energies for polycyclic aromatic hydrocarbon ions.

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of CH to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E) for loss of H from sp-C and sp-C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene.

VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes.

Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 - 20 eV range from the synchrotron SOLEIL beamline, DESIRS.