Ultraviolet and vacuum ultraviolet photo-processing of protonated benzonitrile (C6H5CNH+)

Context. The recent detection in pre-stellar sources of cyano-substituted and pure hydrocarbon cycles has emphasized the importance of aromatic chemistry in the earliest stages of star formation. Ultraviolet (UV) and vacuum-UV (VUV) radiation is ubiquitous in space and thus the photo-processing of small cyclic ions may open a window onto rich chemical networks and lead to the formation of larger aromatics in space. Aims. The aim is to investigate the fate of protonated benzonitrile species after UV and VUV photoexcitation and the subsequent potential impact on stellar and interstellar chemistry. Methods. Protonated benzonitrile was isolated in a linear ion trap prior to irradiation with UV and VUV radiation (4.5–13.6 eV) from the DESIRS beamline at synchrotron SOLEIL. The study was extended down to 3.5 eV using a cryogenic Paul ion trap coupled to an OPO laser at the PIIM laboratory. Photodissociation action spectra were obtained by monitoring the photofragment yields as a function of photon energy. Results. The UV/VUV photodissociation action spectra of protonated benzonitrile show structured bands from 3.8 to 9 eV. The primary dissociation channel of protonated benzonitrile corresponds to HCN/HNC loss and formation of the phenylium cation (C6H5+); whereas at high energies, a minor channel is observed that correlates with HC3N loss and formation of C4H5+. Conclusions. The UV and VUV photodestruction of protonated benzonitrile leads to the formation of a highly reactive cationic species, C6H5+, predicted to be an important precursor of larger aromatic molecules in space, such as polycyclic aromatic hydrocarbons. The inclusion of C6H5+ – a precursor of benzene and, by extension, of benzonitrile – as the result of formation via the photodissociation of protonated benzonitrile in current astrochemical models could improve the predicted abundance of benzonitrile, which is currently underestimated.