Infrared Spectroscopy of Pentagon-Containing PAHs: Indenyl and Fluorenyl Anions and Indenyl Cation.

Polycyclic aromatic hydrocarbon (PAH) ions are crucial intermediates in interstellar chemistry and may play a key role in the infrared emission features observed in space. Here, we investigate the infrared spectra of the indenyl (CH) and fluorenyl (CH) anions and the indenyl cation (CH) using infrared predissociation (IRPD) spectroscopy. The experiments were performed in a cryogenic 22 pole ion trap at the FELion beamline of the tunable free electron laser FELIX. Spectral analysis of the two anionic PAHs, in combination with density functional theory (DFT) computations, revealed key vibrational modes near 1300 cm, making these ions potential carriers of the 7.7 μm PAH emission band seen in many astronomical objects. The feature-rich spectrum of cationic indenyls could not be entirely explained by modeling through time-independent anharmonic DFT calculations. Although a better match has been achieved through molecular dynamics simulations, we cannot completely rule out the presence of multiple cationic isomers of the H-loss fragments of indene in the experiments.