Infrared spectroscopy of gas-phase polycyclic aromatic hydrocarbon cations in the 10-50 mu m spectral range

The gas-phase infrared spectra of four polycyclic aromatic hydrocarbon (PAH) cations have been recorded in the 10-50 {mu}m (or 1000-200 cm{sup -1}) spectral range via IR multiple photon dissociation (IRMPD) spectroscopy. Ionized PAHs are formed by UV laser ionization in an effusive beam and subsequently irradiated with a single pulse of narrowband tunable infrared light produced by the Free-Electron Laser for IntraCavity Experiments FELICE. The ion population is then analyzed in a time-of-flight mass spectrometer. Upon resonance, dissociation is induced so that IR spectra can be recorded by monitoring either the depleted parent ion intensity or the appearance of fragment ions as a function of the wavelength. The intracavity IR fluence enables the recording of IRMPD spectra of strongly bound PAH cations in the hitherto inaccessible far-IR spectral range. Experimental spectra are presented for the radical cations of anthracene, tetracene, pentacene, and coronene. Spectra calculated with density functional theory at the B3LYP/6-311g(2df,2pd) level reproduce IR frequencies reasonably accurately in this spectral range when a uniform scaling factor of 0.94 over the complete 10-50 {mu}m spectral range is employed. We show that even vibrational modes with a calculated IR intensity lower than 1 km mol{sup -1} can be observed. For themore » catacondensed PAH cations we find CH out-of-plane bending vibrations involving four adjacent CH groups within a few wavenumbers of 733 cm{sup -1}, closely matching the 13.6 {mu}m UIR band. For the larger systems, pentacene and coronene, we observe a continuous structureless background absorption above 400 cm{sup -1} which is attributed to the high density of IR dipole allowed combination modes for these systems.« less