Pulsed discharge nozzle cavity ringdown spectroscopy of cold polycyclic aromatic hydrocarbon ions

The gas-phase electronic absorption spectra of the naphthalene (C10H8+) and acenaphthene (C12H10+) cations have been measured in the visible range in a free jet planar expansion in an attempt to collect data in an astrophysically relevant environment. The direct absorption spectra of two out of four bands measured of the gas-phase cold naphthalene cation along with the gas-phase vibronic absorption spectrum of the cold acenaphthene cation are reported for the first time. Direct absorption spectra of their van der Waals complexes with argon are also reported for the first time. The study has been carried out using the ultrasensitive and versatile technique of cavity ringdown spectroscopy (CRDS) coupled to a pulsed discharge slit nozzle (PDN). The new PDN-CRDS set up is described and its characteristics are evaluated. The direct-absorption spectra of the polycyclic aromatic hydrocarbon (PAH) ions are discussed and compared to the gas-phase and solid-phase data available in the literature. The analysis of the results show that cold, free flying PAH ions are generated in the argon discharge primarily through soft Penning ionization. This enables the intrinsic band profiles to be measured, a key requirement for astrophysical applications. (C) 2003 American Institute of Physics.