Gas-phase infrared photodissociation spectroscopy of cationic polyaromatic hydrocarbons

Infrared spectra of gas-phase cationic naphthalene, phenanthrene, anthracene, and pyrene are recorded in the 500-1600 cm(-1) range using multiphoton dissociation in an ion trap. Gas-phase polyaromatic hydrocarbons are photoionized by an excimer laser and stored in a quadrupole ion trap. Subsequent interaction with the intense infrared radiation of a free electron laser that is tuned in resonance with an infrared-allowed transition of the ion leads to sequential multiphoton absorption facilitated by rapid intramolecular vibrational redistribution. Absorption of more than 50-100 infrared photons raises the internal energy to above the dissociation threshold, leading eventually to fragmentation of the ion. Mass selective detection of the cationic species stored in the trap yields the infrared absorption spectrum of the parent ion.