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The electronic spectra of gas-phase cationic polycyclic aromatic hydrocarbons(PAHs), trapped in the Fourier Transform Ion Cyclotron Resonance cell of thePIRENEA experiment, have been measured by multiphoton dissociation spectroscopyin the 430-480 nm spectral range using the radiation of a mid-band opticalparametric oscillator laser. We present here the spectra recorded for differentspecies of increasing size, namely the pyrene cation (C16H10+), the1-methylpyrene cation (CH3-C16H9+), the coronene cation (C24H12+), and itsdehydrogenated derivative C24H10+. The experimental results are interpretedwith the help of time-dependent density functional theory calculations andanalysed using spectral information on the same species obtained from matrixisolation spectroscopy data. A kinetic Monte Carlo code has also been used, inthe case of pyrene and coronene cations, to estimate the absorptioncross-sections of the measured electronic transitions. Gas-phase spectra ofhighly reactive species such as dehydrogenated PAH cations are reported for thefirst time.

Visible photodissociation spectroscopy of PAH cations and derivatives in the PIRENEA experiment