IRMPD spectroscopy of a PAH cation using FELICE: The infrared spectrum and photodissociation of dibenzo[a,l]pyrene

Abstract We present the experimental InfraRed Multiple Photon Dissociation (IRMPD) spectrum and fragmentation mass spectrum of the irregular, cationic PAH dibenzo[a,l]pyrene (C 24 H 14 + ) in the 6– 40 μ m /250–1650 cm−1 range. The use of the Free-Electron Laser for IntraCavity Experiments (FELICE) enabled us to record its Far-InfraRed (FIR) spectrum for the first time. We aim to understand how irregularity affects the infrared spectrum and fragmentation chemistry of PAHs. Dibenzo[a,l]pyrene is an asymmetric, non-planar molecule, for which all vibrational modes are in principle IR-active. Calculated harmonic Density Function Theory (DFT) and anharmonic Density Functional based Tight Binding Molecular Dynamics (DFTB-MD) spectra show a large wealth of bands, which match the experiment well, but with a few differences. The periphery of the molecule contains several edge geometries, but out of all possible modes in the 11– 14 μ m out-of-plane C H bending region, only one band at 13 . 5 μ m is prominent. This fact and the richness of the C C stretching range make irregular PAHs a possible contributor to D-class interstellar spectra. The fragmentation mass spectra reveal facile 2H-loss and no [2C, 2H]-loss, which is attributed to the sterically hindered, non-planar cove region, which could protect irregular PAHs from radiation damage.