Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

Abstract

Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600–1600 cm<sup>-1<sup/> region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where they are irradiated with an IR free electron laser. The PANHs were studied in their radical cation (PANH<sup>+<sup/>) and protonated (H<sup>+<sup/>PANH) forms, and include quinoline, isoquinoline, phenanthridine, benzo[h]quinoline, acridine, and dibenzo[f,h]quinoline. Experimental IRMPD spectra were interpreted with the aid of density functional theory methods. The PANH<sup>+<sup/> IR spectra are found to resemble those of their respective non-nitrogenated PAH cations. The IR spectra of H<sup>+<sup/>PANHs are significantly different owing to the NH inplane bending vibration, which generally couples very well with the aromatic CH bending and CC stretching modes. Implications of the NPAH (+, H<sup>+<sup/>) laboratory spectra are discussed for the astrophysical IR emissions and, in particular, for the band at 6.2 <i>μ<i/>m.