Computational study of neutral and cationic pericondensed polycyclic aromatic hydrocarbons

Abstract

Quantum chemical calculations using density functional theory are presented for small to medium sized pericondensed PAHs including some being reported for the first time. Bond lengths and charge distribution have been computed for these PAHs in both neutral and cationic forms. Upon ionization, significant change in fractional charge on atoms is present particularly for the outer carbon atoms. The charge on the internal carbon atoms tends towards zero in cations. Vibrational frequencies and infrared intensities have been calculated for the optimized structures of PAH neutrals and cations. The drastic intensity alterations occurring upon ionization are discussed and related to specific changes occurring in the charge distribution. The C–H stretch intensity depends on the partial charge on peripheral hydrogen atoms and reduces in cations as hydrogen atoms become more positive. Pericondensed PAHs show better matching with the observed interstellar infrared bands. The co-added model spectra show profiles similar to the observed astrophysical bands.