Study of vibrational spectra of polycyclic aromatic hydrocarbons with phenyl side group

Abstract

Computational study of polycyclic aromatic hydrocarbons (PAHs) with phenyl side group substituted at different positions is reported. The infrared spectral variations due to the position of phenyl substitution, ionization state and the size of the molecules are discussed and possible contribution of phenyl-PAHs to the mid-infrared emission features from astrophysical objects is analysed. Structurally phenyl group substitution at 2nd position gives more stable species compared to substitution at other positions. Phenyl-PAHs exhibit new aromatic bands near 695 and 741 cm−1 (14.4 and 13.5μm), due to contribution from quintet CH wag, that compare well with minor features at 14.2 and 13.5μm observed in several astrophysical objects. Just as in plain PAHs, the C–C stretch vibrational modes (∼1600 cm−1) have negligible intensity in neutrals, but the cations of all phenyl-PAHs exhibit significantly strong phenyl group C–C stretch peak close to class B type 6.2μm astrophysical band. In 2-phenylpyrene, it is the neutral molecule that exhibits this strong feature in the 6.2μm range along with other features that match with sub-features at 6.66 and 6.9μm, observed in astronomical spectra of some late type objects. The substitution of phenyl side group at solo position shifts the C–C stretch mode of parent PAH close to the region of 6.2μm astrophysical band. The results indicate possibility of phenyl-PAHs in space and the bottom-up formation of medium sized compact PAHs with phenyl side group in carbon rich cool circumstellar shells. Phenyl-PAHs need to be considered in modelling mid-infrared emission spectra of various astrophysical objects.