Theoretical infrared spectra of large polycyclic aromatic hydrocarbons

Abstract

Theoretical and experimental spectroscopic studies have underlined the contribution of large PAHs towards the astrophysical mid-infrared emission bands. Quantum chemical study of eight large PAHs using density functional theory approach is reported along with their infrared spectra. Systematic variation of bands with PAH size is noted and a better agreement with the observed astrophysical bands is obtained. Compared to small and medium sized PAHs there is substantial C–H stretch intensity in the cation spectra. This is attributed to smaller change in charge on the hydrogens upon ionization. For the C–H out-of-plane mode large PAHs correlate well with observed features on the shorter wavelength side of the 11.2 μ m band. Presence of two sub-components of the broad 7.7 μ m band in large PAHs compares very well with the corresponding astrophysical band and point to the abundance of large PAH cations in interstellar environments. The data presented here may be used for a more detailed study on the profile variations accompanying the mid-IR bands in various interstellar environments.