THE INFRARED SPECTROSCOPY OF COMPACT POLYCYCLIC AROMATIC HYDROCARBONS CONTAINING UP TO 384 CARBONS

Abstract

The mid- and the far-infrared spectra of polycyclic aromatic hydrocarbons (PAHs) have been computed using density functional theory. This study has focused on PAHs in the highly symmetric, compact, coronene family with sizes up to 384 carbons. We have identified trends in the peak position and intrinsic strength of the vibrational modes of these species and compared these to trends previously reported for less symmetric and smaller PAHs. The computed spectral modes have been used to calculate the IR emission spectrum of PAHs pumped by UV photons. The results have been compared to observed interstellar spectra to elucidate the characteristics of the interstellar PAH family. The calculations show that highly symmetric PAHs are very stable and, hence, might be favored under the harsh conditions of interstellar space. Our calculated vibrational properties confirm and extend previous studies for small PAHs to the large compact PAHs studied here, specifically in terms of the dependence of the spectral characteristics on ionization and on H-adjacency. The calculations show that for PAHs larger than 150 carbons, the 6.3 μm feature becomes very broad and shifts to longer wavelengths, the 8.6 μm band becomes stronger than the "7.7" μm band, and the 11.0/12.7 band strength ratio gets too large compared with observations. Thus, PAHs with 150 carbons or more are unlikely to be the dominant species in interstellar space. The simplicity of the observed spectra in the 15–20 μm range points toward a preponderance of compact PAHs in the interstellar PAH family.