The C--H Stretching Features at 3.2--3.5 Micrometer of Polycyclic Aromatic Hydrocarbons with Aliphatic Sidegroups

Abstract

The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 micrometer are ubiquitously seen in a wide variety of astrophysical regions. The UIE features are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, e.g., polycyclic aromatic hydrocarbon (PAH) molecules. The 3.3 micrometer aromatic C--H stretching feature is often accompanied by a weaker feature at 3.4 micrometer. The latter is often thought to result from the C--H stretch of aliphatic groups attached to the aromatic systems. The ratio of the observed intensity of the 3.3 micrometer aromatic C--H feature to that of the 3.4 micrometer aliphatic C--H feature allows one to estimate the aliphatic fraction of the UIE carriers, provided that the intrinsic oscillator strengths of the 3.3 micrometer aromatic C--H stretch (A3.3) and the 3.4 micrometer aliphatic C--H stretch (A3.4) are known. While previous studies on the aliphatic fraction of the UIE carriers were mostly based on the A3.4/A3.3 ratios derived from the mono-methyl derivatives of small PAH molecules, in this work we employ density functional theory to compute the infrared vibrational spectra of several PAH molecules with a wide range of sidegroups including ethyl, propyl, butyl, and several unsaturated alkyl chains, as well as all the isomers of dimethyl-substituted pyrene. We find that, except PAHs with unsaturated alkyl chains, the corresponding A3.4/A3.3 ratios are close to that of mono-methyl PAHs. This confirms the predominantly-aromatic nature of the UIE carriers previously inferred from the A3.4/A3.3 ratio derived from mono-methyl PAHs.