Interstellar PAH emission in the 11-14 micron region: new insights from laboratory data and a tracer of ionized PAHs

The Ames infrared spectral database of isolated, neutral and ionized polycyclic aromatic hydrocarbons (PAHS) shows that aromatic CH out-of-plane bending frequencies are significantly shifted upon ionization. For solo- and duet-CH groups, the shift is pronounced and consistently toward higher frequencies. The solo-CH modes are blueshifted by an average of 27 cm-1 and the duet-CH modes by an average of 17 cm-1. For trio- and quartet-CH groups, the ionization shifts of the out-of-plane modes are more erratic and typically more modest. As a result of these ionization shifts, the solo-CH out-of-plane modes move out of the region classically associated with these vibrations in neutral PAHS, falling instead at frequencies well above those normally attributed to out-of-plane bending, vibrations of any type. In addition, for the compact PAHs studied, the duet-CH out-of-plane modes are shifted into the frequency range traditionally associated with the solo-CH modes. These results refine our understanding of the origin of the dominant interstellar infrared emission feature near 11.2 microns, whose envelope has traditionally been attributed only to the out-of-plane bending of solo-CH groups on PAHS, and provide a natural explanation for the puzzling emission feature near 11.0 microns within the framework of the PAH model. Specifically, the prevalent but variable long-wavelength wing or shoulder that is often observed near 11.4 microns likely reflects the contributions of duet-CH units in PAH cations. Also, these results indicate that the emission between 926 and 904 cm-1 (10.8 and 11.1 microns) observed in many sources can be unambiguously attributed to the out-of-plane wagging, of solo-CH units in moderately sized (fewer than 50 carbon atom) PAH cations, making this emission an unequivocal tracer of ionized interstellar PAHS.