We present 15-20 um spectral maps towards the reflection nebula NGC2023 obtained with the Infrared Spectrograph in short-wavelength, high-resolution mode on board the Spitzer Space Telescope. These spectra reveal emission from PAHs, C60, and H2 super
posed on a dust continuum. These emission components exhibit distinct spatial distributions: with increasing distance from the illuminating star, we observe the PAH emission followed by the dust continuum emission and the H2 emission. The C60 emission is located closest to the illuminating star in the south while in the north, it seems to be associated with the H/H2 transition. Emission from PAHs and PAH-related species produce features at 15.8, 16.4, 17.4, and 17.8 um and the 15-18 um plateau. These different PAH features show distinct spatial distributions. The 15.8 um band and 15-18 um plateau correlate with the 11.2 um PAH band and with each other, and are attributed to large, neutral PAHs. Conversely, the 16.4 um feature correlates with the 12.7 um PAH band, suggesting that both arise from species that are favored by the same conditions that favor PAH cations. The PAH contribution to the 17.4 um band is displaced towards the illuminating star with respect to the 11.2 and 12.7 um emission and is assigned to doubly ionized PAHs and/or a subset of cationic PAHs. The spatial distribution of the 17.8 um band suggests it arises from both neutral and cationic PAHs. In contrast to their intensities, the profiles of the PAH bands and the 15-18 um plateau do not vary spatially. Consequently, we conclude that the carrier of the 15-18 um plateau is distinct from that of the PAH bands.
The infrared spectra of many galactic and extragalactic objects are dominated by emission features at 3.3, 6.2, 7.7, 8.6 and 11.2 mu m. The carriers of these features remained a mystery for almost a decade, hence the bands were dubbed the unidentifie
d infrared (UIR) bands. Since the mid-80s, the UIR bands are generally attributed to the IR fluorescence of Polycyclic Aromatic Hydrocarbon molecules (PAHs) upon absorption of UV photons -- the PAH hypothesis. Here we review the progress made over the past 25 years in understanding the UIR bands and their carriers.
The mid-IR spectra of six large, irregular PAHs with formulae (C84H24 - C120H36) have been computed using Density Functional Theory (DFT). Trends in the dominant band positions and intensities are compared to those of large, compact PAHs as a functio
n of geometry, size and charge. Irregular edge moieties that are common in terrestrial PAHs, such as bay regions and rings with quartet hydrogens, are shown to be uncommon in astronomical PAHs. As for all PAHs comprised solely of C and H reported to date, mid-IR emission from irregular PAHs fails to produce a strong CCstr band at 6.2 um, the position characteristic of the important, class A astronomical PAH spectra. Earlier studies showed inclusion of nitrogen within a PAH shifts this to 6.2 um for PAH cations. Here we show this band shifts to 6.3 um in nitrogenated PAH anions, close to the position of the CC stretch in class B astronomical PAH spectra. Thus nitrogenated PAHs may be important in all sources and the peak position of the CC stretch near 6.2 um appears to directly reflect the PAH cation to anion ratio. Large irregular PAHs exhibit features at 7.8 um but lack them near 8.6 um. Hence, the 7.7 um astronomical feature is produced by a mixture of small and large PAHs while the 8.6 um band can only be produced by large compact PAHs. As with the CCstr, the position and profile of these bands reflect the PAH cation to anion ratio.
The mid-infrared spectra of large PAHs ranging from C54H18 to C130H28 are determined computationally using Density Functional Theory. Trends in the band positions and intensities as a function of PAH size, charge and geometry are discussed. Regarding
the 3.3, 6.3 and 11.2 micron bands similar conclusions hold as with small PAHs. This does not hold for the other features. The larger PAH cations and anions produce bands at 7.8 micron and, as PAH sizes increases, a band near 8.5 micron becomes prominent and shifts slightly to the red. In addition, the average anion peak falls slightly to the red of the average cation peak. The similarity in behavior of the 7.8 and 8.6 micron bands with the astronomical observations suggests that they arise from large, cationic and anionic PAHs, with the specific peak position and profile reflecting the PAH cation to anion concentration ratio and relative intensities of PAH size. Hence, the broad astronomical 7.7 micron band is produced by a mixture of small and large PAH cations and anions, with small and large PAHs contributing more to the 7.6 and 7.8 micron component respectively. For the CH out-of-plane vibrations, the duo hydrogens couple with the solo vibrations and produce bands that fall at wavelengths slightly different than their counterparts in smaller PAHs. As a consequence, previously deduced PAH structures are altered in favor of more compact and symmetric forms. In addition, the overlap between the duo and trio bands may reproduce the blue-shaded 12.8 micron profile.
