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  • Title: Interstellar polycyclic aromatic hydrocarbons: the infrared emission bands, the excitation/emission mechanism, and the astrophysical implications.
    Author: Allamandola LJ, Tielens AG, Barker JR.
    Journal: Astrophys J Suppl Ser; 1989 Dec; 71():733-75. PubMed ID: 11542189.
    Abstract:
    This article presents a comprehensive treatment of the polycyclic aromatic hydrocarbon (PAH) hypothesis. The interstellar, infrared spectral features which have been attributed to emission from highly vibrationally excited PAHs are discussed in detail. These include major (most intense) bands at 3040, 1615, "1310," 1150, and 885 cm-1 (3.29, 6.2 "7.7," 8.7, and 11.3 micrometers), minor bands and broad features in the 3200-2700 cm-1 [correction of 3200-2700-1] (3.1-3.7 micrometers), 1600-1100 cm-1 (6.0-9 micrometers) and 910-770 cm-1 (11-13 micrometers) regions, as well as the vibrational quasi-continuum spanning the entire mid-IR and the electronic transitions which contribute to the high-frequency IR continuum. All the major and minor bands, as well as the quasi-continuum, can be attributed to vibrational transitions in molecular-sized PAHs. The latter two broad features probably arise from very large PAHs, PAH clusters, and amorphous carbon particles. A precise match of the interstellar spectra with laboratory spectra is not yet possible because laboratory spectra are not available of PAHs in the forms probably present in the interstellar medium (completely isolated, ionized, some completely dehydrogenated, and containing between about 20 and 40 carbon atoms). The method with which one can calculate the IR fluorescence spectrum from a vibrationally excited molecule is also described in detail. Fluorescence band intensities, relaxation rates, and dependence on molecule size and energy content are treated explicitly. Analysis of the interstellar spectra indicates that the PAHs which dominate the infrared spectra contain between about 20 and 40 carbon atoms. The results obtained with this method are compared with the results obtained using a thermal approximation. It is shown that for high levels of vibrational excitation and emission from low-frequency modes, the two methods give similar results. However, at low levels of vibrational excitation and for the high-frequency modes (for example, the 3040 cm-1, 3.3 micrometers band), the thermal approach overestimates the emission intensities. For calculations of molecular reactions (such as H-loss, deuterium enrichment, and carbon skeleton rearrangement) a thermal approximation is invalid. The relationship between PAH molecules and amorphous carbon particles is presented and their production in circumstellar shells is described. The most likely interstellar PAH molecular structures are discussed and the possibility of destructive reactions with interstellar oxygen and hydrogen atoms is considered in detailed and found to be unimportant. Interstellar PAH size and abundance estimates are made. On the order of a few percent of the available interstellar carbon is tied up in the small (20-40 carbon atom) PAHs which are responsible for the sharp features, and a similar amount is tied up in the larger (200-500 carbon atom) PAHs or PAH clusters and amorphous carbon particles which are responsible for the broad components underlying the 1600-1100 and 900-770 cm-1 (6-9 and 11-13 micrometers) regions. It is shown that the spectroscopic structure these PAHs and PAH-related materials produce in the UV portion of the interstellar extinction curve lie just below current detection limits but fall in the range detectable by the Hubble Space Telescope. Finally, the influence of PAH charge on the ultraviolet, visible, and infrared regions is described.
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