ON THE ELECTRONIC STRUCTURE OF ISOLATED MONO-DEHYDROGENATED POLYAROMATIC HYDROCARBON IONS AND THEIR ASTROPHYSICAL RELEVANCE
- FOM Institute for Plasma Physics 'Rijnhuizen', Edisonbaan 14, 3439MN Nieuwegein (Netherlands)
The attribution of the unidentified infrared bands to polycyclic aromatic hydrocarbon (PAH) molecules is a key argument for their abundant occurrence in interstellar environments, which has important implications for interstellar chemistry. In contrast to terrestrial conditions, their transient forms are of importance in the low-density astrophysical environments. Here, the gas-phase IR spectra of three PAH molecules in a carbocation state (naphthyl{sup +}, C{sub 10}H{sub 7}{sup +}; phenanthryl{sup +}, C{sub 14}H{sub 9}{sup +}; and pyrenyl{sup +}, C{sub 16}H{sub 9}{sup +}) are investigated by action spectroscopy methods using an infrared free electron laser and an ion-trap mass spectrometer. The IR spectra of the mono-dehydrogenated PAH{sup +} (aryl) ions in the 6-18 {mu}m spectral range are compared to computed IR spectra for various structural isomers of the aryl ions; the comparison indicates that the most stable structures under isolated conditions have a triplet electronic configuration. Electronic structure calculations on systems as large as the mono-dehydrogenated circumcoronene cation (C{sub 54}H{sub 17}{sup +}) provide further evidence for the higher stability of a triplet state as compared with the singlet state. Moreover, the gas-phase IR spectra reveal that the IR signatures of a PAH cation before and after H-atom loss are very similar, in particular in the 6-9 {mu}m region involving the skeletal CC stretching modes, so that triplet mono-dehydrogenated PAH ions are similarly compliant with the general match between PAH mid-IR features and the interstellar unidentified infrared emissions. The establishment of a triplet electronic ground state suggests that interstellar scenarios should consider the possible influence of triplet aromatic chemistry as well as the possible influence of the altered optical properties of triplet PAH species.
- OSTI ID:
- 22011766
- Journal Information:
- Astrophysical Journal, Vol. 746, Issue 1; Other Information: Country of input: International Atomic Energy Agency (IAEA); ISSN 0004-637X
- Country of Publication:
- United States
- Language:
- English
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