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تسجيل مستخدم جديدLaboratory Photo-chemistry of PAHs: Ionization versus Fragmentation
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Interstellar polycyclic aromatic hydrocarbons (PAHs) are expected to be strongly processed by vacuum ultraviolet photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C24H12), ovalene (C32H14) and hexa-peri-hexabenzocoronene (HBC; C42H18) cations by exposure to synchrotron radiation in the range of 8--40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs, fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium are briefly discussed.
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The fullerene C$_{60}$, one of the largest molecules identified in the interstellar medium (ISM), has been proposed to form top-down through the photo-chemical processing of large (more than 60 C-atoms) polycyclic aromatic hydrocarbon (PAH) molecules
. In this article, we focus on the opposite process, investigating the possibility that fullerenes form from small PAHs, in which bowl-forming plays a central role. We combine laboratory experiments and quantum chemical calculations to study the formation of larger PAHs from charged fluorene clusters. The experiments show that with visible laser irradiation, the fluorene dimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{9}$]$^+$ - and the fluorene trimer cation - [C$_{13}$H$_{9}$$-$C$_{13}$H$_{8}$$-$C$_{13}$H$_{9}$]$^+$ - undergo photo-dehydrogenation and photo-isomerization resulting in bowl structured aromatic cluster-ions, C$_{26}$H$_{12}$$^+$ and C$_{39}$H$_{20}$$^+$, respectively. To study the details of this chemical process, we employ quantum chemistry that allows us to determine the structures of the newly formed cluster-ions, to calculate the hydrogen loss dissociation energies, and to derive the underlying reaction pathways. These results demonstrate that smaller PAH clusters (with less than 60 C-atoms) can convert to larger bowled geometries that might act as building blocks for fullerenes, as the bowl-forming mechanism greatly facilitates the conversion from dehydrogenated PAHs to cages. Moreover, the bowl-forming induces a permanent dipole moment that - in principle - allows to search for such species using radio astronomy.
Besides buckminsterfullerene (C60), other fullerenes and their derivatives may also reside in space. In this work, we study the formation and photo-dissociation processes of astronomically relevant fullerene/anthracene (C14H10) cluster cations in the
gas phase. Experiments are carried out using a quadrupole ion trap (QIT) in combination with time-of-flight (TOF) mass spectrometry. The results show that fullerene (C60, and C70)/anthracene (i.e., [(C14H10)nC60]+ and [(C14H10)nC70]+), fullerene (C56 and C58)/anthracene (i.e., [(C14H10)nC56]+ and [(C14H10)nC58]+) and fullerene (C66 and C68)/anthracene (i.e., [(C14H10)nC66]+ and [(C14H10)nC68]+) cluster cations, are formed in the gas phase through an ion-molecule reaction pathway. With irradiation, all the fullerene/anthracene cluster cations dissociate into mono$-$anthracene and fullerene species without dehydrogenation. The structure of newly formed fullerene/anthracene cluster cations and the bonding energy for these reaction pathways are investigated with quantum chemistry calculations. Our results provide a growth route towards large fullerene derivatives in a bottom-up process and insight in their photo-evolution behavior in the ISM, and clearly, when conditions are favorable, fullerene/PAH clusters can form efficiently. In addition, these clusters (from 80 to 154 atoms or ~ 2 nm in size) offer a good model for understanding the physical-chemical processes involved in the formation and evolution of carbon dust grains in space, and provide candidates of interest for the DIBs that could motivate spectroscopic studies.
Polycyclic aromatic hydrocarbons (PAHs) are key species in astrophysical environments in which vacuum ultraviolet (VUV) photons are present, such as star-forming regions. The interaction with these VUV photons governs the physical and chemical evolut
ion of PAHs. Models show that only large species can survive. However, the actual molecular properties of large PAHs are poorly characterized and the ones included in models are only an extrapolation of the properties of small and medium-sized species. We discuss here experiments performed on trapped ions including some at the SOLEIL VUV beam line DESIRS. We focus on the case of the large dicoronylene cation, C48H20+ , and compare its behavior under VUV processing with that of smaller species. We suggest that C2H2 is not a relevant channel in the fragmentation of large PAHs. Ionization is found to largely dominate fragmentation. In addition, we report evidence for a hydrogen dissociation channel through excited electronic states. Although this channel is minor, it is already effective below 13.6 eV and can significantly influence the stability of astro-PAHs. We emphasize that the competition between ionization and dissociation in large PAHs should be further evaluated for their use in astrophysical models.
Aim. We investigate the role of PAHs as a sink for deuterium in the interstellar medium and study UV photolysis as a potential process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various
isotopologues of D-enriched, protonated anthracene and phenanthrene ions was recorded in a FTICR mass spectrometer. IRMPD spectroscopy using FELIX provided the IR spectra that were compared to DFT vibrational spectra; reaction barriers and rates were also calculated and related to the product abundances. Results. The mass spectra for both UV and IRMPD photolysis show the loss of H from [D-C$_{14}$H$_{10}$]$^+$, whereas [H-C$_{14}$D$_{10}$]$^+$ shows a strong preference for D loss. Calculations reveal facile 1,2-H and -D shift reactions, with barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes in the 2 PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The $sim$0.1 eV difference in zero-point energy between C-H and C-D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D. Conclusion. Scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to an aromatic site, protecting it from elimination. This could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C-HD group on solo sites might be responsible for the majority of aliphatic C-D stretching bands seen in astronomical spectra.
We show results from the radiation hydrodynamics (RHD) simulations of tidal disruption of a star on a parabolic orbit by a supermassive black hole (SMBH) based on a three-dimensional smoothed particle hydrodynamics code with radiative transfer. We fi
nd that such a tidally disrupted star fragment and form clumps soon after its tidal disruption. The fragmentation results from the endothermic processes of ionization and dissociation that reduce the gas pressure, leading to local gravitational collapse. Radiative cooling is less effective because the stellar debris is still highly optically thick in such an early time. Our simulations reveal that a solar-type star with a stellar density profile of n=3 disrupted by a 10^6 solar mass black hole produces $sim20$ clumps of masses in the range of 0.1 to 12 Jupiter masses. The mass fallback rate decays with time, with pronounced spikes from early to late time. The spikes provide evidence for the clumps of the returning debris, while the clumps on the unbound debris can be potentially freely-floating planets and brown dwarfs. This ionization and dissociation induced fragmentation on a tidally disrupted star are a promising candidate mechanism to form low-mass stars to planets around an SMBH.
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