Interstellar molecules are thought to build up in the shielded environment of molecular clouds or in the envelope of evolved stars. This follows many sequential reaction steps of atoms and simple molecules in the gas phase and/or on (icy) grain surfaces. However, these chemical routes are highly inefficient for larger species in the tenuous environment of space as many steps are involved and, indeed, models fail to explain the observed high abundances. This is definitely the case for the C 60 fullerene, recently identified as one of the most complex molecules in the interstellar medium. Observations have shown that, in some PDRs, its abundance increases close to strong UV-sources. In this letter we report laboratory findings in which C 60 formation can be explained by characterizing the photochemical evolution of large PAHs. Sequential H losses lead to fully dehydrogenated PAHs and subsequent losses of C 2 units convert graphene into cages. Our results present for the first time experimental evidence that PAHs in excess of 60 C-atoms efficiently photo-isomerize to Buckminsterfullerene, C 60 . These laboratory studies also attest to the importance of top-down synthesis routes for chemical complexity in space.

Polycyclic aromatic hydrocarbons (PAHs) constitute a major component of the interstellar medium carbon budget, locking up to 10-20% of the elemental carbon. Sequential fragmentation induced by energetic photons leads to the formation of new species, including fullerenes. However, the exact chemical routes involved in this process remain largely unexplored. In this work, we focus on the first photofragmentation steps, which involve the dehydrogenation of these molecules. For this, we consider a multidisciplinary approach, taking into account the results from experiments, density functional theory (DFT) calculations, and modeling using dedicated Monte-Carlo simulations. By considering the simplest isomerization pathways -i.e., hydrogen roaming along the edges of the moleculewe are able to characterize the most likely photodissociation pathways for the molecules studied here. These comprise nine PAHs with clearly different structural properties. The formation of aliphatic-like side groups is found to be critical in the first fragmentation step and, furthermore, sets the balance of the competition between H-and H 2 -loss. We show that the presence of trio hydrogens, especially in combination with bay regions in small PAHs plays an important part in the experimentally established variations in the odd-to-even H-atom loss ratios. In addition, we find that, as PAH size increases, H 2 formation becomes dominant, and sequential hydrogen loss only plays a marginal role. We also find disagreements between experiments and calculations for large, solo containing PAHs, which need to be accounted for. In order to match theoretical and experimental results, we have modified the energy barriers and restricted the H-hopping to tertiary atoms. The formation of H 2 in large PAHs upon irradiation appears to be the dominant fragmentation channel, suggesting an efficient formation path for molecular hydrogen in photodissociation regions (PDRs).

Interstellar Polycyclic Aromatic Hydrocarbons (PAH) are expected to be strongly processed by Vacuum Ultra-Violet (VUV) photons. Here, we report experimental studies on the ionization and fragmentation of coronene (CH), ovalene (CH) and hexa-peri-hexabenzocoronene (HBC; CH) 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 (ISM) are briefly discussed.

The diffuse cm wave IR-correlated signal, the 'anomalous' CMB foreground, is thought to arise in the dust in cirrus clouds. We present Cosmic Background Imager (CBI) cm wave data of two translucent clouds, ζ Oph and LDN 1780 with the aim of characterizing the anomalous emission in the translucent cloud environment.In ζ Oph, the measured brightness at 31 GHz is 2.4σ higher than an extrapolation from 5-GHz measurements assuming a free-free spectrum on 8 arcmin scales. The SED of this cloud on angular scales of 1• is dominated by free-free emission in the cm range. In LDN 1780 we detected a 3σ excess in the SED on angular scales of 1• that can be fitted using a spinning dust model. In this cloud, there is a spatial correlation between the CBI data and IR images, which trace dust. The correlation is better with near-IR templates (IRAS 12 and 25 µm) than with IRAS 100 µm, which suggests a very small grain origin for the emission at 31 GHz.We calculated the 31-GHz emissivities in both clouds. They are similar and have intermediate values between that of cirrus clouds and dark clouds. Nevertheless, we found an indication of an inverse relationship between emissivity and column density, which further supports the VSGs origin for the cm emission since the proportion of big relative to small grains is smaller in diffuse clouds.

Emission bands from polycyclic aromatic hydrocarbons (PAHs) dominate the mid-infrared spectra of a wide variety of astronomical sources, encompassing nearly all stages of stellar evolution. Despite their similarities, details in band positions and shapes have allowed a classification of PAH emission to be developed. It has been suggested that this classification is in turn associated with the degree of photoprocessing of PAHs. Over the past decade, a more complete picture of the PAH interstellar life-cycle has emerged, in which a wide range of PAH species are formed during the later stages of stellar evolution. After this they are photoprocessed, increasing the relative abundance of the more stable (typically larger and compact) PAHs. For this work we have tested the effect of the symmetry, size, and structure of PAHs on their fragmentation pattern and infrared spectra by combining experiments at the free electron laser for infrared experiments (FELIX) and quantum chemical computations. Applying this approach to the cations of four molecular species, perylene (C 20 H 12 ), peropyrene (C 26 H 14 ), ovalene (C 32 H 14 ) and isoviolanthrene (C 34 H 18 ), we find that a reduction of molecular symmetry causes the activation of vibrational modes in the 7-9 µm range. We show that the IR characteristics of less symmetric PAHs can help explain the broad band observed in the class D spectra, which are typically associated with a low degree of photoprocessing. Such large, nonsymmetrical irregular PAHs are currently largely missing from the NASA Ames PAH database. The band positions and shapes of the largest more symmetric PAH measured here, show the best resemblance with class A and B sources, representative of regions with high radiation fields and thus heavier photoprocessing. Furthermore, the dissociation patterns observed in the mass spectra hint to an enhanced stability of the carbon skeleton in more symmetric PAHs with respect to the irregular and less symmetric species, which tend to loose carbon containing units. Although not a direct proof, these findings are fully in line with the grandPAH hypothesis, which claims that symmetric large PAHs can survive as the radiation field increases, while their less symmetric counterparts are destroyed or converted to symmetric PAHs.