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Fullerenes have recently been detected in various circumstellar and interstellar environments, raising the question of their formation pathway. It has been proposed that they can form at the low densities found in the interstellar medium by the photo-chemical processing of large polycyclic aromatic hydrocarbons (PAHs). Following our previous work on the evolution of PAHs in the NGC 7023 reflection nebula, we evaluate, using photochemical modelling, the possibility that the PAH C66H20 (i.e. circumovalene) can lead to the formation of the C60 fullerene upon irradiation by ultraviolet photons. The chemical pathway involves full dehydrogenation of C66H20, folding into a floppy closed cage and shrinking of the cage by loss of C2 units until it reaches the symmetric C60 molecule. At 10'' from the illuminating star and with realistic molecular parameters, the model predicts that 100% of C66H20 is converted into C60 in ~105 yr, a timescale comparable to the age of the nebula. Shrinking appears to be the kinetically limiting step of the whole process. Hence, PAHs larger than C66H20 are unlikely to contribute significantly to the formation of C60, while PAHs containing between 60 and 66 C atoms should contribute to the formation of C60 with shorter timescales, and PAHs containing fewer than 60 C atoms will be destroyed. Assuming a classical size distribution for the PAH precursors, our model predicts that absolute abundances of C60 are up to several 10-4 of the elemental carbon, that is, less than a percent of the typical interstellar PAH abundance, which is consistent with observational studies. According to our model, once formed, C60 can survive much longer (>107 yr for radiation fields below G0 = 104) than other fullerenes because of the remarkable stability of the C60 molecule at high internal energies. Hence, a natural consequence is that C60 is more abundant than other fullerenes in highly irradiated environments. [ABSTRACT FROM AUTHOR]

Context. Clusters of polycyclic aromatic hydrocarbons (PAHs) have been proposed as candidates for evaporating very small grains, which are thought to be precursors of free-flying PAHs. Evaporation rates have been calculated so far only for species containing up to a few 100-C atoms, whereas interstellar PAH clusters could contain up to ~1000 C atoms. Aims. We present a method that generalises the calculation of the statistical evaporation rate of large PAH clusters and provides rates for species containing up to ~1000 C-atoms. Methods. The evaporation of non-rotating neutral homo-molecular PAH clusters containing up to 12 molecules from a family of highly symmetric compact PAHs is studied. Statistical calculations were performed and completed with molecular dynamics simulations at high internal energies to provide absolute values for the evaporation rate and distributions of kinetic energy released. The calculations used explicit atom-atom Lennard-Jones potentials in the rigid molecule approximation. A new method is proposed to take both interand intra-molecular vibrations into account. Results.Without any parameter adjustment, the calculated evaporation rates agree well with available experimental data.We find that the non-rotation assumption has a limited impact on the evaporation rates. The photostability of PAH clusters increases dramatically with the size of molecules in the clusters, and to a lesser extent with the number of molecules in the clusters. For values of the UV radiation field that are typical of the regions where evaporating very small grains are observed, the smallest clusters in this study (~50 C-atoms) are found to be quickly photo-evaporated, whereas the largest clusters (~1000 C-atoms) are photostable. Conclusions. Our results support the idea that large PAH clusters are good candidates for evaporating very small grains. [ABSTRACT FROM AUTHOR]

Context. Various studies have emphasised variations in the charge state and composition of the interstellar polycyclic aromatic hydrocarbon (PAH) population in photodissociation regions (PDRs). These changes are expected to affect the energetics and chemistry in these regions, thereby calling for a quantitative description. Aims. We aim to model the spatial evolution of the charge and hydrogenation states of PAHs in PDRs. We focus on the specific case of the north-west (NW) PDR of NGC 7023, for which many observational constraints are available. We also discuss the case of the diffuse interstellar medium (ISM). Methods. We modelled the physical conditions in NGC 7023 NW using a state-of-the-art PDR code. We then used a new PAH chemical evolution model that includes recent experimental data on PAHs and describes multiphoton events. We considered a family of compact PAHs bearing up to 96 carbon atoms. Results. The calculated ionization ratio is in good agreement with the observed ratio in NGC 7023 NW. Within the PDR, PAHs evolve into three major populations. We find medium-sized PAHs (50 ≲ NC ≳ 90) to be normally hydrogenated, while larger PAHs (NC & 90) can be superhydrogenated, and smaller species (NC ≲ 50) are fully dehydrogenated. In the more diffuse gas of the cavity, where the fullerene C60 has recently been detected, all the studied PAHs are found to be quickly fully dehydrogenated. PAH chemical evolution exhibits a complex non-linear behaviour as a function of the UV radiation field because of multiphoton events. Steady state for hydrogenation is reached on timescales ranging from less than a year for small PAHs, up to 104 years for large PAHs at AV = 1. Critical reactions that would need more studies are the recombination of cations with electrons, the reactivity of cations with H2, and the reactivity of neutral PAHs with H. Conclusions. We have developed a new model of PAH chemical evolution based on the most recent available molecular data. This model allows us to rationalise the observational constraints without any fitting parameter. PAHs smaller than 50 carbon atoms are not expected to survive in the NGC 7023 NW PDR. A similar conclusion is obtained for the diffuse ISM. Carbon clusters turn out to be end products of PAH photodissociation, and the evolution of these clusters needs to be investigated further to evaluate their impact on the chemical and physical evolution of PDRs. [ABSTRACT FROM AUTHOR]

Context. In photo-dissociation regions (PDRs), polycyclic aromatic hydrocarbons (PAHs) may be produced by evaporation of very small grains (VSGs) by the impinging UV radiation field from a nearby star. Aims. We quantitatively investigate the transition zone between evaporating VSGs (eVSGs) and PAHs in several PDRs. Methods. We studied the relative contribution of PAHs and eVSGs to the mid-IR emission in a wide range of excitation conditions. We fitted the observed mid-IR emission of PDRs by using a set of template band emission spectra of PAHs, eVSGs, and gas lines. The fitting tool PAHTAT (PAH Toulouse Astronomical Templates) is made available to the community as an IDL routine. From the results of the fit, we derived the fraction of carbon feVSG locked in eVSGs and compared it to the intensity of the local UV radiation field. Results. We show a clear decrease of feVSG with increasing intensity of the local UV radiation field, which supports the scenario of photo-destruction of eVSGs. Conversely, this dependence can be used to quantify the intensity of the UV radiation field for different PDRs, including unresolved ones. Conclusions. PAHTAT can be used to trace the intensity of the local UV radiation field in regions where eVSGs evaporate, which correspond to relatively dense (nH = [100,105] cm-3) and UV irradiated PDRs (G0 = [100,5 × 104] ) where H2 emits in rotational lines. [ABSTRACT FROM AUTHOR]

An active carbon chemistry is observed at the border of photo-dissociation regions (PDRs), involving small hydrocarbons, polycyclic aromatic hydrocarbon (PAH) macromolecules and evaporating very small grains (VSGs). In this context, we aim at quantifying the physical and chemical evolution of PAHs (hydrogenation and charge states, aggregation, and complexation with heavy atoms) as a function of the local physical conditions (radiation field, temperature, density, abundances of atomic and molecular hydrogen, electrons and heavy atoms). We have developed a numerical model that follows the time dependency of the abundance and internal energy of each species. In this paper, we use this model to calculate the hydrogenation and charge states of coronene C24H12 as an interstellar PAH prototype. We take advantage of recent results on photodissociation and reaction rates and provide guidelines for future laboratory studies. Reaction rates of coronene-derived radical cations with H and H2 are found to be sufficiently constrained by experiments, whereas the absence of experimental data for neutral species is critical. [ABSTRACT FROM AUTHOR]

The analysis of mid-IR emission suggests that a population of PAH-related very small grains containing a few hundreds of atoms are present in the deep regions of molecular clouds, although no specific species has been identified yet. In this review, we discuss several candidates for these grains: neutral and ionised PAH clusters and complexes of PAHs with Si atoms. The theoretical modelling of the properties of such molecular complexes or nanograins is a challenging task. We first present an overview of quantum chemistry derived models which can be efficiently used on-the-fly in extensive sampling of the potential energy surfaces, as required by structural optimization, classical molecular dynamics or Monte Carlo algorithms. From the simulations, various observables can be determined, such as the binding energies, finite temperature IR spectra, nucleation and evaporation rates. We discuss the relevance of those candidates in the molecular clouds photodissociation regions and propose constrains and perspectives for the nature and size of those very small grains. [ABSTRACT FROM AUTHOR]