Absolute evaporation rates of non-rotating neutral PAH clusters

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. 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. 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 inter- and intra-molecular vibrations into account. 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. Our results support the idea that large PAH clusters are good candidates for evaporating very small grains.Comment: 13 pages, 10 figure

Detection of the buckminsterfullerene cation (C60+) in space

In the early 90s, C60+ was proposed as the carrier of two diffuse interstellar bands (DIBs) at 957.7 and 963.2 nm, but a firm identification still awaits gas-phase spectroscopic data. Neutral C60, on the other hand, was recently detected through its infrared emission bands in the interstellar medium and evolved stars. In this contribution, we present the detection of C60+ through its infrared vibrational bands in the NGC 7023 nebula, based on spectroscopic observations with the Spitzer space telescope, quantum chemistry calculation, and laboratory data from the literature. This detection supports the idea that C60+ could be a DIB carrier, and provides robust evidence that fullerenes exist in the gas-phase in the interstellar medium. Modeling efforts to design specific observations, combined with new gas-phase data, will be essential to confirm this proposal. A definitive attribution of the 957.7 and 963.2 nm DIBs to C60+ would represent a significant step forward in the field.Comment: To appear in "Proceedings of IAU 297 symposium on the Diffuse Interstellar Bands", eds. J. Cami and N. Cox (5 pages

Evolution of PAHs in photodissociation regions: Hydrogenation and charge states

Various studies have emphasized variations of the charge state and composition of the interstellar polycyclic aromatic hydrocarbon (PAH) population in photodissociation regions (PDRs). 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 and also discuss the case of the diffuse interstellar medium (ISM). The physical conditions in NGC 7023 NW are modelled using a state-of-the-art PDR code. We then use a new PAH chemical evolution model that includes recent experimental data on PAHs and describes multiphoton events. We consider a family of compact PAHs bearing up to 96 carbon atoms. The calculated ionization ratio is in good agreement with observations in NGC 7023 NW. Within the PDR, PAHs evolve into three major populations: medium-sized PAHs (50<Nc<90) are normally hydrogenated, larger PAHs (Nc>90) can be superhydrogenated, and smaller species (Nc<50) are fully dehydrogenated. In the cavity, where the fullerene C60 was recently 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 10000 years for large PAHs at Av=1. We identified critical reactions that need more studies. Our new model allows us to rationalize 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.Comment: 16 pages, 10 figures; Accepted for publication in A&

Top-down formation of fullerenes in the interstellar medium

[Abridged] Fullerenes have been recently detected in various circumstellar and interstellar environments, raising the question of their formation pathway. It has been proposed that they can form 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 modeling, the possibility that the PAH C$_{66}$H$_{20}$ (i.e. circumovalene) can lead to the formation of C$_{60}$ upon irradiation by ultraviolet photons. The chemical pathway involves full dehydrogenation, folding into a floppy closed cage and shrinking of the cage by loss of C$_2$ units until it reaches the symmetric C$_{60}$ molecule. At 10" from the illuminating star and with realistic molecular parameters, the model predicts that 100% of C$_{66}$H$_{20}$ is converted into C$_{60}$ in $\sim$ 10$^5$ years, 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 C$_{66}$H$_{20}$ are unlikely to contribute significantly to the formation of C$_{60}$, while PAHs containing between 60 and 66 C atoms should contribute to the formation of C$_{60}$ with shorter timescales, and PAHs containing less than 60 C atoms will be destroyed. Assuming a classical size distribution for the PAH precursors, our model predicts absolute abundances of C$_{60}$ are up to several $10^{-4}$ of the elemental carbon, i.e. less than a percent of the typical interstellar PAH abundance, which is consistent with observational studies. According to our model, once formed, C$_{60}$ can survive much longer than other fullerenes because of the remarkable stability of the C$_{60}$ molecule at high internal energies.Hence, a natural consequence is that C$_{60}$ is more abundant than other fullerenes in highly irradiated environments.Comment: Accepted for publication in A&A. Latest version contains the corrected version of Fig.

Blind Signal Separation Methods for the Identification of Interstellar Carbonaceous Nanoparticles

The use of Blind Signal Separation methods (ICA and other approaches) for the analysis of astrophysical data remains quite unexplored. In this paper, we present a new approach for analyzing the infrared emission spectra of interstellar dust, obtained with NASA's Spitzer Space Telescope, using FastICA and Non-negative Matrix Factorization (NMF). Using these two methods, we were able to unveil the source spectra of three different types of carbonaceous nanoparticles present in interstellar space. These spectra can then constitute a basis for the interpretation of the mid-infrared emission spectra of interstellar dust in the Milky Way and nearby galaxies. We also show how to use these extracted spectra to derive the spatial distribution of these nanoparticles

The infrared signatures of very small grains in the Universe seen by JWST

The near- and mid-IR spectrum of many astronomical objects is dominated by emission bands due to UV-excited polycyclic aromatic hydrocarbons (PAH) and evaporating very small grains (eVSG). Previous studies with the ISO, Spitzer and AKARI space telescopes have shown that the spectral variations of these features are directly related to the local physical conditions that induce a photo-chemical evolution of the band carriers. Because of the limited sensitivity and spatial resolution, these studies have focused mainly on galactic star-forming regions. We discuss how the advent of JWST will allow to extend these studies to previously unresolved sources such as near-by galaxies, and how the analysis of the infrared signatures of PAHs and eVSGs can be used to determine their physical conditions and chemical composition.Comment: To appear in the Proceedings of the annual meeting of the French society of astronomy and astrophysics (SF2A 2015

Evaporating Very Small Grains as tracers of the UV radiation field in Photo-dissociation Regions

Context. In photo-dissociation regions (PDRs), Polycyclic Aromatic Hydrocarbons (PAHs) could be produced by evaporation of Very Small Grains (VSGs) by the impinging UV radiation field from a nearby star. Aims. We investigate quantitatively the transition zone between evaporating Very Small Grains (eVSGs) and PAHs in several PDRs. Methods. We study the relative contribution of PAHs and eVSGs to the mid-IR emission in a wide range of excitation conditions. We fit 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 derive the fraction of carbon f_eVSG locked in eVSGs and compare it to the intensity of the local UV radiation field. Results. We show a clear decrease of f_eVSG 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 non resolved 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, 10^5 ] cm-3) and UV irradiated PDRs (G0 = [100, 5x10^4]) where H2 emits in rotational lines.Comment: 13 pages, 11 figures. Accepted for publication in A&A. Typos correcte

Mixed aliphatic and aromatic composition of evaporating very small grains in NGC 7023 revealed by the 3.4/3.3 μ\mum ratio

In photon-dominated regions (PDRs), UV photons from nearby stars lead to the evaporation of very small grains (VSGs) and the production of gas-phase polycyclic aromatic hydrocarbons (PAHs). Our goal is to achieve better insight into the composition and evolution of evaporating very small grains (eVSGs) and PAHs through analyzing the infrared (IR) aliphatic and aromatic emission bands. We combined spectro-imagery in the near- and mid-IR to study the spatial evolution of the emission bands in the prototypical PDR NGC 7023. We used near-IR spectra obtained with AKARI to trace the evolution of the 3.3$\mu$m and 3.4$\mu$m bands, which are associated with aromatic and aliphatic C-H bonds on PAHs. The spectral fitting involves an additional broad feature centred at 3.45$\mu$m. Mid-IR observations obtained with Spitzer are used to discriminate the signatures of eVSGs, neutral and cationic PAHs. We correlated the spatial evolution of all these bands with the intensity of the UV field to explore the processing of their carriers. The intensity of the 3.45$\mu$m plateau shows an excellent correlation with that of the 3.3$\mu$m aromatic band (correlation coefficient R = 0.95), indicating that the plateau is dominated by the emission from aromatic bonds. The ratio of the 3.4$\mu$m and 3.3$\mu$m band intensity ($I_{3.4}/I_{3.3}$) decreases by a factor of 4 at the PDR interface from the more UV-shielded to the more exposed layers. The transition region between the aliphatic and aromatic material is found to correspond spatially with the transition zone between neutral PAHs and eVSGs. We conclude that the photo-processing of eVSGs leads to the production of PAHs with attached aliphatic sidegroups that are revealed by the 3.4$\mu$m emission band. Our analysis provides evidence for the presence of very small grains of mixed aromatic and aliphatic composition in PDRs.Comment: Accepted for publication in A&A. Abstract abridged, language editing applied in v