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.

30 years of cosmic fullerenes

In 1985, "During experiments aimed at understanding the mechanisms by which long-chain carbon molecules are formed in interstellar space and circumstellar shells", Harry Kroto and his collaborators serendipitously discovered a new form of carbon: fullerenes. The most emblematic fullerene (i.e. C$_{60}$ "buckminsterfullerene"), contains exactly 60 carbon atoms organized in a cage-like structure similar to a soccer ball. Since their discovery impacted the field of nanotechnologies, Kroto and colleagues received the Nobel prize in 1996. The cage-like structure, common to all fullerene molecules, gives them unique properties, in particular an extraordinary stability. For this reason and since they were discovered in experiments aimed to reproduce conditions in space, fullerenes were sought after by astronomers for over two decades, and it is only recently that they have been firmly identified by spectroscopy, in evolved stars and in the interstellar medium. This identification offers the opportunity to study the molecular physics of fullerenes in the unique physical conditions provided by space, and to make the link with other large carbonaceous molecules thought to be present in space : polycyclic aromatic hydrocarbons.Comment: To appear in the Proceedings of the annual meeting of the French society of astronomy and astrophysics (SF2A 2015

Polycyclic aromatic hydrocarbons and molecular hydrogen in oxygen-rich planetary nebulae: the case of NGC6720

Evolved stars are primary sources for the formation of polycyclic aromatic hydrocarbons (PAHs) and dust grains. Their circumstellar chemistry is usually designated as either oxygen-rich or carbon-rich, although dual-dust chemistry objects, whose infrared spectra reveal both silicate- and carbon-dust features, are also known. The exact origin and nature of this dual-dust chemistry is not yet understood. Spitzer-IRS mid-infrared spectroscopic imaging of the nearby, oxygen-rich planetary nebula NGC6720 reveals the presence of the 11.3 micron aromatic (PAH) emission band. It is attributed to emission from neutral PAHs, since no band is observed in the 7 to 8 micron range. The spatial distribution of PAHs is found to closely follow that of the warm clumpy molecular hydrogen emission. Emission from both neutral PAHs and warm H2 is likely to arise from photo-dissociation regions associated with dense knots that are located within the main ring. The presence of PAHs together with the previously derived high abundance of free carbon (relative to CO) suggest that the local conditions in an oxygen-rich environment can also become conducive to in-situ formation of large carbonaceous molecules, such as PAHs, via a bottom-up chemical pathway. In this scenario, the same stellar source can enrich the interstellar medium with both oxygen-rich dust and large carbonaceous molecules.Comment: Accepted by MNRAS. 5 page

Extended Red Emission and the evolution of carbonaceaous nanograins in NGC 7023

Extended Red Emission (ERE) was recently attributed to the photo-luminescence of either doubly ionized Polycyclic Aromatic Hydrocarbons (PAH$^{++}$), or charged PAH dimers. We analysed the visible and mid-infrared (mid-IR) dust emission in the North-West and South photo-dissociation regions of the reflection nebula NGC 7023.Using a blind signal separation method, we extracted the map of ERE from images obtained with the Hubble Space Telescope, and at the Canada France Hawaii Telescope. We compared the extracted ERE image to the distribution maps of the mid-IR emission of Very Small Grains (VSGs), neutral and ionized PAHs (PAH$^0$ and PAH$^+$) obtained with the Spitzer Space Telescope and the Infrared Space Observatory. ERE is dominant in transition regions where VSGs are being photo-evaporated to form free PAH molecules, and is not observed in regions dominated by PAH$^+$. Its carrier makes a minor contribution to the mid-IR emission spectrum. These results suggest that the ERE carrier is a transition species formed during the destruction of VSGs. Singly ionized PAH dimers appear as good candidates but PAH$^{++}$ molecules seem to be excluded.Comment: Accepted for publication in A&

Laboratory studies of polycyclic aromatic hydrocarbons: the search for interstellar candidates

Polycyclic Aromatic Hydrocarbons (PAHs) are considered as a major constituent of interstellar dust. They have been proposed as the carriers of the Aromatic Infrared Bands (AIBs) observed in emission in the mid-IR. They likely have a significant contribution to various features of the extinction curve such as the 220 nm bump,the far-UV rise and the diffuse interstellar bands. Emission bands are also expected in the far-IR, which are better fingerprints of molecular identity than the AIBs. They will be searched for with the Herschel Space Observatory. Rotational emission is also expected in the mm range for those molecules which carry significant dipole moments. Despite spectroscopic studies in the laboratory, no individual PAH species could be identified. This emphasises the need for an investigation on where interstellar PAHs come from and how they evolve due to environmental conditions: ionisation and dissociation upon UV irradiation, interactions with electrons, gas and dust. There is also evidence for PAH species to contribute to the depletion of heavy atoms from the gas phase, in particular Si and Fe. This paper illustrates how laboratory work can be inspired from observations. In particular there is a need for understanding the chemical properties of PAHs and PAH-related species, including very small grains, in physical conditions that mimic those found in interstellar space. This motivates a joint effort between astrophysicists, physicists and chemists. Such interdisciplinary studies are currently performed, taking advantage of the PIRENEA set-up, a cold ion trap dedicated to astrochemistry.Comment: to appear in "Cosmic Dust - Near and Far", Th. Henning, E. Grun, J. Steinacker (eds.

Formation of buckminsterfullerene (C60) in interstellar space

Buckminsterfullerene (C60) was recently confirmed to be the largest molecule identified in space. However, it remains unclear how, and where this molecule is formed. It is generally believed that C60 is formed from the build up of small carbonaceous compounds, in the hot and dense envelopes of evolved stars. Analyzing infrared observations, obtained by Spitzer and Herschel, we found that C60 is efficiently formed in the tenuous and cold environment of an interstellar cloud illuminated by strong ultraviolet (UV) radiation fields. This implies that another formation pathway, efficient at low densities, must exist. Based on recent laboratory and theoretical studies, we argue that Polycyclic Aromatic Hydrocarbons are converted into graphene, and subsequently C60, under UV irradiation from massive stars. This shows that alternative - top-down - routes are key to understanding the organic inventory in space.Comment: 22 pages, 4 figures, 3 sup. figures, 1 sup. vide

Time Resolved Correlation measurements of temporally heterogeneous dynamics

Time Resolved Correlation (TRC) is a recently introduced light scattering technique that allows to detect and quantify dynamic heterogeneities. The technique is based on the analysis of the temporal evolution of the speckle pattern generated by the light scattered by a sample, which is quantified by $c\_I(t,\tau)$, the degree of correlation between speckle images recorded at time $t$ and $t+\tau$. Heterogeneous dynamics results in significant fluctuations of $c\_I(t,\tau)$ with time $t$. We describe how to optimize TRC measurements and how to detect and avoid possible artifacts. The statistical properties of the fluctuations of $c\_I$ are analyzed by studying their variance, probability distribution function, and time autocorrelation function. We show that these quantities are affected by a noise contribution due to the finite number $N$ of detected speckles. We propose and demonstrate a method to correct for the noise contribution, based on a $N\to \infty$ extrapolation scheme. Examples from both homogeneous and heterogeneous dynamics are provided. Connections with recent numerical and analytical works on heterogeneous glassy dynamics are briefly discussed.Comment: 19 pages, 15 figures. Submitted to PR

On the fine vertical structure of the low troposphere over the coastal margins of East Antarctica

In this study, 8 years of high-resolution radiosonde data at nine Antarctic stations are analysed to provide the first large-scale characterization of the fine vertical structure of the low troposphere up to 3&thinsp;km altitude over the coastal margins of East Antarctica. Radiosonde data show a large spatial variability of wind, temperature and humidity profiles, with different features between stations in katabatic regions (e.g., Dumont d'Urville and Mawson stations), stations over two ice shelves (Neumayer and Halley stations) and regions with complex orography (e.g., McMurdo). At the Dumont d'Urville, Mawson and Davis stations, the yearly median wind speed profiles exhibit a clear low-level katabatic jet. During precipitation events, the low-level flow generally remains of continental origin and its speed is even reinforced due to the increase in the continent–ocean pressure gradient. Meanwhile, the relative humidity profiles show a dry low troposphere, suggesting the occurrence of low-level sublimation of precipitation in katabatic regions but such a phenomenon does not appreciably occur over the ice shelves near Halley and Neumayer. Although ERA-Interim and ERA5 reanalyses assimilate radiosoundings at most stations considered here, substantial – and sometimes large – low-level wind and humidity biases are revealed but ERA5 shows overall better performance. A free simulation with the regional polar version of the Weather Research and Forecasting model (Polar WRF) (at a 35&thinsp;km resolution) over the entire continent shows too-strong and too-shallow near-surface jets in katabatic regions especially in winter. This may be a consequence of an underestimated coastal cold air bump and associated sea–continent pressure gradient force due to the coarse 35&thinsp;km resolution of the Polar WRF simulation. Beyond documenting the vertical structure of the low troposphere over coastal East Antarctica, this study gives insights into the reliability and accuracy of two major reanalysis products in this region on the Earth. The paper further underlines the difficulty of modeling the low-level flow over the margins of the ice sheet with a state-of-the-art atmospheric model.</p

Polycyclic aromatic hydrocarbons with SPICA

Thanks to high sensitivity and angular resolution and broad spectral coverage, SPICA will offer a unique opportunity to better characterize the nature of polycyclic aromatic hydrocarbons (PAHs) and very small grains (VSGs), to better use them as probes of astrophysical environments. The angular resolution will enable to probe the chemical frontiers in the evolution process from VSGs to neutral PAHs, to ionized PAHs and to "Grand-PAHs" in photodissotiation regions and HII regions, as a function of G$_0$/n (UV radiation field / density). High sensitivity will favor the detection of the far-IR skeletal emission bands of PAHs, which provide specific fingerprints and could lead to the identification of individual PAHs. This overall characterization will allow to use PAH and VSG populations as tracers of physical conditions in spatially resolved protoplanetary disks and nearby galaxies (using mid-IR instruments), and in high redshift galaxies (using the far-IR instrument), thanks to the broad spectral coverage SPICA provides. Based on our previous experience with ISO and Spitzer we discuss how these goals can be reached.Comment: To appear in Proc. Workshop "The Space Infrared Telescope for Cosmology & Astrophysics: Revealing the Origins of Planets and Galaxies". Eds. A.M. Heras, B. Swinyard, K. Isaak, and J.R. Goicoeche