Transformation of amorphous carbon clusters to fullerenes

Transformation of amorphous carbon clusters into fullerenes under high temperature is studied using molecular dynamics simulations at microsecond times. Based on the analysis of both structure and energy of the system, it is found that fullerene formation occurs in two stages. Firstly, fast transformation of the initial amorphous structure into a hollow sp$^2$ shell with a few chains attached occurs with a considerable decrease of the potential energy and the number of atoms belonging to chains and to the amorphous domain. Then, insertion of remaining carbon chains into the sp$^2$ network takes place at the same time with the fullerene shell formation. Two types of defects remaining after the formation of the fullerene shell are revealed: 7-membered rings and single one-coordinated atoms. One of the fullerene structures obtained contains no defects at all, which demonstrates that defect-free carbon cages can be occasionally formed from amorphous precursors directly without defect healing. No structural changes are observed after the fullerene formation, suggesting that defect healing is a slow process in comparison with the fullerene shell formation. The schemes of the revealed reactions of chain atoms insertion into the fullerene shell just before its completion are presented. The results of the performed simulations are summarized within the paradigm of fullerene formation due to selforganization of the carbon system.Comment: 35 pages, 9 figure

Infrared Study of Fullerene Planetary Nebulae

We present a study of 16 PNe where fullerenes have been detected in their Spitzer spectra. This large sample of objects offers an unique opportunity to test conditions of fullerene formation and survival under different metallicity environments as we are analyzing five sources in our own Galaxy, four in the LMC, and seven in the SMC. Among the 16 PNe under study, we present the first detection of C60 (possibly also C70) fullerenes in the PN M 1-60 as well as of the unusual 6.6, 9.8, and 20 um features (possible planar C24) in the PN K 3-54. Although selection effects in the original samples of PNe observed with Spitzer may play a potentially significant role in the statistics, we find that the detection rate of fullerenes in C-rich PNe increases with decreasing metallicity (5% in the Galaxy, 20% in the LMC, and 44% in the SMC). CLOUDY photoionization modeling matches the observed IR fluxes with central stars that display a rather narrow range in effective temperature (30,000-45,000 K), suggesting a common evolutionary status of the objects and similar fullerene formation conditions. The observed C60 intensity ratios in the Galactic sources confirm our previous finding in the MCs that the fullerene emission is not excited by the UV radiation from the central star. CLOUDY models also show that line- and wind-blanketed model atmospheres can explain many of the observed [NeIII]/[NeII] ratios by photoionization suggesting that possibly the UV radiation from the central star, and not shocks, are triggering the decomposition of the circumstellar dust grains. With the data at hand, we suggest that the most likely explanation for the formation of fullerenes and graphene precursors in PNe is that these molecular species are built from the photo-chemical processing of a carbonaceous compound with a mixture of aromatic and aliphatic structures similar to that of HAC dust.Comment: Accepted for publication in ApJ (43 pages, 11 figures, and 4 tables). Small changes to fit the proof-corrected article to be published in Ap

On the Excitation and Formation of Circumstellar Fullerenes

We compare and analyze the Spitzer mid-infrared spectrum of three fullerene-rich planetary nebulae in the Milky Way and the Magellanic Clouds; Tc1, SMP SMC16, and SMP LMC56. The three planetary nebulae share many spectroscopic similarities. The strongest circumstellar emission bands correspond to the infrared active vibrational modes of the fullerene species C60 and little or no emission is present from Polycyclic Aromatic Hydrocarbons (PAHs). The strength of the fullerene bands in the three planetary nebulae is very similar, while the ratio of the [NeIII]15.5um/[NeII]12.8um fine structure lines, an indicator of the strength of the radiation field, is markedly different. This raises questions about their excitation mechanism and we compare the fullerene emission to fluorescent and thermal models. In addition, the spectra show other interesting and common features, most notably in the 6-9um region, where a broad plateau with substructure dominates the emission. These features have previously been associated with mixtures of aromatic/aliphatic hydrocarbon solids. We hypothesize on the origin of this band, which is likely related to the fullerene formation mechanism, and compare it with modeled Hydrogenated Amorphous Carbon that present emission in this region.Comment: 13 pages, 2 tables, 7 figures, Accepted for publication in Ap

The Formation of Fullerenes in Planetary Nebulae

In the last decade, fullerenes have been detected in a variety of astrophysical environments, with the majority being found in planetary nebulae. Laboratory experiments have provided us with insights into the conditions and pathways that can lead to fullerene formation, but it is not clear precisely what led to the formation of astrophysical fullerenes in planetary nebulae. We review some of the available evidence, and propose a mechanism where fullerene formation in planetary nebulae is the result of a two-step process where carbonaceous dust is first formed under unusual conditions; then, the fullerenes form when this dust is being destroyed

Constraints on Exotic Heavily Ionizing Particles from the Geological Abundance of Fullerenes

The C_{60} molecule exhibits a remarkable stability and inertness that leads to its survival in ancient carbonaceous rocks initially subject to the high temperatures requisite for its formation. Elementary particles having very high electronic stopping powers can similarly form C_{60} and higher fullerenes in their wake. Combined, these two features point at the possibility of using the C_{60} presence (or absence) in selected bulk geological samples as a new type of solid-state nuclear track detector, with applications in astro-particle physics.Comment: Final version (few modifications). Phys. Rev. Lett. (in press). 4 pages LaTeX, 1 eps figure embedde

Formation of fullerenes in H-containing Planetary Nebulae

Hydrogen depleted environments are considered an essential requirement for the formation of fullerenes. The recent detection of C60 and C70 fullerenes in what was interpreted as the hydrogen-poor inner region of a post-final helium shell flash Planetary Nebula (PN) seemed to confirm this picture. Here, we present evidence that challenges the current paradigm regarding fullerene formation, showing that it can take place in circumstellar environments containing hydrogen. We report the simultaneous detection of Polycyclic Aromatic Hydrocarbons (PAHs) and fullerenes towards C-rich and H-containing PNe belonging to environments with very different chemical histories such as our own Galaxy and the Small Magellanic Cloud. We suggest that PAHs and fullerenes may be formed by the photochemical processing of hydrogenated amorphous carbon. These observations suggest that modifications may be needed to our current understanding of the chemistry of large organic molecules as well as the chemical processing in space.Comment: accepted for publication in The Astrophysical Journal Letters (14 pages, 4 figures and 1 Table). Replaced version with slight changes in the abstrac