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Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures

Abstract

For the past decades, the hydrogen-abstraction/acetylene-addition (HACA) mechanism has been instrumental in attempting to untangle the origin of polycyclic aromatic hydrocarbons (PAHs) as identified in carbonaceous meteorites such as Allende and Murchison. However, the fundamental reaction mechanisms leading to the synthesis of PAHs beyond phenanthrene (C14H10) are still unknown. By exploring the reaction of the 4-phenanthrenyl radical (C14H9) with acetylene (C2H2) under conditions prevalent in carbon-rich circumstellar environments, we show evidence of a facile, isomer-selective formation of pyrene (C16H10). Along with the hydrogen-abstraction/vinylacetylene-addition (HAVA) mechanism, molecular mass growth processes from pyrene may lead through systematic ring expansions not only to more complex PAHs, but ultimately to 2D graphene-type structures. These fundamental reaction mechanisms are crucial to facilitate an understanding of the origin and evolution of the molecular universe and, in particular, of carbon in our Galaxy.

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Fig. 1: Possible structures of isomers of aromatic molecules detected in carbonaceous meteorites.
Fig. 2: Vacuum ultraviolet photoionization mass spectra.
Fig. 3: Photoionization efficiency (PIE) curves for m/z = 202 and 203. The black curves are experimentally derived PIE curves, with the grey area defining the error.
Fig. 4: Potential energy surface (PES) for the 4-phenanthrenyl (C14H9) reaction with acetylene (C2H2) calculated at the G3(MP2,CC)//B3LYP/6-311 G(d,p) level of theory.
Fig. 5: Molecular mass growth processes to PAHs involving HACA and HAVA.

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Acknowledgements

This work was supported by the US Department of Energy, Basic Energy Sciences DE-FG02-03ER15411 (experimental studies), DE-FG02-04ER15570 (computational studies) and DE-SC0010409 (synthesis of precursor molecules) to the University of Hawaii, to Florida International University, and the University of California Berkeley, respectively. M.A., U.A., B.X. and the experiments at the chemical dynamics beamline at the ALS were supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231, through the Gas Phase Chemical Physics Program, Chemical Sciences Division. D.J. acknowledges support through a National Science Foundation Graduate Research Fellowship under grant no. DGE-1106400. The authors also thank X. Tielens (University of Leiden, The Netherlands) for helpful discussions.

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D.J. and G.V. synthesized the molecular precursor; L.Z., B.X. and U.A. carried out the experimental measurements; L.Z. performed the data analysis; A.M.M. carried out the theoretical analysis; R.I.K., A.M.M. and M.A. discussed the data; F.R.F. supervised the synthesis of the molecular precursor; and R.I.K. designed the experiments and wrote the manuscript.

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Correspondence to Ralf I. Kaiser.

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Zhao, L., Kaiser, R.I., Xu, B. et al. Pyrene synthesis in circumstellar envelopes and its role in the formation of 2D nanostructures. Nat Astron 2, 413–419 (2018). https://doi.org/10.1038/s41550-018-0399-y

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