DOI: 10.1073/pnas.1113827108. Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium

Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium

10.1073/pnas.1113827108

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are regarded as key molecules in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest prototype—naphthalene (C 10 H 8 )—has remained an open question. Here, we show in a combined crossed beam and theoretical study that naphthalene can be formed in the gas phase via a barrierless and exoergic reaction between the phenyl radical (C 6 H 5 ) and vinylacetylene (CH 2 = CH-C ≡ CH) involving a van-der-Waals complex and submerged barrier in the entrance channel. Our finding challenges conventional wisdom that PAH-formation only occurs at high temperatures such as in combustion systems and implies that low temperature chemistry can initiate the synthesis of the very first PAH in the interstellar medium. In cold molecular clouds, barrierless phenyl-type radical reactions could propagate the vinylacetylene-mediated formation of PAHs leading to more complex structures like phenanthrene and anthracene at temperatures down to 10 K.

Bibliography

Parker, D. S. N., Zhang, F., Kim, Y. S., Kaiser, R. I., Landera, A., Kislov, V. V., Mebel, A. M., & Tielens, A. G. G. M. (2011). Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium. Proceedings of the National Academy of Sciences, 109(1), 53â58.

Authors 8

Dorian S. N. Parker (first)
Fangtong Zhang (additional)
Y. Seol Kim (additional)
Ralf I. Kaiser (additional)
Alexander Landera (additional)
Vadim V. Kislov (additional)
Alexander M. Mebel (additional)
A. G. G. M. Tielens (additional)

References 57 Referenced 219

10.1016/S0273-1177(97)00349-9
10.1073/pnas.0609396104
10.1017/S0074180900164939
10.1088/0004-637X/702/1/301
10.1086/307978
10.1039/b516323d
10.1039/b517676j
10.1146/annurev-astro-082708-101654
10.1146/annurev.aa.27.090189.001113
10.1073/pnas.0912157107
10.1146/annurev.astro.46.060407.145211
10.1073/pnas.0602277103
10.1051/eas/1146019
10.1142/p562
10.1016/j.gca.2004.09.009
10.1073/pnas.0801860105
10.1016/S0010-2180(99)00135-2
10.1086/167501
10.1021/j100095a033
10.1086/172059
10.1016/S0010-2180(97)00068-0
10.1016/j.proci.2010.06.159
10.1016/S0082-0784(00)80673-6
10.1021/jp200201c
10.1016/S0010-2180(02)00347-4
10.1086/592349
ER Micelotta, AP Jones, AGGM Tielens, Polycyclic aromatic hydrocarbon processing in a hot gas. Astron Astrophys 510, A37/1–A37/14 (2010). / Astron Astrophys / Polycyclic aromatic hydrocarbon processing in a hot gas by Micelotta ER (2010)
ER Micelotta, AP Jones, AGGM Tielens, Polycyclic aromatic hydrocarbon processing in interstellar shocks. Astron Astrophys 510, A36/1–A36/14 (2010). / Astron Astrophys / Polycyclic aromatic hydrocarbon processing in interstellar shocks by Micelotta ER (2010)
10.1051/0004-6361/201015741
10.1051/eas/1146017
10.1086/185519
10.1088/0004-637X/699/1/585
10.1039/c003599h
PJ Linstrom WG Mallard NIST Chemistry WebBook. NIST Chemistry WebBook NIST Standard Reference Database Number 69.
RD Levine Molecular Reaction Dynamics and Chemical Reactivity (Oxford University Press, Oxford), pp. 140–141 (1987). / Molecular Reaction Dynamics and Chemical Reactivity by Levine RD (1987)
10.1021/ct0500491
10.1021/jp049950n
10.1039/b600721j
10.1016/j.proci.2004.08.127
T Allain, S Leach, E Sedlmayr, Photodestruction of PAHs in the interstellar medium. I. Photodissociation rates for the loss of an acetylenic group. Astron Astrophys 305, 602–615 (1996). / Astron Astrophys / Photodestruction of PAHs in the interstellar medium. I. Photodissociation rates for the loss of an acetylenic group by Allain T (1996)
10.1021/jp053218m
10.1086/376587
10.1051/0004-6361:20021849
10.1016/j.combustflame.2009.06.001
10.1073/pnas.1012468108
10.1063/1.1423945
10.1086/303834
10.1086/587734
10.1088/0067-0049/181/2/543
10.1063/1.464913
10.1103/PhysRevB.37.785
10.1063/1.478676
10.1016/S0009-2614(99)01126-4
10.1063/1.477422
MJ Frisch et al. Gaussian 98 revision A11 (Gaussian Inc. PA 1998).
H-J Werner MOLPRO version 2006.1 (University College Cardiff Consultants Ltd United Kingdom 2006).
MJ Frisch Gaussian 09 revision A.02 (Gaussian Inc. CT 2009).

Dates

Type	When
Created	13 years, 8 months ago (Dec. 23, 2011, 1:22 a.m.)
Deposited	3 years, 4 months ago (April 15, 2022, 2:58 a.m.)
Indexed	2 days, 21 hours ago (Sept. 3, 2025, 6:35 a.m.)
Issued	13 years, 8 months ago (Dec. 22, 2011)
Published	13 years, 8 months ago (Dec. 22, 2011)
Published Online	13 years, 8 months ago (Dec. 22, 2011)
Published Print	13 years, 8 months ago (Jan. 3, 2012)

Funders 0

None

BibTeX

@article{Parker_2011, title={Low temperature formation of naphthalene and its role in the synthesis of PAHs (Polycyclic Aromatic Hydrocarbons) in the interstellar medium}, volume={109}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.1113827108}, DOI={10.1073/pnas.1113827108}, number={1}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Parker, Dorian S. N. and Zhang, Fangtong and Kim, Y. Seol and Kaiser, Ralf I. and Landera, Alexander and Kislov, Vadim V. and Mebel, Alexander M. and Tielens, A. G. G. M.}, year={2011}, month=dec, pages={53–58} }

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