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Title: Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth

Abstract

Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering–reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical–chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.

Authors:
ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468885
Alternate Identifier(s):
OSTI ID: 1477324
Report Number(s):
[SAND-2018-10657J]
[Journal ID: ISSN 0036-8075; /sci/361/6406/997.atom]
Grant/Contract Number:  
[AC02-05CH11231; AC04-94AL85000]
Resource Type:
Published Article
Journal Name:
Science
Additional Journal Information:
[Journal Name: Science Journal Volume: 361 Journal Issue: 6406]; Journal ID: ISSN 0036-8075
Publisher:
American Association for the Advancement of Science (AAAS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Johansson, K. O., Head-Gordon, M. P., Schrader, P. E., Wilson, K. R., and Michelsen, H. A. Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth. United States: N. p., 2018. Web. doi:10.1126/science.aat3417.
Johansson, K. O., Head-Gordon, M. P., Schrader, P. E., Wilson, K. R., & Michelsen, H. A. Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth. United States. doi:10.1126/science.aat3417.
Johansson, K. O., Head-Gordon, M. P., Schrader, P. E., Wilson, K. R., and Michelsen, H. A. Thu . "Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth". United States. doi:10.1126/science.aat3417.
@article{osti_1468885,
title = {Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth},
author = {Johansson, K. O. and Head-Gordon, M. P. and Schrader, P. E. and Wilson, K. R. and Michelsen, H. A.},
abstractNote = {Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering–reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical–chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.},
doi = {10.1126/science.aat3417},
journal = {Science},
number = [6406],
volume = [361],
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1126/science.aat3417

Citation Metrics:
Cited by: 52 works
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    Works referencing / citing this record:

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