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.
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. https://doi.org/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 = {Thu Sep 06 00:00:00 EDT 2018},
month = {Thu Sep 06 00:00:00 EDT 2018}
}
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