Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K

Frankcombe, Terry J. and Smith, Sean C. (2002) Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K. Faraday Discussions, 119 159-171. doi:10.1039/b102562g


Author Frankcombe, Terry J.
Smith, Sean C.
Title Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K
Journal name Faraday Discussions   Check publisher's open access policy
ISSN 1364-5498
1359-6640
0301-7249
Publication date 2002
Sub-type Article (original research)
DOI 10.1039/b102562g
Open Access Status Not Open Access
Volume 119
Start page 159
End page 171
Total pages 13
Place of publication London, United Kingdom
Publisher Royal Society of Chemistry
Collection year 2001
Language eng
Abstract Computational simulations of the title reaction are presented, covering a temperature range from 300 to 2000 K. At lower temperatures we find that initial formation of the cyclopropene complex by addition of methylene to acetylene is irreversible, as is the stabilisation process via collisional energy transfer. Product branching between propargyl and the stable isomers is predicted at 300 K as a function of pressure for the first time. At intermediate temperatures (1200 K), complex temporal evolution involving multiple steady states begins to emerge. At high temperatures (2000 K) the timescale for subsequent unimolecular decay of thermalized intermediates begins to impinge on the timescale for reaction of methylene, such that the rate of formation of propargyl product does not admit a simple analysis in terms of a single time-independent rate constant until the methylene supply becomes depleted. Likewise, at the elevated temperatures the thermalized intermediates cannot be regarded as irreversible product channels. Our solution algorithm involves spectral propagation of a symmetrised version of the discretized master equation matrix, and is implemented in a high precision environment which makes hitherto unachievable low-temperature modelling a reality.
Keyword Chemistry, physical
Unimolecular reactions
Thermal-decomposition
Rate coefficients
Energy-transfer
Multiple-well
Isomerization
Propargyl
System
Acetylene
Radicals
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 19 times in Thomson Reuters Web of Science Article | Citations
Google Scholar Search Google Scholar
Created: Tue, 14 Aug 2007, 15:48:42 EST