A master equation model for bimolecular reaction via multi-well isomerization intermediates

Frankcombe, Terry J., Smith, Sean C., Gates, Kevin E. and Robertson, Struan H. (2000) A master equation model for bimolecular reaction via multi-well isomerization intermediates. Physical chemistry chemical physics, 2 4: 793-803. doi:10.1039/a908180a


Author Frankcombe, Terry J.
Smith, Sean C.
Gates, Kevin E.
Robertson, Struan H.
Title A master equation model for bimolecular reaction via multi-well isomerization intermediates
Journal name Physical chemistry chemical physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2000-01-01
Sub-type Article (original research)
DOI 10.1039/a908180a
Open Access Status Not Open Access
Volume 2
Issue 4
Start page 793
End page 803
Total pages 11
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Abstract A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.
Keyword Potential-energy surface
Chemical activation
Activated unimolecular reactions
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Physical Sciences Publications
 
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