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Detailed chemical kinetic modeling of JP‐10 ( exo ‐tetrahydrodicyclopentadiene) high‐temperature oxidation: Exploring the role of biradical species in initial decomposition steps
Author(s) -
Magoon Gregory R.,
AguileraIparraguirre Jorge,
Green William H.,
Lutz Jesse J.,
Piecuch Piotr,
Wong HsiWu,
Oluwole Oluwayemisi O.
Publication year - 2012
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20702
Subject(s) - disproportionation , chemistry , complete active space , intramolecular force , computational chemistry , decomposition , thermal decomposition , density functional theory , stereochemistry , organic chemistry , catalysis , basis set
The initial pathways of JP‐10 ( exo ‐tetrahydrodicyclopentadiene) decomposition are expected to have a significant effect on combustion and pyrolysis behavior of the fuel, affecting, for example, product distribution and ignition delay. Modeling of JP‐10 decomposition should capture these initial decomposition processes as accurately as possible. Two classes of computational approaches have been applied to study intramolecular disproportionation—an important class of reactions in the initial stages of JP‐10 decomposition: (1) the second‐order, multiconfigurational, quasidegenerate perturbation theory employing the complete active space self‐consistent field (CASSCF) reference; and (2) the size‐extensive, left‐eigenstate, completely renormalized (CR) coupled‐cluster (CC) method with singles, doubles, and noniterative triples, termed CR‐CC(2,3), capable of describing reaction pathways involving biradicals. Applying higher levels of theory to points along the CASSCF reaction paths, the barriers to intramolecular disproportionation are much smaller and some barriers appear to vanish. The conventional ring‐opening + disproportionation pathway is compared with an alternative concerted reaction pathway. Overall, this investigation has yielded insights into alkyl disproportionation and ring‐opening reactions that may be of more general use in chemical kinetic modeling. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 179–193, 2012