Ab initio studies of the isomerization and decomposition reactions of the 1-butoxy radical

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Abstract

The unimolecular reactions of the 1-butoxy radical, a prototype of atmospherically important alkoxy radicals, are studied. The structures of the isomers of the C4H9O radical and the transition structures of the isomerization and main decomposition reactions of 1-butoxy are determined by ab initio quantum chemical methods. The energy-dependent rate coefficients of the unimolecular reactions involved were obtained in RRKM calculations. The threshold energy for the fastest channel, the 1,5 intramolecular H-atom transfer is 8.12, 9.23, 9.16, and 9.51 kcal mol-1 according to the MP-SAC2, BAC-MP4, DFT, and an additively corrected MP4 method, respectively. For the β-C-C dissociation reaction we found a barrier of 16.03, 13.34, and 12.39 kcal mol-1 at the BAC-MP4, DFT, and additively corrected MP4 level. The barrier height for the 1,4 isomerization is close to that of the C-C bond rupture. The fastest reaction of the radical is isomerization involving a six-member transition structure, converting the alkoxy radical into an OH-substituted alkyl radical. The decomposition reaction can compete with the 1,5 isomerization step at high excitation or at combustion temperatures.

Original languageEnglish
Pages (from-to)10777-10786
Number of pages10
JournalJournal of Physical Chemistry A
Volume102
Issue number52
Publication statusPublished - Dec 24 1998

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Isomerization
isomerization
Decomposition
decomposition
Discrete Fourier transforms
Isomers
combustion temperature
Atoms
isomers
prototypes
dissociation
thresholds
energy
coefficients
Temperature
excitation
atoms
alkoxyl radical

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Ab initio studies of the isomerization and decomposition reactions of the 1-butoxy radical. / Lendvay, G.; Viskolcz, B.

In: Journal of Physical Chemistry A, Vol. 102, No. 52, 24.12.1998, p. 10777-10786.

Research output: Contribution to journalArticle

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N2 - The unimolecular reactions of the 1-butoxy radical, a prototype of atmospherically important alkoxy radicals, are studied. The structures of the isomers of the C4H9O radical and the transition structures of the isomerization and main decomposition reactions of 1-butoxy are determined by ab initio quantum chemical methods. The energy-dependent rate coefficients of the unimolecular reactions involved were obtained in RRKM calculations. The threshold energy for the fastest channel, the 1,5 intramolecular H-atom transfer is 8.12, 9.23, 9.16, and 9.51 kcal mol-1 according to the MP-SAC2, BAC-MP4, DFT, and an additively corrected MP4 method, respectively. For the β-C-C dissociation reaction we found a barrier of 16.03, 13.34, and 12.39 kcal mol-1 at the BAC-MP4, DFT, and additively corrected MP4 level. The barrier height for the 1,4 isomerization is close to that of the C-C bond rupture. The fastest reaction of the radical is isomerization involving a six-member transition structure, converting the alkoxy radical into an OH-substituted alkyl radical. The decomposition reaction can compete with the 1,5 isomerization step at high excitation or at combustion temperatures.

AB - The unimolecular reactions of the 1-butoxy radical, a prototype of atmospherically important alkoxy radicals, are studied. The structures of the isomers of the C4H9O radical and the transition structures of the isomerization and main decomposition reactions of 1-butoxy are determined by ab initio quantum chemical methods. The energy-dependent rate coefficients of the unimolecular reactions involved were obtained in RRKM calculations. The threshold energy for the fastest channel, the 1,5 intramolecular H-atom transfer is 8.12, 9.23, 9.16, and 9.51 kcal mol-1 according to the MP-SAC2, BAC-MP4, DFT, and an additively corrected MP4 method, respectively. For the β-C-C dissociation reaction we found a barrier of 16.03, 13.34, and 12.39 kcal mol-1 at the BAC-MP4, DFT, and additively corrected MP4 level. The barrier height for the 1,4 isomerization is close to that of the C-C bond rupture. The fastest reaction of the radical is isomerization involving a six-member transition structure, converting the alkoxy radical into an OH-substituted alkyl radical. The decomposition reaction can compete with the 1,5 isomerization step at high excitation or at combustion temperatures.

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