Direct dynamics studies for the reactions of CH 3 CH 2 Br with O ( 3 P) and Cl ( 2 P) atoms

Li Wang, Jing yao Liu, Gang Zhang, Ze sheng Li

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

A dual-level direct dynamics method is employed to perform the dynamics calculations for the multi-channel reactions CH 3 CH 2 Br + O( 3 P) → products (R1) and CH 3 CH 2 Br + Cl → products (R2). Four reaction channels, i.e., one α-hydrogen, two β-hydrogen, and one bromine-abstractions, are identified for each reaction. The geometries and frequencies of all the stationary points are optimized at the BH&H-LYP/6-311G(d, p) level. The complexes with energies less than those of the reactants or products are found at entrance or exit of each reaction channel, which indicate that the reactions may proceed via an indirect mechanism. The energy profiles are further refined at the G3//BH&H-LYP level. Then, the rate constants are calculated by canonical variational transition-state (CVT) theory incorporating the small-curvature tunneling method (SCT) correction in the temperature range of 220-2000 K. The theoretical rate constants are in good agreement with the experimental ones. Theoretical calculations show that the Br-abstraction channel should be negligible due to its much higher barrier height than the others. As to the three hydrogen-abstraction channels, α-hydrogen abstraction is the major pathway and the contribution of β-hydrogen abstraction become important with the temperature increasing.

Original languageEnglish (US)
Pages (from-to)36-41
Number of pages6
JournalJournal of Molecular Structure: THEOCHEM
Volume897
Issue number1-3
DOIs
StatePublished - Mar 15 2009

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Hydrogen
methylidyne
Atoms
hydrogen
atoms
Rate constants
products
Bromine
Temperature
bromine
entrances
curvature
temperature
Geometry
energy
profiles
geometry

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Wang, Li ; Liu, Jing yao ; Zhang, Gang ; Li, Ze sheng. / Direct dynamics studies for the reactions of CH 3 CH 2 Br with O ( 3 P) and Cl ( 2 P) atoms In: Journal of Molecular Structure: THEOCHEM. 2009 ; Vol. 897, No. 1-3. pp. 36-41.
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abstract = "A dual-level direct dynamics method is employed to perform the dynamics calculations for the multi-channel reactions CH 3 CH 2 Br + O( 3 P) → products (R1) and CH 3 CH 2 Br + Cl → products (R2). Four reaction channels, i.e., one α-hydrogen, two β-hydrogen, and one bromine-abstractions, are identified for each reaction. The geometries and frequencies of all the stationary points are optimized at the BH&H-LYP/6-311G(d, p) level. The complexes with energies less than those of the reactants or products are found at entrance or exit of each reaction channel, which indicate that the reactions may proceed via an indirect mechanism. The energy profiles are further refined at the G3//BH&H-LYP level. Then, the rate constants are calculated by canonical variational transition-state (CVT) theory incorporating the small-curvature tunneling method (SCT) correction in the temperature range of 220-2000 K. The theoretical rate constants are in good agreement with the experimental ones. Theoretical calculations show that the Br-abstraction channel should be negligible due to its much higher barrier height than the others. As to the three hydrogen-abstraction channels, α-hydrogen abstraction is the major pathway and the contribution of β-hydrogen abstraction become important with the temperature increasing.",
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Direct dynamics studies for the reactions of CH 3 CH 2 Br with O ( 3 P) and Cl ( 2 P) atoms . / Wang, Li; Liu, Jing yao; Zhang, Gang; Li, Ze sheng.

In: Journal of Molecular Structure: THEOCHEM, Vol. 897, No. 1-3, 15.03.2009, p. 36-41.

Research output: Contribution to journalArticle

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AB - A dual-level direct dynamics method is employed to perform the dynamics calculations for the multi-channel reactions CH 3 CH 2 Br + O( 3 P) → products (R1) and CH 3 CH 2 Br + Cl → products (R2). Four reaction channels, i.e., one α-hydrogen, two β-hydrogen, and one bromine-abstractions, are identified for each reaction. The geometries and frequencies of all the stationary points are optimized at the BH&H-LYP/6-311G(d, p) level. The complexes with energies less than those of the reactants or products are found at entrance or exit of each reaction channel, which indicate that the reactions may proceed via an indirect mechanism. The energy profiles are further refined at the G3//BH&H-LYP level. Then, the rate constants are calculated by canonical variational transition-state (CVT) theory incorporating the small-curvature tunneling method (SCT) correction in the temperature range of 220-2000 K. The theoretical rate constants are in good agreement with the experimental ones. Theoretical calculations show that the Br-abstraction channel should be negligible due to its much higher barrier height than the others. As to the three hydrogen-abstraction channels, α-hydrogen abstraction is the major pathway and the contribution of β-hydrogen abstraction become important with the temperature increasing.

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