Theoretical study on the Br + CH3SCH3 reaction

Hui Zhang; Gui Ling Zhang; Li Wang; Bo Liu; Xiao Yang Yu; Ze Sheng Li

doi:10.1002/jcc.20646

Theoretical study on the Br + CH₃SCH₃ reaction

Hui Zhang, Gui Ling Zhang, Li Wang, Bo Liu^*, Xiao Yang Yu, Ze Sheng Li

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

The multiple-channel reactions Br + CH₃SCH₃ → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the G3(MP2) (single-point) theory. The rate constants for every reaction channels, Br + CH₃SCH₃ → CH₃SCH₂ + HBr (R1), Br + CH₃SCH₃ → CH₃SBr + CH₃ (R2), and Br + CH₃SCH₃ → CH₃S + CH ₃Br (R3), are calculated by canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data, and the two-parameter expression k(T) = 2.68 × 10 ^-12 exp(-1235.24/7) cm³/(molecule s) over the temperature range 200-3000 K is given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smallest barrier height among three channels considered, and the other two channels to yield CH₃SBr + CH₃ and CH₃S + CH₂Br are minor channels over the whole temperature range.

Original language	English
Pages (from-to)	1153-1159
Number of pages	7
Journal	Journal of Computational Chemistry
Volume	28
Issue number	7
DOIs	https://doi.org/10.1002/jcc.20646
Publication status	Published - May 2007
Externally published	Yes

Keywords

Canonical variational transition state theory
Rate constants
Transition state

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10.1002/jcc.20646

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Zhang, H., Zhang, G. L., Wang, L., Liu, B., Yu, X. Y., & Li, Z. S. (2007). Theoretical study on the Br + CH₃SCH₃ reaction. Journal of Computational Chemistry, 28(7), 1153-1159. https://doi.org/10.1002/jcc.20646

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title = "Theoretical study on the Br + CH3SCH3 reaction",

abstract = "The multiple-channel reactions Br + CH3SCH3 → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the G3(MP2) (single-point) theory. The rate constants for every reaction channels, Br + CH3SCH3 → CH3SCH2 + HBr (R1), Br + CH3SCH3 → CH3SBr + CH3 (R2), and Br + CH3SCH3 → CH3S + CH 3Br (R3), are calculated by canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data, and the two-parameter expression k(T) = 2.68 × 10 -12 exp(-1235.24/7) cm3/(molecule s) over the temperature range 200-3000 K is given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smallest barrier height among three channels considered, and the other two channels to yield CH3SBr + CH3 and CH3S + CH2Br are minor channels over the whole temperature range.",

keywords = "Canonical variational transition state theory, Rate constants, Transition state",

author = "Hui Zhang and Zhang, {Gui Ling} and Li Wang and Bo Liu and Yu, {Xiao Yang} and Li, {Ze Sheng}",

year = "2007",

month = may,

doi = "10.1002/jcc.20646",

language = "English",

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pages = "1153--1159",

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T1 - Theoretical study on the Br + CH3SCH3 reaction

AU - Zhang, Hui

AU - Zhang, Gui Ling

AU - Wang, Li

AU - Liu, Bo

AU - Yu, Xiao Yang

AU - Li, Ze Sheng

PY - 2007/5

Y1 - 2007/5

N2 - The multiple-channel reactions Br + CH3SCH3 → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the G3(MP2) (single-point) theory. The rate constants for every reaction channels, Br + CH3SCH3 → CH3SCH2 + HBr (R1), Br + CH3SCH3 → CH3SBr + CH3 (R2), and Br + CH3SCH3 → CH3S + CH 3Br (R3), are calculated by canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data, and the two-parameter expression k(T) = 2.68 × 10 -12 exp(-1235.24/7) cm3/(molecule s) over the temperature range 200-3000 K is given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smallest barrier height among three channels considered, and the other two channels to yield CH3SBr + CH3 and CH3S + CH2Br are minor channels over the whole temperature range.

AB - The multiple-channel reactions Br + CH3SCH3 → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the G3(MP2) (single-point) theory. The rate constants for every reaction channels, Br + CH3SCH3 → CH3SCH2 + HBr (R1), Br + CH3SCH3 → CH3SBr + CH3 (R2), and Br + CH3SCH3 → CH3S + CH 3Br (R3), are calculated by canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data, and the two-parameter expression k(T) = 2.68 × 10 -12 exp(-1235.24/7) cm3/(molecule s) over the temperature range 200-3000 K is given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smallest barrier height among three channels considered, and the other two channels to yield CH3SBr + CH3 and CH3S + CH2Br are minor channels over the whole temperature range.

KW - Canonical variational transition state theory

KW - Rate constants

KW - Transition state

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Theoretical study on the Br + CH₃SCH₃ reaction

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