Direct ab initio dynamics study on the hydrogen abstraction reaction of CH3CCl3 + OH → CH2CCl3 + H 2O

Jing Yao Liu; Ze Sheng Li; Zhen Wen Dai; Xu Ri Huang; Chia Chung Sun

doi:10.1021/jp034019a

Direct ab initio dynamics study on the hydrogen abstraction reaction of CH₃CCl₃ + OH → CH₂CCl₃ + H ₂O

Jing Yao Liu, Ze Sheng Li^*, Zhen Wen Dai, Xu Ri Huang, Chia Chung Sun

^*Corresponding author for this work

Jilin University

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

11 Citations (Scopus)

Abstract

The ab initio direct dynamics approach is employed to study the hydrogen abstraction reaction of CH₃CCl₃ + OH. The potential energy surface (PES) information is obtained at the MP2/6-311G(d,p) and G3(MP2) (single-point) levels of theory. A hydrogen-bonded complex is located in the reactant channel. Dynamics calculations are performed by variational transition-state theory with the interpolated single-point energy approach (VTST-ISPE). Canonical variational transition-state theory and a small curvature tunneling correction are included to calculate the rate constants within 200-2000 K. Both theoretical rate constants and activation energy are in good agreement with experimental ones over the measured temperature range, 222-761 K. The calculations show that the variational effect is small and the tunneling effect is significant in the lower temperature range.

Original language	English
Pages (from-to)	6231-6235
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	107
Issue number	32
DOIs	https://doi.org/10.1021/jp034019a
Publication status	Published - 14 Aug 2003
Externally published	Yes

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Liu, J. Y., Li, Z. S., Dai, Z. W., Huang, X. R., & Sun, C. C. (2003). Direct ab initio dynamics study on the hydrogen abstraction reaction of CH₃CCl₃ + OH → CH₂CCl₃ + H ₂O. Journal of Physical Chemistry A, 107(32), 6231-6235. https://doi.org/10.1021/jp034019a

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title = "Direct ab initio dynamics study on the hydrogen abstraction reaction of CH3CCl3 + OH → CH2CCl3 + H 2O",

abstract = "The ab initio direct dynamics approach is employed to study the hydrogen abstraction reaction of CH3CCl3 + OH. The potential energy surface (PES) information is obtained at the MP2/6-311G(d,p) and G3(MP2) (single-point) levels of theory. A hydrogen-bonded complex is located in the reactant channel. Dynamics calculations are performed by variational transition-state theory with the interpolated single-point energy approach (VTST-ISPE). Canonical variational transition-state theory and a small curvature tunneling correction are included to calculate the rate constants within 200-2000 K. Both theoretical rate constants and activation energy are in good agreement with experimental ones over the measured temperature range, 222-761 K. The calculations show that the variational effect is small and the tunneling effect is significant in the lower temperature range.",

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AU - Liu, Jing Yao

AU - Li, Ze Sheng

AU - Dai, Zhen Wen

AU - Huang, Xu Ri

AU - Sun, Chia Chung

PY - 2003/8/14

Y1 - 2003/8/14

N2 - The ab initio direct dynamics approach is employed to study the hydrogen abstraction reaction of CH3CCl3 + OH. The potential energy surface (PES) information is obtained at the MP2/6-311G(d,p) and G3(MP2) (single-point) levels of theory. A hydrogen-bonded complex is located in the reactant channel. Dynamics calculations are performed by variational transition-state theory with the interpolated single-point energy approach (VTST-ISPE). Canonical variational transition-state theory and a small curvature tunneling correction are included to calculate the rate constants within 200-2000 K. Both theoretical rate constants and activation energy are in good agreement with experimental ones over the measured temperature range, 222-761 K. The calculations show that the variational effect is small and the tunneling effect is significant in the lower temperature range.

AB - The ab initio direct dynamics approach is employed to study the hydrogen abstraction reaction of CH3CCl3 + OH. The potential energy surface (PES) information is obtained at the MP2/6-311G(d,p) and G3(MP2) (single-point) levels of theory. A hydrogen-bonded complex is located in the reactant channel. Dynamics calculations are performed by variational transition-state theory with the interpolated single-point energy approach (VTST-ISPE). Canonical variational transition-state theory and a small curvature tunneling correction are included to calculate the rate constants within 200-2000 K. Both theoretical rate constants and activation energy are in good agreement with experimental ones over the measured temperature range, 222-761 K. The calculations show that the variational effect is small and the tunneling effect is significant in the lower temperature range.

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Direct ab initio dynamics study on the hydrogen abstraction reaction of CH₃CCl₃ + OH → CH₂CCl₃ + H ₂O

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