Theoretical study on the Cl + CH3S(O)CH3 reaction

Hui Zhang; Jia yan Wu; Ze sheng Li; Jing yao Liu; Chia chung Sun

doi:10.1016/j.chemphys.2005.10.002

Theoretical study on the Cl + CH₃S(O)CH₃ reaction

Hui Zhang
, Jia yan Wu
, Ze sheng Li^*
, Jing yao Liu
, Chia chung Sun

^*Corresponding author for this work

Harbin University of Science and Technology
Jilin University

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

1 Citation (Scopus)

Abstract

By means of direct dynamics methods theoretical investigations are carried out on the multiple-channel reaction system Cl + CH₃S(O)CH₃. The optimized geometries, frequencies and minimum energy path (MEP) are all obtained at the BH&H-LYP/6-311G(2d,2p) level, and energetic information is further refined by the MC-QCISD (single-point) theory. The rate constants for two main reaction channels, to yield CH₃S(O)CH₂ + HCl and to yield CH₃S(O)Cl + CH₃, are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions over the wide temperature region 200-2000 K. The theoretical overall rate constants and the branching ratio are in good agreement with the available experimental data; and the three-parameter formula k = 1.32 × 10^-16 T^2.18exp(-48.12/T) cm³ molecule^-1 s^-1 over the temperature region 200-2000 K is given. For the title reaction, CH₃S(O)CH₂ + HCl is the major product, and CH₃S(O)Cl + CH₃ is a minor product over the whole temperature region.

Original language	English
Pages (from-to)	291-297
Number of pages	7
Journal	Chemical Physics
Volume	324
Issue number	2-3
DOIs	https://doi.org/10.1016/j.chemphys.2005.10.002
Publication status	Published - 31 May 2006
Externally published	Yes

Keywords

Rate constant
Transition state
Tunneling effect

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10.1016/j.chemphys.2005.10.002

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title = "Theoretical study on the Cl + CH3S(O)CH3 reaction",

abstract = "By means of direct dynamics methods theoretical investigations are carried out on the multiple-channel reaction system Cl + CH3S(O)CH3. The optimized geometries, frequencies and minimum energy path (MEP) are all obtained at the BH\&H-LYP/6-311G(2d,2p) level, and energetic information is further refined by the MC-QCISD (single-point) theory. The rate constants for two main reaction channels, to yield CH3S(O)CH2 + HCl and to yield CH3S(O)Cl + CH3, are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions over the wide temperature region 200-2000 K. The theoretical overall rate constants and the branching ratio are in good agreement with the available experimental data; and the three-parameter formula k = 1.32 {\texttimes} 10-16 T2.18exp(-48.12/T) cm3 molecule-1 s-1 over the temperature region 200-2000 K is given. For the title reaction, CH3S(O)CH2 + HCl is the major product, and CH3S(O)Cl + CH3 is a minor product over the whole temperature region.",

keywords = "Rate constant, Transition state, Tunneling effect",

author = "Hui Zhang and Wu, \{Jia yan\} and Li, \{Ze sheng\} and Liu, \{Jing yao\} and Sun, \{Chia chung\}",

year = "2006",

month = may,

day = "31",

doi = "10.1016/j.chemphys.2005.10.002",

language = "English",

volume = "324",

pages = "291--297",

journal = "Chemical Physics",

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TY - JOUR

T1 - Theoretical study on the Cl + CH3S(O)CH3 reaction

AU - Zhang, Hui

AU - Wu, Jia yan

AU - Li, Ze sheng

AU - Liu, Jing yao

AU - Sun, Chia chung

PY - 2006/5/31

Y1 - 2006/5/31

N2 - By means of direct dynamics methods theoretical investigations are carried out on the multiple-channel reaction system Cl + CH3S(O)CH3. The optimized geometries, frequencies and minimum energy path (MEP) are all obtained at the BH&H-LYP/6-311G(2d,2p) level, and energetic information is further refined by the MC-QCISD (single-point) theory. The rate constants for two main reaction channels, to yield CH3S(O)CH2 + HCl and to yield CH3S(O)Cl + CH3, are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions over the wide temperature region 200-2000 K. The theoretical overall rate constants and the branching ratio are in good agreement with the available experimental data; and the three-parameter formula k = 1.32 × 10-16 T2.18exp(-48.12/T) cm3 molecule-1 s-1 over the temperature region 200-2000 K is given. For the title reaction, CH3S(O)CH2 + HCl is the major product, and CH3S(O)Cl + CH3 is a minor product over the whole temperature region.

AB - By means of direct dynamics methods theoretical investigations are carried out on the multiple-channel reaction system Cl + CH3S(O)CH3. The optimized geometries, frequencies and minimum energy path (MEP) are all obtained at the BH&H-LYP/6-311G(2d,2p) level, and energetic information is further refined by the MC-QCISD (single-point) theory. The rate constants for two main reaction channels, to yield CH3S(O)CH2 + HCl and to yield CH3S(O)Cl + CH3, are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions over the wide temperature region 200-2000 K. The theoretical overall rate constants and the branching ratio are in good agreement with the available experimental data; and the three-parameter formula k = 1.32 × 10-16 T2.18exp(-48.12/T) cm3 molecule-1 s-1 over the temperature region 200-2000 K is given. For the title reaction, CH3S(O)CH2 + HCl is the major product, and CH3S(O)Cl + CH3 is a minor product over the whole temperature region.

KW - Rate constant

KW - Transition state

KW - Tunneling effect

UR - https://www.scopus.com/pages/publications/33646783632

U2 - 10.1016/j.chemphys.2005.10.002

DO - 10.1016/j.chemphys.2005.10.002

M3 - Article

AN - SCOPUS:33646783632

SN - 0301-0104

VL - 324

SP - 291

EP - 297

JO - Chemical Physics

JF - Chemical Physics

IS - 2-3

ER -

Theoretical study on the Cl + CH₃S(O)CH₃ reaction

Abstract

Keywords

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