Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms

Hui Zhang; Gui ling Zhang; Jing yao Liu; Wen jie Hou; Bo Liu; Ze sheng Li

doi:10.1007/s00214-009-0664-3

Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms

Hui Zhang, Gui ling Zhang, Jing yao Liu, Wen jie Hou, Bo Liu^*, Ze sheng Li

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

The multiple-channel reactions Cl + Si(CH₃)₄ and Br + Si(CH₃)₄ are investigated by direct dynamics method. The minimum energy path is calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for individual reaction channel are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3,000 K. The theoretical three-parameter expression k₁(T) = 9. 97 × 10^-13T^{0. 54}exp(613. 22/T) and k₂(T) = 1. 16 × 10^-17T^{2. 30}exp(-3525. 88/T) (in unit of cm³ molecule^-1 s^-1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among feasible channels considered.

Original language	English
Pages (from-to)	75-82
Number of pages	8
Journal	Theoretical Chemistry Accounts
Volume	125
Issue number	1
DOIs	https://doi.org/10.1007/s00214-009-0664-3
Publication status	Published - Jan 2009
Externally published	Yes

Keywords

Gas-phase reaction
Rate constants
Transition state

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10.1007/s00214-009-0664-3

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title = "Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms",

abstract = "The multiple-channel reactions Cl + Si(CH3)4 and Br + Si(CH3)4 are investigated by direct dynamics method. The minimum energy path is calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for individual reaction channel are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3,000 K. The theoretical three-parameter expression k1(T) = 9. 97 × 10-13T0. 54exp(613. 22/T) and k2(T) = 1. 16 × 10-17T2. 30exp(-3525. 88/T) (in unit of cm3 molecule-1 s-1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among feasible channels considered.",

keywords = "Gas-phase reaction, Rate constants, Transition state",

author = "Hui Zhang and Zhang, {Gui ling} and Liu, {Jing yao} and Hou, {Wen jie} and Bo Liu and Li, {Ze sheng}",

year = "2009",

month = jan,

doi = "10.1007/s00214-009-0664-3",

language = "English",

volume = "125",

pages = "75--82",

journal = "Theoretical Chemistry Accounts",

issn = "1432-881X",

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T1 - Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms

AU - Zhang, Hui

AU - Zhang, Gui ling

AU - Liu, Jing yao

AU - Hou, Wen jie

AU - Liu, Bo

AU - Li, Ze sheng

PY - 2009/1

Y1 - 2009/1

N2 - The multiple-channel reactions Cl + Si(CH3)4 and Br + Si(CH3)4 are investigated by direct dynamics method. The minimum energy path is calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for individual reaction channel are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3,000 K. The theoretical three-parameter expression k1(T) = 9. 97 × 10-13T0. 54exp(613. 22/T) and k2(T) = 1. 16 × 10-17T2. 30exp(-3525. 88/T) (in unit of cm3 molecule-1 s-1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among feasible channels considered.

AB - The multiple-channel reactions Cl + Si(CH3)4 and Br + Si(CH3)4 are investigated by direct dynamics method. The minimum energy path is calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for individual reaction channel are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-3,000 K. The theoretical three-parameter expression k1(T) = 9. 97 × 10-13T0. 54exp(613. 22/T) and k2(T) = 1. 16 × 10-17T2. 30exp(-3525. 88/T) (in unit of cm3 molecule-1 s-1) are given. Our calculations indicate that hydrogen abstraction channel is the major channel due to the smaller barrier height among feasible channels considered.

KW - Gas-phase reaction

KW - Rate constants

KW - Transition state

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DO - 10.1007/s00214-009-0664-3

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SN - 1432-881X

VL - 125

SP - 75

EP - 82

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

IS - 1

ER -

Dual-level direct dynamics studies on the reactions of tetramethylsilane with chlorine and bromine atoms

Abstract

Keywords

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