Theoretical study on the reactions of trimethylsilane with chlorine and bromine atoms

Yuan Zhang; Hui Zhang; Jing Yao Liu; Xue Mei Duan; Ze Sheng Li

doi:10.1007/s00214-011-0998-5

Theoretical study on the reactions of trimethylsilane with chlorine and bromine atoms

Yuan Zhang, Hui Zhang^*, Jing Yao Liu, Xue Mei Duan, Ze Sheng Li

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

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

Abstract

Theoretical studies are carried out on the multi-channel reactions of SiH(CH₃)₃ with Cl (reaction 1, R1) and Br atoms (R2) 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 channels, R1a, R1b-in, R1b-out, R1c, R1d, R2a, R2b-in, R2b-out, R2c, and R2d, are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1,500 K. The theoretical three-parameter expressions k₁(T) = 6.30 × 10^-15T^1.36exp(704.94/T) and k₂(T) = 9.41 × 10^-26T^4.89exp(-1,033.80/T) cm³ molecule^-1 s^-1 are given. Our calculations indicate that reaction channels R1c and R2c are the major channel.

Original language	English
Pages (from-to)	115-125
Number of pages	11
Journal	Theoretical Chemistry Accounts
Volume	130
Issue number	1
DOIs	https://doi.org/10.1007/s00214-011-0998-5
Publication status	Published - Sept 2011

Keywords

Gas-phase reaction
Rate constants
Transition state

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title = "Theoretical study on the reactions of trimethylsilane with chlorine and bromine atoms",

abstract = "Theoretical studies are carried out on the multi-channel reactions of SiH(CH3)3 with Cl (reaction 1, R1) and Br atoms (R2) 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 channels, R1a, R1b-in, R1b-out, R1c, R1d, R2a, R2b-in, R2b-out, R2c, and R2d, are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1,500 K. The theoretical three-parameter expressions k1(T) = 6.30 × 10-15T1.36exp(704.94/T) and k2(T) = 9.41 × 10-26T4.89exp(-1,033.80/T) cm3 molecule-1 s-1 are given. Our calculations indicate that reaction channels R1c and R2c are the major channel.",

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

author = "Yuan Zhang and Hui Zhang and Liu, \{Jing Yao\} and Duan, \{Xue Mei\} and Li, \{Ze Sheng\}",

year = "2011",

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doi = "10.1007/s00214-011-0998-5",

language = "English",

volume = "130",

pages = "115--125",

journal = "Theoretical Chemistry Accounts",

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T1 - Theoretical study on the reactions of trimethylsilane with chlorine and bromine atoms

AU - Zhang, Yuan

AU - Zhang, Hui

AU - Liu, Jing Yao

AU - Duan, Xue Mei

AU - Li, Ze Sheng

PY - 2011/9

Y1 - 2011/9

N2 - Theoretical studies are carried out on the multi-channel reactions of SiH(CH3)3 with Cl (reaction 1, R1) and Br atoms (R2) 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 channels, R1a, R1b-in, R1b-out, R1c, R1d, R2a, R2b-in, R2b-out, R2c, and R2d, are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1,500 K. The theoretical three-parameter expressions k1(T) = 6.30 × 10-15T1.36exp(704.94/T) and k2(T) = 9.41 × 10-26T4.89exp(-1,033.80/T) cm3 molecule-1 s-1 are given. Our calculations indicate that reaction channels R1c and R2c are the major channel.

AB - Theoretical studies are carried out on the multi-channel reactions of SiH(CH3)3 with Cl (reaction 1, R1) and Br atoms (R2) 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 channels, R1a, R1b-in, R1b-out, R1c, R1d, R2a, R2b-in, R2b-out, R2c, and R2d, are calculated by the improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1,500 K. The theoretical three-parameter expressions k1(T) = 6.30 × 10-15T1.36exp(704.94/T) and k2(T) = 9.41 × 10-26T4.89exp(-1,033.80/T) cm3 molecule-1 s-1 are given. Our calculations indicate that reaction channels R1c and R2c are the major channel.

KW - Gas-phase reaction

KW - Rate constants

KW - Transition state

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DO - 10.1007/s00214-011-0998-5

M3 - Article

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SP - 115

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JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

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Theoretical study on the reactions of trimethylsilane with chlorine and bromine atoms

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Keywords

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