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

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

来源：Theoretical Chemistry Accounts, 2010, 125(1-2): 75-82.

DOI：10.1007/s00214-009-0664-3

• Gas-phase reaction
• Transition state
• Rate constants

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 k(1)(T) = 9.97 x 10(-13)T(0.54)exp(613.22/T) and k(2)(T) = 1.16 x 10(-17)T(2.30)exp(-3525.88/T) (in unit of cm(3) 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.

• 出版日期2010-1
• 单位哈尔滨学院; 哈尔滨工业大学; 吉林大学