TY - JOUR
T1 - Theoretical studies on the reactions of hydroxyl radicals with trimethylsilane and tetramethylsilane
AU - Zhang, Hui
AU - Zhang, Gui Ling
AU - Wang, Ying
AU - Yu, Xiao Yang
AU - Liu, Bo
AU - Liu, Jing Yao
AU - Li, Ze Sheng
PY - 2008/3
Y1 - 2008/3
N2 - The multiple-channel reactions OH + SiH(CH3)3 → products (R1) and the single-channel reaction OH + Si(CH3) 4 → Si(CH3)3CH2 + H 2O (R2) have been studied by means of the direct dynamics method at the BMC-CCSD//MP2/6-311+G(2d,2p) level. The optimized geometries, frequencies and minimum energy path are all obtained at the MP2/6-311+G(2d,2p) levels, and energy information is further refined by the BMC-CCSD (single-point) level. The rate constants for every reaction channels are calculated by canonical variational transition states theory (CVT) with small-curvature tunneling (SCT) contributions over the temperature range 200-2,000 K. The theoretical total rate constants are in good agreement with the available experimental data, and the three-parameter expression k 1 = 2.53×10-21 T 3.14 exp(1, 352.86/T), k 2 = 6.00 × 10-19 T 2.54 exp(-106.11/T) (in unit of cm3 molecule -1 s-1) over the temperature range 200-2,000 K are given. Our calculations indicate that at the low temperature range, for reaction R1, H-abstraction is favored for the SiH group, while the abstraction from the CH3 group is a minor channel.
AB - The multiple-channel reactions OH + SiH(CH3)3 → products (R1) and the single-channel reaction OH + Si(CH3) 4 → Si(CH3)3CH2 + H 2O (R2) have been studied by means of the direct dynamics method at the BMC-CCSD//MP2/6-311+G(2d,2p) level. The optimized geometries, frequencies and minimum energy path are all obtained at the MP2/6-311+G(2d,2p) levels, and energy information is further refined by the BMC-CCSD (single-point) level. The rate constants for every reaction channels are calculated by canonical variational transition states theory (CVT) with small-curvature tunneling (SCT) contributions over the temperature range 200-2,000 K. The theoretical total rate constants are in good agreement with the available experimental data, and the three-parameter expression k 1 = 2.53×10-21 T 3.14 exp(1, 352.86/T), k 2 = 6.00 × 10-19 T 2.54 exp(-106.11/T) (in unit of cm3 molecule -1 s-1) over the temperature range 200-2,000 K are given. Our calculations indicate that at the low temperature range, for reaction R1, H-abstraction is favored for the SiH group, while the abstraction from the CH3 group is a minor channel.
UR - http://www.scopus.com/inward/record.url?scp=39749143888&partnerID=8YFLogxK
U2 - 10.1007/s00214-007-0387-2
DO - 10.1007/s00214-007-0387-2
M3 - Article
AN - SCOPUS:39749143888
SN - 1432-881X
VL - 119
SP - 319
EP - 327
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 4
ER -
