Theoretical study on the OH + CH3NHCOOCH3 reaction.
The multiple-channel reactions OH + CH3NHC(O)OCH3 --> products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-311+G(d,p) level, and energetic information is further refined by the BMC-CCSD (single-point) method. The rate constants for every reaction channels, R1, R2, R3, and R4, are calculated by canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1000 K. The total rate constants are in good agreement with the available experimental data and the two-parameter expression k(T) = 3.95 x 10(-12) exp(15.41/T) cm3 molecule(-1) s(-1) over the temperature range 200-1000 K is given. Our calculations indicate that hydrogen abstraction channels R1 and R2 are the major channels due to the smaller barrier height among four channels considered, and the other two channels to yield CH3NC(O)OCH3 + H2O and CH3NHC(O)(OH)OCH3 + H2O are minor channels over the whole temperature range.
Zhang
Hui
H
College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, People's Republic of China.
Zhang
Gui-Ling
GL
Liu
Jing-Yao
JY
Liu
Bo
B
Yu
Xiao-Yang
XY
Li
Ze-Sheng
ZS
D002219:Carbamates / Q000138:chemical synthesis / Q000737:chemistry*; D003198:Computer Simulation; D017665:Hydroxyl Radical / Q000737:chemistry*; D008956:Models, Chemical; D013696:Temperature; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D002219:Carbamates; D014867:Water; D017665:Hydroxyl Radical