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Published on: January 19, 2016
Theoretical study on the reaction mechanism of chlordimeform with OH radicals
Shengmin Sun1, Kun Zhang, Yang Lu
1College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin, 150080, People's Republic of China.
Abstract:
A theoretical investigation on the multiple-channel degradation mechanism of chlordimeform with OH radicals in the atmosphere was completed using a dual-level direct dynamics method. The equilibrium geometries and the corresponding harmonic vibrational frequencies of the stationary points were obtained at the M06-2X/6-311++G(d,p) level. The minimum energy paths (MEP) were calculated at the same level, and energetic information was further refined at M06-2X/6-311++G(3df,2p) level. The rate constants for the 15 reaction channels were calculated by improved canonical variational transition state theory with small-curvature tunneling correction over the temperature range 200-1,000 K. The total rate constants are in good agreement with the available experimental data and the three-parameter expression k(T) =2.62 × 10(-18) T (2.71) exp (899.61/T) cm(3)molecule(-1) s(-1) was given. The calculated results indicate that the addition reaction of the carbon-nitrogen double bond is the major channel, while the abstraction reaction from the benzene ring of chlordimeform is the least competitive channel.
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