Theoretical Study of CH_3CH=CH_2+O(~1D) Reaction: Mechanism and Kinetics  

作　　者：WU Nan-nan, LIU Hong-xia, DUAN Xue-mei and LIU Jing-yao State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130021, P. R. China 

出　　处：《Chemical Research in Chinese Universities》2012年第1期147-152,共6页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China(Nos.20303007, 20333050, 20973077);the Program for New Century Excellent Talents(NCET) in Universities of China

摘　　要：The mechanism and kinetics for the reaction of propene（CH3CH=CH2） molecule with O（1D） atom were investigated theoretically. The electronic structure information of the potential energy surface（PES） was obtained at the B3LYP/6-311＋G（d,p） level, and the single-point energies were refined by the multi-level MCG3-MPWB method. The calculated results show that O（1D） atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C（OH）CH2（IM1）, CH3CHCHOH（IM2）, CH2OHCHCH2（IM3） and cyclo CH2OCHCH3（IM4）, respectively, on the singlet PES. The branching ratios as well as the pressure and temperature dependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus（RRKM） theories. The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2＋O（1D） reaction.The mechanism and kinetics for the reaction of propene（CH3CH=CH2） molecule with O（1D） atom were investigated theoretically. The electronic structure information of the potential energy surface（PES） was obtained at the B3LYP/6-311＋G（d,p） level, and the single-point energies were refined by the multi-level MCG3-MPWB method. The calculated results show that O（1D） atom can attack CH3CH=CH2 via the barrierless insertion mechanism to form four energy-riched intermediates CH3C（OH）CH2（IM1）, CH3CHCHOH（IM2）, CH2OHCHCH2（IM3） and cyclo CH2OCHCH3（IM4）, respectively, on the singlet PES. The branching ratios as well as the pressure and temperature dependence of various product channels for this multi-well reaction were predicted by variational transition-state and Rice-Ramsperger-Kassel-Marcus（RRKM） theories. The present results will be useful to gain a deep insight into the reaction mechanism and kinetics of CH3CH=CH2＋O（1D） reaction.

关 键 词：PROPENE O（lD） MECHANISM KINETICS 

分 类 号：O621.25[理学—有机化学]