Acta Phys. -Chim. Sin. ›› 2002, Vol. 18 ›› Issue (05): 446-450.doi: 10.3866/PKU.WHXB20020513

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The Reaction Path and Variational Rate Constant of the Hydrogen Abstraction Reaction CH2O+O[3P]→CHO+OH

Li Hui-Ying;Feng Wen-Lin;Ji Yong-Qiang;Xu Zhen-Feng;Lei Ming   

  1. Department of Applied Chemistry,Beijing University of Chemical Technology,Beijing 100029
  • Received:2001-10-09 Revised:2001-12-05 Published:2002-05-15
  • Contact: Feng Wen-Lin E-mail:wlfeng@buct.edu.cn

Abstract: Using ab initio molecular orbital theory,the hydrogen abstraction reaction CH2O+O[3P]→CHO+OH has been studied.The geometries of the reactants,transition state and products have been optimized at the QCISD/6311G[d,p] level.The forward and reverse reaction potential barriers are 38.86 kJ•mol-1 and 67.23 kJ•mol-1 respectively at the QCISD(t,full)/6311G[d,p]//QCISD/6311G[d,p].By analyzing the changes of the generalized normalmode vibrational frequencies along the IRC,we found that the C-H bond breaking and the O-H bond forming took place as a concerted process.And there is a reactive vibrational normalmode which leads to the process of reaction from reactants to products.At the temperature range of 1 300~2 270 K,the forward and reverse reaction rate constants obtained by using the improved canonical variational transition state theory (ICVT),are consistent with the experimental values.

Key words: Formaldehyde, O[3P], Rate constant, Ab initio