Ab Initio direct classical trajectory investigation on the SN2 reaction of F- with NH2F: Nonstatistical central barrier recrossing dynamics

作者：Yu Feng^*

来源：Journal of Computational Chemistry, 2012, 33(4): 401-405.

DOI：10.1002/jcc.21979

• SN2 reaction
• F-
• NH2F
• ab initio direct classical trajectory
• central barrier recrossing

The bimolecular nucleophilic substitution ( SN2) reaction of Fa with NH2Fb has been investigated with the ab initio direct classical trajectory method. According to our trajectory calculations, a dynamic behavior of nonstatistical central barrier recrossing is revealed. Among the 64 trajectories calculated in this work, 45 trajectories follow the dynamic reaction pathways as assumed by statistical theory and other 19 trajectories with central barrier recrossings are nonstatistical. For the nonstatistical trajectories, the central barrier recrossings may originate from the inefficient kinetic energy transfer from the intramolecular modes of the NH2Fa moiety in the dynamic Fb . HANHAFa complex to the intermolecular modes of the dynamic Fb . HANHAFa complex on the exit- channel potential energy surface. With respect to the dynamic behavior of the nonstatistical central barrier recrossing, the statistical theories such as the RiceRamsperger- Kassel- Marcus and transition state theories without further corrections cannot be used to model the reaction kinetics for this SN2 reaction. VC 2011 Wiley Periodicals, Inc. J Comput Chem 33: 401- 405, 2012

• 出版日期2012-2-5
• 单位西安工业大学