Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (04): 801-807.doi: 10.3866/PKU.WHXB20110409

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Anionic Production Pathways Involved in the Reaction between OH- and CH2ClF

SONG Lei1, YU Feng2, WU Li-Xia1, ZHOU Xiao-Guo1, LIU Shi-Lin1   

  1. 1. Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China;
    2. Department of Mathematics and Physics, Xi′an Technological University, Xi′an 710032, P. R. China
  • Received:2010-11-24 Revised:2011-01-24 Published:2011-03-29
  • Contact: ZHOU Xiao-Guo E-mail:xzhou@ustc.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20603033, 10979042) and National Key Basic Research Program of China (973) (2007CB815204).

Abstract:

The anionic production pathways involved in the reaction between hydroxide anion (OH-) and chlorofluoromethane (CH2ClF) were theoretically investigated. The optimized geometries of all the important species on the reaction potential energy surface were obtained at the B3LYP/6-31+G(d,p) and B3LYP/6-311++G(2d,p) levels. Consequently, harmonic vibrational frequencies and zero point energies (ZPEs) were calculated. Based on the relative energies of all the species that were calculated at the CCSD(T)/6-311+G(3df,3dp) level, the anionic production channels for the H+-abstraction and the bimolecular nucleophilic substitution (SN2) reaction processes are elaborated upon. According to the calculated barrier heights for the production pathways, the H+-abstraction channel is dominant, which agrees very well with previous experimental conclusions. In addition, non-typical anionic products are suggested to form during the SN2 reaction processes where the serious dynamic effect probably causes the SN2 reaction process to produce F-.

Key words: Hydroxide anion, Chlorofluoromethane, Reaction mechanism, Proton transfer, Nucleophilic substitution (SN2) reaction

MSC2000: 

  • O641