Chemical Research in Chinese Universities ›› 2011, Vol. 27 ›› Issue (1): 117-122.

• Articles • Previous Articles     Next Articles

Theoretical Investigation on Hyperfine Structures of Perfluoropolyether Radicals

DONG Su-li and LIU Ya-jun*   

  1. Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China
  • Received:2010-03-08 Revised:2010-06-29 Online:2011-01-25 Published:2011-01-04
  • Contact: LIU Ya-jun E-mail:yajun.liu@bnu.edu.cn
  • Supported by:

    Supported by the Major State Basic Research Development Programs of China(No.2007CB815206), the National Natural Science Foundation of China(Nos.20873010, 20720102038) and the Fundamental Research Funds for the Central Universities of China.

Abstract: The geometries of CF3OCF2·, CF3OCFCF3· and CF3OCF2CF2· radicals were investigated by density functional theory(DFT) method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the αC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling constants(hfcc’s) of the 19F atoms of the three radicals were calculated by B3LYP, MP2(full) and QCISD(full) methods. The calculated values agree with the experimental values, especially for the a values of Fα, the a values are 125.6×10–4, 104.2×10–4, and 83.2×10–4 T of CF3OCF2·, CF3OCFCF3· and CF3OCF2CF2·, respectively. These results better explain the experimental observation.

Key words: Perfluoropolyether radical, Hyperfine coupling constant, Density functional theory