Acta Phys. -Chim. Sin. ›› 2002, Vol. 18 ›› Issue (01): 45-49.doi: 10.3866/PKU.WHXB20020110

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A Density Functional Method(DFT) Study on the Cyclic Reaction Kinetics

Wang Yong-Cheng;Geng Zhi-Yuan;Chen Hong-Shan   

  1. Department of Chemistry, Department of Physics, Northwest Normal University, Lanzhou 730070
  • Received:2001-05-18 Revised:2001-09-27 Published:2002-01-15
  • Contact: Wang Yong-Cheng E-mail:chenhs@nwnu.edu.cn

Abstract: The cyclic reaction kinetics of carbonyl oxides (H2COO, HFCOO, F2COO and Me2COO) has been studied using the density functional method(DFT) at B3LYP(full)/6311G level. The energies and structures of reactants and products were optimized in full geometries. The transition states were found by the QST2(or QST3) method and were proved by IRC calculations. The activation thermodynamic data were calculated, based on the transition states theory, and the rate constants and frequency factors were obtained from 148.15 K to 398.15 K. The dynamic calculation results show that the carbonyl oxides easily isomering to form dioxiranes at room temperature, and the electronegative substituent can enhance cyclization of the carbonyl oxides.

Key words: Cyclic reaction of carbonyl oxide, Dynamics research, Density function method(DFT), Activation energy, Rate constant