三氟化氯和环氧丙烷反应的理论研究

Theoretical Study on the Reaction of Chlorine Trifluoride with Propylene Oxide by Density Functional Theory

应用密度泛函理论对三氟化氯和环氧丙烷反应产生C3H5O和C1F2自由基的机理进行了研究.在B3PW91/6-31+G(d,p)水平优化了12个不同反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,并计算了它们的振动频率和零点振动能.采用CCSD(T)/6-31+G(d,p)//B3PW91/6-31+G(d,p)单点能计算方法求得各物种的能量,并作了零点能校正.计算结果表明,三氟化氯和环氧丙烷反应可经过不同的反应路径引发C3H5O自由基和C1F2自由基,其中,三氟化氯呈对称的F原子与环氧丙烷的C(1)上与CH3在同一侧的H原子结合的活化能最低,仅为16.81kJ/mol.

Using density functional theory （DFT）, the reaction of chlorine trifluoride with propylene oxide was studied. At the B3PW91/6-31＋G（d,p） level of DFT, the geometries of all species （reactants, transition states, and products） were optimized and the vibration frequencies and zero point vibrational energies （ZPVE） calculated. All the energies of the species were obtained with the CCSD（T）/6-31＋G（d,p）// B3PW91/6-31＋G（d,p） method and ZPVE correction. The calculated results suggest that the reaction should have various channels, yielding the products of C3H5O radical, C1F2 radical and HF molecule. The main reaction channel is C3H6O＋C1F3→TS7→P2 （C3H5O＋HF＋C1F2）, and the corresponding activation energy is 16.81 kJ/mol.