Theoretical Investigations On The Reactions Mechanisms And Rate Constants Of Organic Peroxides And Haloethers With Several Radicals

By the quantum chemistry theory, we investigated （CH₃）₃COOH,（CH₃）₂CHOOH and CHF₂OCF₂CHFCl with some radicals reactions. We calculateddynamics properties for the title reactions, such as the rate constants, the temperaturedependence and so on. What’s more, the relative geometries of organic peroxides andhaloethers and the potential energy surface （PES） are obtained. The existing results ofthis work are summarized as follows:1. The theoretical study of the （CH₃）₃COOH/（CH₃）₂CHOOH+OH reaction arecalculated using BH&H-LYP, MP2, CCSD（T） and QCISD（T） methods with6-311G（d,p） basis set. The potential energy surfaces （PESs） including geometries,vibrational frequencies are obtained. The reaction enthalpies (Δ H_r,298⁰) and reactiongibbs free energies (ΔG_r,298⁰) are obtained at the same methods. The rate constantsstudied by variational transition state theory and small-curvature tunneling （CVT/SCT）theory.2. The theoretical investigation on the mechanism of the reactionCHF2OCF₂CHFCl+Cl. The frequencies, geometries of all the stationary points arecarried out at the B3LYP/6-311G（d,p）, BH&H-LYP/6-311G（d,p） and CCSD（T）//B3LYP/6-311G（d,p）levels. The theoretical reaction gibbs free energiesΔG_r,298⁰andreaction enthalpies (ΔH_r,298⁰) are also calculated.