Effect of the deformation of the double bond in chlorinated ethylene on the rate and mechanism of the reaction with ozone
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The reactivity of the strained C=C bond of the 1-chloroethylene molecule in the reaction with ozone was studied using ab initio (MP2, CASSCT, MRMP2) and DFT (B3LYP) calculations in conjunction with the 6–31+G** basis set. The mechanisms of concerted and nonconcerted addition were examined. The strain ɛ was introduced into the problem by changing the length of the C=C bond and specifying it as a non-optimized coordinate. It is shown that, at least at ɛ ≤ 2%, the activation energy E a decreases linearly with increasing strain. The sensitivities of both channels of the reaction to the strain are similar and only slightly dependent on the method of calculation. The results are analyzed within the framework of a previously developed approach, which makes it possible to obtain an analytical dependence of E a on the force and to relate the change in E a during deformation to the length and rigidity of the initial and transition states.
Keywordsdeformation activation energy rate constant rigidity sensitivity
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