DFT study of trichloroethene reaction with permanganate in aqueous solution.

The mechanism of the environmentally important reaction between permanganate anion and trichloroethene (TCE) has been studied theoretically using modern DFT functional. It has been shown that IEFPCM/M05-2X/aug-cc-pVDZ theory level yields activation parameters and carbon isotopic fractionation factor in excellent agreement with the experimental data. Obtained results indicate that this reaction proceeds via the 3+2 mechanism with a very early transition state, in which the new C-O bonds are formed only in about 20%. An alternative, stepwise mechanism that involves initial formation of a single new C-O bond and a C-Mn bond, followed by rearrangement to the permanganate-TCE adduct, has been found to be more energetically demanding and in disagreement with the experimental isotopic fractionation.