DFT Study of Trichloroethene Reaction with Permanganate in Aqueous Solution

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Institute of Applied Radiation Chemistry, Faculty of Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland
*Phone: +48 42 631 3199. E-mail: [email protected]
Cite this: Environ. Sci. Technol. 2011, 45, 7, 3006–3011
Publication Date (Web):March 7, 2011
Copyright © 2011 American Chemical Society
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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.

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Tables reporting activation free energies (kcal/mol) and carbon isotopic fractionations (‰), key geometrical parameters of the calculated transition state structures of the 3 + 2 reaction at all studied levels of theory, structures of proximity complexes and transitions states of the 2 + 2 reaction, and the Cartesian coordinates for transition states for both mechanisms. This material is available free of charge via the Internet at http://pubs.acs.org.

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