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ABSTRACT: The isomerization reaction processes of acetone molecule CH3COCH3 has been calculated using the DFT-B3LYP method combined with the standard 6-31G(d,p) basis set. In order to obtain more accurate single-point energy the QCISD(T)/cc-pVDZ method is used. Altogether five isomerization reaction channels are confirmed using the IRC method and the corresponding isomerization products are methyl vinyl ether (cis- and trans-), allyl alcohol, and propen-2-ol, respectively. Acetone isomerizes to trans-methyl vinyl ether in one channel, and in the other four channels it isomerizes through the intermediate propylene oxide. In two of the four channels, acetone isomerizes to cis-methyl vinyl ether. Obviously, propylene oxide is an important intermediate in the isomerization process of acetone molecule. From the number of transition states and intermediates and the heights of barriers we infer that the most possible product is allyl alcohol. Based on the isomerization products and intermediates the possible dissociation channels and product fragments are discussed.
Journal of Molecular Structure-theochem - J MOL STRUC-THEOCHEM. 01/2003; 638(1):215-228.