6533b821fe1ef96bd127c1a5

RESEARCH PRODUCT

Ab Initio Study on the Mechanism of the Reactions of the Nitrate Radical with Haloalkenes:  1,2-Dichloroethene, 1,1-Dichloroethene, Trichloroethene, and Tetrachloroethene

subject

description

A general mechanism for the reactions of the NO3 radical with 1,2-dichloroethene, 1,1-dichloroethene, trichloroethene, and tetrachloroethene is proposed from ab initio DFT calculations. The calculated mechanism shows three main parallel reaction pathways. For the systems where the two carbon atoms are differently substituted, the study includes both the attacks with Markownikoff and contra-Markownikoff orientation. The first reaction pathway leads to the formation of an epoxide along with the NO2 radical, the second one to the formation of carbonyl compounds, and the third one leads, through the cleavage of the C−C bond, to the formation of carbonyl compounds with a lower number of carbon atoms. The stationary points on the potential energy surface (PES) were found by means of density functional theory (DFT) calculations with the B3LYP functional and the 6-31G* basis set. For each stationary point, the geometry was optimized and the obtained conformation was characterized as an equilibrium structure (reac...