Theoretical insights into the reaction mechanisms between 2,3,7,8-tetrachlorodibenzofuran and the methylidyne radical

To explore the potential role of the methylidyne radical (CH) in the transformation of 2,3,7,8-tetrachlorodibenzofuran (TCDF), in this study, the detailed reaction mechanisms between TCDF and CH radical have been systematically investigated employing the B3LYP method of density functional theory (DFT) in combination with the atoms in molecules (AIM) theory and ab initio molecular dynamics. It was found that the title reaction is a multi-channel reaction, i.e., the CH radical can attack the C–X (X = C, Cl, H, O) bonds of TCDF via the insertion modes, resulting in the formation of 13 products. Thermodynamically, the whole reaction processes are exothermic and spontaneous since all the enthalpy and Gibbs free energy changes are negative values in the formation processes. Moreover, the thermodynamic stability of the products is controlled by the distribution of the single unpaired electron. Kinetically, the most favorable reaction channel is the insertion of the CH radical into the C–C bond except for the C atoms attached to the chlorine atom. Moreover, the dominant products have been further confirmed by the molecular dynamics. Meanwhile, the IR spectra and hyperfine coupling constants of the dominant products have been investigated to provide helpful information for their identification experimentally. In addition, the reactivity of the CH radical toward the F- and Br-substituted TCDFs has also been investigated. Expectedly, the present findings can enable us to better understand the reactivity of the CH radical toward organic pollutants analogous to TCDF in the atmosphere.