Electron affinity and inversion distortion of dibenzo-p-dioxin

The photochemical fate of polychlorinated dibenzo-p-dioxins, ubiquitous environmental pollutants, could be highly influenced by electron-donors such as triethylamine. Therefore, it is essential to have electron affinities of these species. We have performed density functional calculations for neutral and anion of dibenzo-p-dioxin (DD) to obtain the adiabatic electron affinity. We find that the order of D2 and D2h structures varies with the level of theory. The D2h neutral DD undergoes inversion distortion into less symmetric D2 anion upon electron attachment due to C–O–C bond cleavage.