A theoretical study of abiotic methylation reactions of gaseous elemental mercury by halogen containing molecules

Abstract. Methylation reactions of gaseous elementary mercury by halogen containing molecules such as halogenomethane species CH₃X (with X=Cl, Br and I) and the dimethylchlorinium ion CH₃ClCH₃⁺ were investigated at the DFT level. With CH₃X, the reaction is predicted to be almost athermic and kinetically demanding for a thermal reaction. The reaction can proceed photochemically in the visible range; therefore sunlight may increase the reaction rate. These results compare well with the experimental data. Consecutive methylation of the CH₃HgX products (with X=Cl, Br and I) and subsequent formation of CH₃HgCH₃ were also studied. These reactions are predicted to be kinetically inaccessible and thermodynamically unfavorable. With CH₃ClCH₃⁺, the reaction is predicted to be athermic but kinetically easy. This is due to the suitability of the methyl transfer reagent. Geometrical and electronic data were systematically analyzed in order to rationalize the results.