Reaction of CHCl•- with HCHO and H2O: A theoretical study

To compare the ion-molecule reaction mechanism of CHCl center dot- with HCHO and H2O, the DFT-BHandHLYP level of theory with the aug-cc-pVDZ basis set was used. Our theoretical findings show that the H-abstraction reaction pattern identified pathway 5 as the preferred pathway for the reactions of CHCl center dot- + H2O. When the direct H- and O-abstraction data are examined, the intramolecular S(N)2 reaction pattern appears to be the preferred pathway for the CHCl center dot- + HCHO reaction. The reaction between CHCl center dot- and H2O should be less competitive based on the principal reactive pathways of CHCl center dot- + HCHO. As a result, in the atmospheric process the reaction of HCHO with CHCl center dot- may not be appreciably accelerated by the breakdown of HCHO with and without the H2O molecule.