A comparable DFT study on reaction of CHCl•- with O3 and S2O

Context In this discussion, we began building two model, S2O + CHCl center dot- and O-3 (+) CHCl center dot-, using DFT-BHandHLYP method, to study their reactions mechanisms on singlet PES. For this purpose, we hope to explore the effects of the difference between sulfur and oxygen atoms on the CHCl center dot- anion. Experimentalists and computer scientists may utilize the collected data to generate a wide range of hypotheses for experimental phenomena and predictions, allowing them to realize their full potential. Methods The ion-molecule reaction mechanism of CHCl center dot- with S2O and O-3 was studied using the DFT-BHandHLYP level of theory with the aug-cc-pVDZ basis set. Our theoretical findings show that Path 6 is the favored reaction pathway for CHCl center dot- + O-3 reaction as identified by the O-abstraction reaction pattern. Comparing to the direct H-and Cl-abstraction mechanisms, the reaction (CHCl center dot- + S2O) prefers the intramolecular S-N(2) reaction pattern. Moreover, the calculated results demonstrated that the CHCl center dot- + S2O reaction is thermodynamically more favorable than the CHCl center dot- + O-3 reaction, which is kinetically more advantageous. As a result, if the required reaction condition in the atmospheric process is met, the O-3 reaction will happen more effectively. In terms of kinetics and thermodynamics viewpoints, the CHCl center dot- anion was very effective in eliminating S2O and O-3.