Theoretical study on mechanisms and pathways of the CF3O2 + ClO reaction

The mechanisms and reaction pathways for the atmospheric CF3O2 + ClO reaction have been investigated by quantum chemistry methods. The CCSD(T)/6-311++G(2d,2p)//B3LYP/6-311++G(d,p) results show that only the singlet potential energy surface (PES) is of importance for the title reaction, and the dominant products included CF3OOOCl and CF3O + ClOO under the normal atmospheric conditions (T < 300 K). While other products such as CF3OClO2, CF3OOClO, CF3O + OClO and CF2O + FClO2 are negligible. TDDFT (Time Dependent Density Functional Theory) calculations indicate that CF3OOClO and CF3OClO2 will undergo photolysis in the troposphere, and CF3OOOCl will photolyze in the stratosphere.