Theoretical Study on the Reaction of Chlorine Trifluoride Oxidewith Propylene Oxide by Density Functional Theory

Using density functional theory (DFT), the reaction of chlorine trifluoride oxide (ClF₃O) with propylene oxide (C₃H₆O) was studied.At the B3PW91/6-31++G(d, p) level, geometries of all species (reactants, transition states and products) were optimized, and the vibrational frequencies and zero point vibrational energies (ZPVE) were calculated.The energies of all species were refined with CCSD(T)/6-31++G(d, p)//B3PW91/6-31++G(d, p) method and ZPVE correction.The calculated results suggest that the initial reaction has various pathways to yield the main products of C₃H₅O and ClOF₂ radicals, and C₃H₆O₂ and ClF₃ molecules.The reactions of C₃H₅O and ClOF₂ radicals have different pathways to yield the main products of C₃H₄O, ClOF and HF molecules.The main reaction channel is C₃H₆O+ClF₃O→TS12→P4 (C₃H₅O+HF+ClOF₂)→P12 (CH₂CHCHO+2HF+ClOF).P4 is produced by C₃H₆O and ClF₃O via TS12 with a low barrier of 15.63 kJ/mol, and P12 can be formed from P4 through a barrierless process.