Theoretical study on the unimolecular decomposition of 2-chlorinated ethyl hydroperoxide

Abstract

Chlorine-containing organic compounds have been of major interest since such compounds would serve as temporary reservoirs for HOX, ROX and ClOX radicals. Moreover, it would transport chlorine species to the atmosphere and stratosphere. However, limited studies have been performed on the 2-chlorinated ethyl hydroperoxide. In this work, the mechanism of unimolecular dissociation of 2-chlorinated ethyl hydroperoxide is theoretically studied. The equilibrium structures are optimized at the Boese–Martin for kinetics (BMK) level. And the energies are further refined at the Balanced multi-coefficient correlation-coupled cluster theory with single and double excitations (BMC-CCSD) level on the basis of the optimized geometries. Fifteen reaction channels are finally confirmed including the direct C–O, O–O, O–H, and C–C bond cleavage or the H2-, H2O-, H2O2-, and CH3Cl-elimination.