Quantum Mechanical Studies of Isomeric and Conformeric Structures of Methyl-Chloro-Peroxide

摘要

Ab initio quantum mechanical studies are carried out for the isomeric structures and the torsional potential of methyl-chloro-peroxide.These species are important intermediates in the atmospheric reactions of methyl,methoxy,and methylperoxy radicals with chlorine dioxide,chlorine monoxide,and atomic chlorine,respectively.The calculations indicate that the peroxide form,CH_3OOC1,with a skew geometry for C,O,O,and Cl atoms,is the lowest minimum energy structure followed by CH_3OC1O.The CH_3C1O_2 adduct is found to be much higher in energy.The calculated isomerization barriers are found to be relatively high to permit possible interconversion pathways.