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Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone 被引量:1

Theoretical Studies on the Kinetics and Mechanisms of Reactions for Methyl Vinyl Ether and Ozone
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摘要 The interconversion between the two distinct isomers of methyl vinyl ether (MVE), the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6311++G(d,p) level of theory for optimized geometries and frequency calculations and at the QCISD/631G(d,p) level for the single point energy calculations. The rate coefficients were calculated for the temperature range 280-440 K by using the canonical transition state theory (TST). For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The intereonversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8× 10^-17 cm^3/(molecule.s) at 298.15 K, which agrees with the experimental value for ethyl vinyl ether.
出处 《Chinese Journal of Chemical Physics》 SCIE CAS CSCD 北大核心 2008年第4期324-332,共9页 化学物理学报(英文)
关键词 Methyl vinyl ether OZONE Reaction pathway Primary ozonide INTERCONVERSION Rate constant Transition state theory 动力学 反作用力 乙烯基醚 臭氧
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