中文摘要：

应用密度泛函理论的MPW1K,BHandHLYP和MPWB1K方法,结合6-31＋G（d,p）基组优化了烯丙醇与臭氧反应势能面上各驻点的几何构型,通过同一水平的振动频率分析确认了中间体和过渡态.反应路径上的驻点都在HL理论水平下进行单点能量校正,并进行了MPW1K/6-31＋G（d,p）水平下的零点振动能校正（ZPE）.对反应机理的详尽分析表明臭氧抽取烯丙醇羟基基团中H的通道的反应势垒比臭氧加合烯丙醇双键基团通道的反应势垒高,臭氧与烯丙醇双键加合生成臭氧化物为最可几反应路径.在加合反应历程中,氢迁移通道需经过氢迁移和离解等复杂过程,最终要产生少量的OH自由基,与烃烯类臭氧化反应产生大量OH自由基的结果相反.

英文摘要：

MPW1K/6-31＋G（d,p）,BHandHLYP/6-31＋G（d,p）,and MPWB1K/6-31＋G（d,p） levels of theory are employed to optimize the geometries of stationary points for the mechanisms of gas-phase ozonolysis of Allyl alcohol.The single-point energy calculations are refined at the HL level of theory based on the MPW1K-optimized geometries.The frequencies at the MPW1K level of theory are used to evaluate ZPVE corrections to the single-point energies.Two different reactive sites of allyl alcohol,C=C and OH groups have been investigated,and results confirm that the C=C group is a highly reactive site.The calculated mechanisms indicate that in ozone-allyl alcohol reaction the yields of OH might be trivial,which is different from the reactions of ozone with unsaturated hydrocarbons.