氟代次甲基自由基与臭氧反应机理的理论研究
首发时间:2014-10-23
摘要:为阐明氟代次甲基自由基(CF)与O3在二重态势能面上的微观反应机理,本研究采用密度泛函理论在B3LYP/6-311G(d, p)水平上对该反应进行了详细的理论研究。通过全参数优化反应物、中间体、过渡态及产物的几何构型,得到相应能量及频率值,并采用内禀反应坐标(IRC)计算方法在同一水平上确认了中间体和过渡态之间的联系。研究发现CF与O3反应有以下5种产物通道:P1(FCO + O2)、P2(FCO2 + O)、P3(CO2 + O + F)、P4(CO2 + FO)和P5(CO + O2 + F)。通过对反应路径上各驻点的能量分析得出P1(FCO + O2)为主要通道,P2(FCO2 + O)、P3(CO2 + O + F)、P4(CO2 + FO)、P5(CO + O2 + F)都是次要通道,其产率依次减小。
关键词: 理论计算 反应机理 氟代次甲基(CF) 臭氧(O3)
For information in English, please click here
Theoretical study on the reaction mechanism of fluorinated methylidyne radical with ozone
Abstract:In order to clarify the microscopic reaction mechanism of fluorinated methylidyne radical (CF) with O3 on the doublet potential energy surface, the reaction was studied theoretically by using density functional method at the B3LYP/6-311G(d, p) level. The geometric structures of reactants, intermediates, transition states and products were optimized, and their vibration frequencies and energy values were obtained. Intrinsic reaction coordinate calculations at the same level were implemented to confirm the connections between transition states and intermediates. It is found that the CF + O3 reaction possesses five product channels: P1(FCO + O2), P2(FCO2 + O), P3(CO2 + O + F), P4(CO2 + FO), P5(CO + O2 + F). Through the energy analysis of the stationary points on each reaction pathway, the conclusion can be drawn that the P1(FCO + O2) channel is the most feasible, P2(FCO2 + O), P3(CO2 + O + F), P4(CO2 + FO), P5(CO + O2 + F) are all secondary channels, their production rate decreases in turn.
Keywords: theoretical calculation reaction mechanism fluorinated methylidyne radical (CF) ozone (O3)
基金:
论文图表:
引用
No.4614987222691414****
同行评议
勘误表
氟代次甲基自由基与臭氧反应机理的理论研究
评论
全部评论0/1000