CH_3F与C_2H_3反应机理的理论研究  

Theoretical study on the reaction mechanism of CH_3F with C_2H_3

作　　者：冯丽霞[1,2] 白英奇[1] 左玉[1] 

机构地区：[1]太原师范学院化学系,山西太原030031 [2]山西大学分子科学研究所,化学生物学与分子工程教育部重点实验室,山西太原030006

出　　处：《分子科学学报》2014年第3期189-195,共7页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(21076138)

摘　　要：采用密度泛函B3LYP/6-311G(d,p)方法对CH3F与C2H3的反应体系进行了理论研究,获得了反应的势能面信息及可能的微观机理.在QCISD(T)/6-311++G(d,p)水平上精确计算了各反应物种的单点能.结果表明,除抽提氢反应外,标题反应还存在抽提氟(R1)、消氟化氢(R2)、消氢(R3)和自由基形成(R4)四类反应.在QCISD(T)/6-311++G(d,p)//B3LYP/6-311G(d,p)水平上,R1,R2,R3和R4反应的能垒分别是163.9,152.2,209.8和224.2kJ·mol-1,相应反应能为-56.6,-164.3,-2.7和-156.0kJ·mol-1,所有反应均放热,为热力学允许的反应.DFT-B3LYP/6-311G（d,p）method has been employed to obtain the potential energy surface information and to study the micro-mechanism of the reaction of CH3F with C2H3.The single-point energies of all the stationary points were further refined at the QCISD（T）/6-311＋＋G（d,p）level.It is shown that besides the hydrogen abstraction reaction,the title reaction also owns four other types of reactions,namely the fluorine abstraction reaction（R1）,the HF elimination reaction（R2）,the hydrogen elimination reaction（R3）and the reaction of radical formation（R4）.At the QCISD（T）/6-311＋＋G（d,p）//B3LYP/6-311G（d,p）level,the potential barriers of the reactions R1,R2,R3 and R4 are 163.9,152.2,209.8 and 224.2kJ·mol-1,and the reaction energies are-56.6,-164.3,-2.7 and-156.0kJ·mol-1,respectively.All the reactions are exothermic and thermodynamically allowed.

关 键 词：CH3F C2H3 反应机理 过渡态 消氟化氢反应 

分 类 号：O641[理学—物理化学]