摘要
在CCSD(T)/6-311+g(d,p)//BH&HLYP/6-311++G(df,pd)+0.9335×ZPE理论水平上,构建了水分子存在与不存在情况下OH自由基与CH3CH2SCH2CH3气相反应的势能面剖面图.研究结果表明,标题反应主要存在H-抽取和加成-消除两种反应机制.水分子存在的情况下,无论是H-抽取反应的还是加成-消除反应的能垒都能够显著地降低.计算结果还表明,无论水分子存在与否,OH自由基抽取CH3CH2SCH2CH3中的CH2基团上的H原子是标题反应的主要反应通道,这与实验结果是一致的.
In this paper,the profiles of potential energy surface for the gas phase reaction of OH radical with CH3 CH2 SCH2 CH3 in the presence and absence of water molecule have been drawn using the CCSD （T）/6-311＋G（d,p）//BH＆HLYP/6-311＋＋G（df,pd）＋0.9335×ZPE levels of theory.The computation-al results indicate that the title reaction mainly exists two kinds of reaction mechanism,namely,H-ab-straction and addition-elimination mechanism.The presence of water molecule can effectively reduce the energy barriers of both H-abstraction and addition-elimination reaction channels.The computational results also show that the H-abstraction channel from the CH2 group in CH 3 CH 2 SCH 2 CH 3 by OH radical is the major pathway for the title reaction in the presence and absence of watermolecule,which is agree with the experimental results well.
出处
《曲阜师范大学学报（自然科学版）》
CAS
2015年第2期53-61,共9页
Journal of Qufu Normal University(Natural Science)
基金
江苏省高校自然科学研究项目(10KJB150017)
关键词
二乙基硫
OH
自由基
水分子
反应机理
势能面剖面图
Diethyl sulfide
OH radical
water molecule
reaction mechanism
potential energy surface
