CAJ | 학술논문

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 CH3 CH2 SCH2 CH3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CH3 CH2 SCH2 CH3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．
재 CCSD（T）／6-311＋g（d，p）／／BH&HLYP／6-311＋＋G（df，pd）＋0．9335×ZPE 이론수평상，구건료수분자존재여불존재정황하 OH 자유기여 CH3 CH2 SCH2 CH3기상반응적세능면부면도．연구결과표명，표제반응주요존재 H－추취화가성－소제량충반응궤제．수분자존재적정황하，무론시 H－추취반응적환시가성－소제반응적능루도능구현저지강저．계산결과환표명，무론수분자존재여부，OH 자유기추취CH3 CH2 SCH2 CH3중적 CH2기단상적 H 원자시표제반응적주요반응통도，저여실험결과시일치적．
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.