摘要
采用密度泛函理论的B3LYP方法,在6-311+G(d,p)基组水平上研究了CH_3SH、CH_3SCH_3、C_4H_4S与CH_3CO_3H的微观反应机理,全参数优化了反应势能面上各驻点的几何构型,振动分析和内禀反应坐标(IRC)分析结果证实了中间体和过渡态的真实性。结果表明,三个反应主要经历了O对S的进攻、H转移以及O-O键断裂的历程。其中噻吩反应的活化能最高,为87.9 kJ/mol,说明噻吩的氧化脱硫最困难。对于甲硫醇、二甲基硫醚、噻吩与过氧化氢反应来说,当加入乙酸做催化剂后,第一步反应的活化能皆得到大幅度的降低。
Density function theory（DFT） B3LYP method was employed to study the reaction mechanism of CH3SH（CH3SCH3,C4H4S） and CH3CO3H at the level of 6-311＋G（d,p） basis sets.Geometries of the stationary points were completely optimized.The transition states were validated by the vibration analysis and the internal reaction coordinate（IRC） calculations.The results showed that the three kinds of reactions were similar to each other,which might involve the attack of O to S,O-O bond cleavage and hydrogen transfer.The reaction of C4H4S and CH3CO3H had the highest activation energy（87.9 kJ/mol）,which indicated the oxidative desulfurization of C4H4S by CH3CO3H can occur most difficultly.When acetic acid was added to H2O2 reaction system as catalyst,the activation energies of first step of three reactions were decreased greatly.
出处
《计算机与应用化学》
CAS
CSCD
北大核心
2014年第12期1547-1551,共5页
Computers and Applied Chemistry
基金
滨州学院国家级大学生创新创业训练计划项目(201210449107)
滨州学院青年人才创新工程项目(BZXYQNLG201202)
滨州学院青年人才创新工程项目(BZXYQNLG200710)
滨州市科技发展计划项目(2013ZC1502)
中央高校基本科研业务费专项资金资助(14CX06002A)
关键词
硫醇
硫醚
噻吩
过氧乙酸
反应机理
thiols
sulfur ether
thiophene
hydrogen peroxide
reaction mechanism
