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_3SCH_3与H2O_2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,计算所得的键鞍点电荷密度的变化情况也确认了反应过程。结果表明,反应共分2步进行,主要经历了O对S的进攻、H转移以及O-O键断裂的历程。并分别考察了其在水中和甲苯的溶剂效应。结果表明,溶剂效应降低了反应的活化能,并使过渡态红外光谱蓝移。
Density function theory （DFT） B3LYP method was employed to study the reaction mechanism of CH3SCH3 and H2O2 at the level of 6-31 1＋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 indicated that the title reaction may involve two similar steps, which might include the attack of O to S, O-O bond cleavage and hydrogen transfer. The solvent effect was also investigated in water and toluene, respectively. The results indicated that the solvent effect lowed the activation energies, also the blue-shifts of transition states were found comparing to the gas phase.
出处
《计算机与应用化学》
CAS
CSCD
北大核心
2012年第12期1433-1437,1436+1435+1437,共5页
Computers and Applied Chemistry
基金
山东省自然科学基金项目(ZR2009BL002)
关键词
二甲基硫醚
过氧化氢
反应机理
电子密度拓扑分析
溶剂效应
thiol, hydrogen peroxide, reaction mechanism, topological analysis of electronic density, Solvent effect
