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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。
The B3LYP method of density functional theory (DFT) was used to study the microscopic reaction mechanism of CH_3SCH_3 and H2O_2 at the 6-311 + G (d, p) basis set. The geometrical configurations of all stationary sites on the reaction potential surface were optimized by all the parameters. Vibration analysis and intrinsic reaction coordinate (IRC) analysis confirmed the authenticity of the intermediate and transition states, and the calculated charge-saddle point charge density also confirmed the reaction process. The results show that the reaction is divided into two steps, mainly under the O attack on the S, H transfer and O-O bond fracture process. Their solvent effects on water and toluene were investigated respectively. The results show that the solvent effect decreases the activation energy of the reaction and shifts the blue-shifted infrared spectra.