CAJ | 학술논문

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C4H4S与H2O2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，决速步骤的活化能为157.3 kJ/mol，能垒高于甲硫醇、甲硫醚和过氧化氢反应的类似步骤。
채용밀도범함이론적B3LYP방법，재6-311＋G(d, p)기조수평상연구료C4H4S여H2O2적미관반응궤리，전삼수우화료반응세능면상각주점적궤하구형，진동분석화내품반응좌표(IRC)분석결과증실료중간체화과도태적진실성，계산소득적건안점전하밀도적변화정황야학인료반응과정。결과표명，반응분2보진행，주요경력료O대S적진공、H전이이급O-O건단렬적역정，결속보취적활화능위157.3 kJ/mol，능루고우갑류순、갑류미화과양화경반응적유사보취。
Density function theory (DFT) B3LYP method was employed to study the reaction mechanism of thiophene and H2O2 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 indicated that the title reaction may involve two steps, which might include the attack of O to S, O-O bond cleavage and hydrogen transfer. The first step of the title reaction constitutes the rate-determining step, the corresponding activation energy is 157.3 kJ/mol. And thiophen has a higher energy barrier than dimethyl sulfide or thiol in the oxidation reaction by H2O2.