摘要
本文运用密度泛函理论DFT-B3LYP方法,对铑、碘元素采用相对论校正赝势基组SDD,对C、O、H采用6-311+G(2d,p)基组,计算研究了顺式羰基铑碘络合物催化甲醇羰基化制乙酸反应的微观机理,优化了各反应物、中间体和过渡态的构型特征,用频率分析方法和内禀反应坐标方法对过渡态进行了验证,运用Kozuch撰写的能量跨度模型获得循环反应的动力学信息,确定了决定循环反应速率的决速过渡态和决速中间体,并利用转化频率评估了催化性能与温度的变化关系.
The carbonylation of methanol to acetic acid catalyzed by cis-Rh（I）-complex has been investigated by using the B3LYP level of density functional theory, with the relativistic effective core potential （RECP） of basis sets （SDD） for Rh and I and the 6-311＋G（2d,p） basis set for C, H and O. The geometries for reactants, the transition states and the products are completely optimized. All the transition states are verified by the vibrational analysis and the internal reaction coordinate （IRC） calculations. The energetic span model coined by Kozuch was applied in this cycle to obtain some kinetic information. Turnover frequency （TOF） determining transition state （TDTS） and the TOF determining intermediate （TDI） were confirmed, and the TOF along with changing in temperatures were calculated by the AUTOF program.
出处
《原子与分子物理学报》
北大核心
2017年第2期213-218,共6页
Journal of Atomic and Molecular Physics
基金
甘肃省高等学校科研项目(2014A-138)
关键词
甲醇羰基化
铑碘络合物
乙酸
密度泛函理论
转化频率
Methanol carbonylation
Rh （I） - complex
Acetic acid
Density functional theory
Turnover frequency
