反式羰基铑碘络合物催化甲醇制乙酸反应的动力学研究
Kinetic study for the reaction of carbonylation of methanol to acetic acid catalyzed by trans-Rh(I)-complex

本文运用密度泛函理论, 选取 B3LYP/6-311+G(2d,p)//B3LYP/SDD方法基组，对反式羰基铑碘络合物催化甲醇羰基化制乙酸反应进行了计算研究, 对势能面上各稳定点进行了全几何参数优化, 通过频率分析确认了过渡态, 并采用内禀反应坐标(IRC)进行了验证, 确定了反应路径. 运用Kozuch撰写的能量跨度模型获得循环反应的动力学信息, 并利用转化频率评估了催化性能与温度的变化关系.
Using the B3LYP method of density functional theory，The carbonylation of methanol to acetic acid catalyzed by trans-Rh(I)-complex has been characterized in detail, while the geometries for all stationary points are completely optimized at the 6-311+G(2d,p) and SDD basis sets. 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, and the change of turnover frequency with temperature was calculated by the AUTOF program.