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用密度泛函理论(DFT)研究了甲醇与一氧化碳的微观反应机理.在B3LYP/6-311++G(d,p)水平上优化了反应物、过渡态及产物的几何构型,并通过振动分析和内禀反应坐标方法(IRC)分别确认了过渡态的结构与反应途径.在CCSD/6-311++G(d,p)水平上进行能量校正,并根据计算的势能面探讨了CH3OH+CO反应机理.结果表明,CH3OH+CO反应体系有三个可能的反应通道,产物分别为甲酸甲酯、乙酸、羟基乙醛.在无催化条件下,计算得到生成甲酸甲酯、乙酸和羟基乙醛的反应活化能分别是364.715,460.775和611.402kJ·mol-1,生成甲酸甲酯和羟基乙醛的反应为吸热反应,而生成乙酸的反应为放热反应.
The reaction mechanism between methanol and carbon monoxide was investigated by using density functional theory (DFT). The reactants, transition states and geometry of the products were optimized at B3LYP / 6-311 ++ G (d, p) Vibration analysis and intrinsic reaction coordinate method (IRC) confirmed the structure and reaction pathway of the transition state respectively. The energy correction was carried out at the level of CCSD / 6-311 ++ G (d, p) and the potential energy surface was discussed CH3OH + CO.The results show that there are three possible reaction channels in CH3OH + CO reaction system, the products are methyl formate, acetic acid and hydroxyacetaldehyde, respectively. Under the condition of no catalysis, the yield of methyl formate, acetic acid and hydroxyl The reaction activation energies of acetaldehyde were 364.715, 460.775 and 611.402 kJ · mol-1, respectively. The reaction of methyl formate and hydroxyacetaldehyde was endothermic and the reaction of acetic acid was exothermic.