将密度泛函理论计算纳入高等化学教学初探——对乙酸乙酯碱性水解机理的理论研究

张春芳,张翠妙,李江涛,韩琳玉,顾芳,王海军

Exploration for the Implementation of Density-Functional-Theory Computations into Chemistry Teaching at College: Theoretical Study on the Alkalescence Hydrolysis Reaction Mechanism of Ethyl Acetate

Chunfang ZHANG,Cuimiao ZHANG,Jiangtao LI,Linyu HAN,Fang GU,Haijun WANG

表1 理论计算反应焓、中间体以及过渡态能量(kJ∙mol−1)

style="border-right:1px solid;" Species B3LYP/6−311G** without solvent effect B3LYP/6−311G** with solvent effect B3LYP/6−311+G* with solvent effect B3LYP/6−311++G** with solvent effect M06−2X/Def2−TZVPP with solvent effect without ZPE with ZPE without ZPE with ZPE without ZPE with ZPE without ZPE with ZPE without ZPE with ZPE OH−+ CH3CH2OOCCH3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 TS([CH3CH2OOCCH3−OH]−) −168.23 −35.22 −25.73 104.41 37.99 43.64 40.51 170.45 22.74 29.70 IM([CH3CH2OOCCH3−OH]−) −236.89 −183.36 −65.03 −12.31 9.45 59.90 13.01 62.96 −15.44 −2.91 CH3CH2O− +CH3COOH −140.10 −151.29 −23.29 −34.57 −6.10 −14.44 23.04 14.88 28.07 32.27 CH3CH2OH +CH3COO− −273.19 −275.21 −138.69 −150.39 −82.30 −93.90 −79.65 −90.91 −80.21 −76.39 Ea −168.23 −35.22 −25.73 104.41 37.99 59.90 40.51 170.45 22.74 29.70 ∆rH −273.19 −275.21 −138.69 −150.39 −82.30 −93.90 −79.65 −90.91 −80.21 −76.39