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用密度泛函理论(DFT)在B3LYP/6鄄31G(d,p)的计算水平上研究了离子液中1鄄乙基鄄3鄄甲基咪唑阳离子(EMIM+)的4鄄H和5鄄H原子催化丁烯双键异构反应的可能途径,优化了反应体系的平衡态和过渡态的几何构型,分析了反应过程中键参数的变化,通过振动分析对平衡态和过渡态进行了验证.计算结果表明,离子液中的EMIM+首先通过4鄄H和5鄄H原子吸附丁烯,进而催化丁烯的双键异构反应,EMIM+的4鄄H和5鄄H催化1鄄丁烯异构为2鄄丁烯的正反应活化能分别为204.2和207.3kJ·mol-1,逆反应活化能约为220.9和223.8kJ·mol-1,反应为基元反应.
The density functional theory (DFT) was used to calculate the 4-H and 5-H of 1-ethyl-3-methylimidazolium cation (EMIM +) in ionic liquid at B3LYP / 6-31G (d, p) The possibility of atom-catalyzed isomerization of butene double bond was optimized. The equilibrium states and transition geometries of the reaction system were optimized. The key parameters of the reaction were analyzed. The equilibrium and transition states were verified by vibration analysis The calculated results show that the EMIM + in ionic liquid firstly adsorbs butene via 4-H and 5-H atoms, and then catalyzes the double bond isomerization of butene. The 4-H and 5-H of EMIM + The activation energies of 2-butene are 204.2 and 207.3 kJ · mol-1, respectively, and the activation energies of reverse reaction are about 220.9 and 223.8 kJ · mol-1, respectively. The reaction is the elementary reaction.