物理化学学报 >> 2002, Vol. 18 >> Issue (06): 522-526.doi: 10.3866/PKU.WHXB20020610

研究论文 上一篇    下一篇

DFT法研究3-羟基丙烯醛的双键旋转异构反应机理

蒲敏;王海霞;冯霄;吴东;孙予罕   

  1. 西安交通大学应用化学系;化学工程系, 西安　710049;中国科学院山西煤炭化学研究所煤转化国家重点实验室，太原　030001
  • 收稿日期:2001-12-07 修回日期:2002-01-23 发布日期:2002-06-15
  • 通讯作者: 王海霞 E-mail:hxwang@mail.xjtu.edu.cn

Research on the Rotation Rearrangement of C=C Double Bond of 3-Hydroxy Acrolein by Density Function Theory

Pu Min;Wang Hai-Xia;Feng Xiao;Wu Dong;Sun Yu-Han   

  1. Department of Applied Chemistry;Department of Chemical Engineering, Xi’an Jiaotong University, Xi’an　710049;State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan　030001
  • Received:2001-12-07 Revised:2002-01-23 Published:2002-06-15
  • Contact: Wang Hai-Xia E-mail:hxwang@mail.xjtu.edu.cn

PDF

3295

赞

摘要： 利用密度泛函理论(DFT)分别在B3LYP/6-31G**和B3LYP/6-311＋＋G**的计算水平上优化了基态3-羟基丙烯醛分子在双键旋转异构反应过程中的平衡态以及过渡态的几何构型，分析了反应过程中键参数的变化，计算了该反应的内禀反应坐标(IRC)，发现在重排反应途径上存在一个四元环骨架的中间体.通过振动分析对平衡态和过渡态进行了确认，并得到了零点能.计算结果表明，基态3-羟基丙烯醛分子的双键旋转异构反应经过两步完成，第一步反应位垒稍高，第二步反应位垒较低，存在着发生重排反应的可能性.

关键词: 3-羟基丙烯醛, 异构反应, 过渡态, 密度泛函理论

Abstract: The geometries of reactants, products and transition states of the rotation rearrangement of 3-hydroxy acrolein molecule have been optimized by density functional theory(DFT) using B3LYP method at 6-31G** and 6-311＋＋G** level. The zero point energy corrections were obtained by vibration analysis, and the transition states were verified by the only virtual frequency. A 4-member ring intermediate was found on the reaction path. The intrinsic reaction coordinates (IRC) were obtained. The results show that the rearrangement of ground state molecule proceeds in two steps. The barrier of the first step is 240.745 kJ•mol－1(B3LYP/6-31G**), 232.858 kJ•mol－1 (B3LYP/6-311＋＋G**), and the second step barrier is 40.412 kJ•mol－1 (B3LYP/6-31G**), 37.568 kJ•mol－1 (B3LYP/6-311＋＋G**). The calculation results show that the rearrangement of ground state 3-hydroxy acrolein molecule is possible.

Key words: 3-hydroxy acrolein, Rearrangement, Transition state, Density functional theory