| DFT法研究3-羟基丙烯醛的双键旋转异构反应机理 |
| |
| 引用本文： | 蒲敏,王海霞,冯霄,吴东,孙予罕. DFT法研究3-羟基丙烯醛的双键旋转异构反应机理[J]. 物理化学学报, 2002, 18(6): 522-526. DOI: 10.3866/PKU.WHXB20020610 |
| |
| 作者姓名： | 蒲敏 王海霞 冯霄 吴东 孙予罕 |
| |
| 作者单位： | 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 |
| |
| 基金项目： | 陕西省自然科学基础研究计划（98H04），西安交通大学理科基金，中国科学院煤转化国家重点实验室基金资助项目 |
| |
| 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 |
| 收稿时间： | 2001-12-07 |
| 修稿时间： | 2002-01-23 |
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. Research on the Rotation Rearrangement of C=C Double Bond of 3-Hydroxy Acrolein by Density Function Theory[J]. Acta Physico-Chimica Sinica, 2002, 18(6): 522-526. DOI: 10.3866/PKU.WHXB20020610 |
| |
| Authors: | Pu Min Wang Hai-Xia Feng Xiao Wu Dong Sun Yu-Han |
| |
| Affiliation: | 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 |
| |
| 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. |
| |
| Keywords: | 3-hydroxy acrolein Rearrangement Transition state Density functional theory |
| 本文献已被 CNKI 维普 万方数据 等数据库收录！ |
| 点击此处可从《物理化学学报》浏览原始摘要信息 |
|
点击此处可从《物理化学学报》下载全文 |
