液相中ENE反应机理及其动力学参数的理论模拟
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- 英文论文题名：Theoretical Studies on the Mechanisms and Thermodynamics of Some Ene Reactions in Solution
- 论文作者：赵浏 ; 李世俊 ; 方德彩
- 英文论文作者：Liu Zhao ; Shi-Jun Li ; De-Cai Fang ; Colledge of Chemistry ; Beijing Normal University
- 年：2016
- 作者机构：北京师范大学化学学院;
- 论文关键词：ENE反应 ; 反应机理 ; 动力学 ; 理论计算
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O643.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：218k
- 原文格式：D
- 会议级别：全国
摘要
在液相中进行的反应的动力学参数的准确计算是计算化学领域最具挑战性的问题之一。特别是对反应前后分子数发生变化的反应,Gaussian程序中默认的气相平动熵模型得到的活化熵数值与实验值差异尤为明显。ENE反应就是其中一类典型反应,实验上有丰富的动力学数据且机理存疑,有待商榷。本文采用密度泛函理论对1,2,4-三唑啉-3,5-二酮等底物参与的ENE反应机理进行理论模拟;并且通过液相平动熵模型(THERMO程序)对平动熵进行校正,进一步获得与实验数据高度吻合的动力学参数数据,为液相中反应的后续理论研究奠定基础。
The thermodynamics study of the ene system from computational insight was initiated, since theoretical methods have so far found a rather limited application in the study of reaction dynamic parameters, especially the contributions of the entropy term during free-energy calculations in solution.Some ene reactions have been characterized with several density functional theory(DFT) methods, and the obtained results indicate that data from solution translational entropies(THERMO program) are quite close to the experimental measurements, whereas gas-phase translational entropies(Gaussian job) do not perform well.
The thermodynamics study of the ene system from computational insight was initiated, since theoretical methods have so far found a rather limited application in the study of reaction dynamic parameters, especially the contributions of the entropy term during free-energy calculations in solution.Some ene reactions have been characterized with several density functional theory(DFT) methods, and the obtained results indicate that data from solution translational entropies(THERMO program) are quite close to the experimental measurements, whereas gas-phase translational entropies(Gaussian job) do not perform well.
引文
[1]Li,Y.;Fang,D.C.Phys.Chem.Chem.Phys.2014,16:15224.
[2]Han,L.L.;Li.S.J.;Fang,D.C.Phys.Chem.Chem.Phys.2016,18:6182.
[4]Fang,D.C.THERMO,Beijing Normal University,Beijing,China,free of charge for academic users.
[2]Han,L.L.;Li.S.J.;Fang,D.C.Phys.Chem.Chem.Phys.2016,18:6182.
[4]Fang,D.C.THERMO,Beijing Normal University,Beijing,China,free of charge for academic users.