物理化学学报 >> 2016, Vol. 32 >> Issue (11): 2685-2692.doi: 10.3866/PKU.WHXB201607212

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丁酸甲酯单分子解离的非谐振效应

丁杨1,宋立国1,余忆玄1,姚丽1,*(),林圣贤2   

  1. 1 大连海事大学轮机工程学院,辽宁大连116026
    2 台湾交通大学应用化学系,台湾新竹10764
  • 收稿日期:2016-03-16 发布日期:2016-11-08
  • 通讯作者: 姚丽 E-mail:yaoli@dlmu.edu.cn
  • 基金资助:
    国家自然科学基金(91441132);中央高校基本科研业务费专项资金(3132016127);中央高校基本科研业务费专项资金(3132016326)

Anharmonic Effect of the Decomposition Reaction of Methyl Butanoate

Yang DING1,Li-Guo SONG1,Yi-Xuan YU1,Li YAO1,*(),Sheng-Hsien LIN2   

  1. 1 Marine Engineering College, Dalian Maritime University, Dalian 116026, P. R. China
    2 Department of Applied Chemistry, National Chiao-Tung University, Hsin-chu 10764, Taiwan, P. R. China
  • Received:2016-03-16 Published:2016-11-08
  • Contact: Li YAO E-mail:yaoli@dlmu.edu.cn
  • Supported by:
    the Major Research Plan of the National Natural Science Foundation of China(91441132);Fundamental Research Funds for the Central Universities, China(3132016127);Fundamental Research Funds for the Central Universities, China(3132016326)

摘要:

使用MP2/6-311++G(2d,2p)方法和基组,计算了丁酸甲酯单分子解离反应体系详细的势能面。应用RRKM理论,计算了在1000-5000 K的温度范围内的正则系综的速率常数。与此同时,在微正则系综下,我们计算了温度为1000-5000 K对应的能量从451.92到1519.52 kJ·mol-1的速率常数。计算结果表明反应通道2、4和5的非谐振效应比较明显。因此对于丁酸甲酯单分子解离反应体系来说其非谐振效应是不能忽视的。

关键词: 非谐振效应, 单分子解离反应, RRKM理论, 速率常数

Abstract:

In this paper, we have used the MP2/6-311++G(2d, 2p) method to conduct a detailed investigation of the potential energy surface for the unimolecular dissociation reaction of methyl butanoate (MB). We have also used the Rice-Ramsperger-Kassel-Marcus (RRKM) theory to calculate the rate constants of the canonical and microcanonical systems at temperatures and total energies ranging from 1000 to 5000 K and 451.92 to 1519.52 kJ·mol-1, respectively. The results indicated that there was an obvious anharmonic effect for the TS2, TS4 and TS5 pathways, and that this effect was too pronounced to be neglected for the unimolecular dissociation reactions of MB.

Key words: Anharmonic effect, Unimolecular decomposition reaction, RRKM theory, Rate constant

MSC2000: 

  • O643