物理化学学报 >> 2017, Vol. 33 >> Issue (11): 2207-2218.doi: 10.3866/PKU.WHXB201705227

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甲基肼自由基在高温燃烧分解反应下的非谐振效应

于洪晶1,夏文文1,宋立国2,丁杨2,郝宇2,康利强2,潘新祥2,姚丽1,*()   

  1. 1 大连海事大学物理系,辽宁大连116026
    2 大连海事大学轮机工程学院,辽宁大连116026
  • 收稿日期:2017-04-24 发布日期:2017-08-25
  • 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);中央高校基本科研业务费专项资金(3132016019)

Anharmonic Effect of the Decomposition Reaction in High-Temperature Combustion of Monomethylhydrazine Radicals

Hong-Jing YU1,Wen-Wen XIA1,Li-Guo SONG2,Yang DING2,Yu HAO2,Li-Qiang KANG2,Xin-Xiang PAN2,Li YAO1,*()   

  1. 1 Department of Physics, Dalian Maritime University, Dalian 116026, Liaoning Province, P. R. China
    2 Marine Engineering College, Dalian Maritime University, Dalian 116026, Liaoning Province, P. R. China
  • Received:2017-04-24 Published:2017-08-25
  • 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);Fundamental Research Funds for the Central Universities, China(3132016019)

摘要:

基于过渡态理论(TST)和RRKM(Rice-Ramsperger-Kassel-Marcus)理论,使用MP2/6-311++G (3df, 2p) //B3LYP/6-311++G (3df, 2p)基组和方法,本文分别计算了甲基肼自由基在高温燃烧下分解反应的谐振以及非谐振速率常数。因此,甲基肼自由基的详细机理得以研究。在正则系综中,谐振以及非谐振速率常数都随着温度的升高而增加;而在微正则系综中,速率常数随着能量的升高而增加。整体上看,在正则系综和微正则系综中,非谐振效应分别随着温度和能量的升高而变得越来越明显。因此甲基肼自由基在高温燃烧下分解反应的非谐振效应是不能被忽视的。

关键词: 非谐振效应, 单分子反应, RRKM理论, 速率常数

Abstract:

In this work, the harmonic and anharmonic rate constants of the decomposition reaction of monomethylhydrazine (MMH) radicals have been calculated by using transition state (TS) and Rice-Ramsperger-Kassel-Marcus (RRKM) theories with either MP2 or B3LYP method at 6-311++G (3df, 2p) basis set, respectively. The reaction mechanism and anharmonic effect of the MMH radicals are studied in detail and both of the harmonic and anharmonic rate constants increase sharply with increasing temperature in the canonical system. In the microcanonical system, these constants also show sharp increase with the energies. Overall, the anharmonic effect becomes more pronounced with the increasing temperature or energy in the canonical and microcanonical systems, respectively. These results indicate that the anharmonic effect of the decomposition reaction of MMH radicals is quite significant and cannot be ignored.

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

MSC2000: 

  • O643