甲基肼自由基在高温燃烧分解反应下的非谐振效应（英文）

发布时间：2018-03-21 10:55

本文选题：非谐振效应　切入点：单分子反应　出处：《物理化学学报》2017年11期 　论文类型：期刊论文

【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。
[Abstract]:Based on the transition state theory (TST) and RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the resonant and non-resonant rate constants of the decomposition reaction of methyl hydrazine radical under high temperature combustion are calculated by using the basic set and method of MP2/6-311 Gn3dfU 2pN / / B3LYP / 6-3LYP6-3dfU 2p, respectively. In the canonical ensemble, the resonant and non-resonant rate constants increase with the increase of temperature, while in the microcanonical ensemble, the rate constants increase with the increase of energy. In canonical ensemble and micro-canonical ensemble, the non-resonance effect becomes more and more obvious with the increase of temperature and energy, respectively, so the non-resonance effect of the decomposition reaction of methyl hydrazine radical under high temperature combustion can not be ignored.
【作者单位】：大连海事大学物理系;大连海事大学轮机工程学院;
【基金】：supported by the Major Research Plan of the National Natural Science Foundation of China(91441132) Fundamental Research Funds for the Central Universities,China(3132016127,3132016326,3132016019)~~
【分类号】：O643.21

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