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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。
Based on the theory of transition state (TST) and RRKM (Rice-Ramsperger-Kassel-Marcus), MP2 / 6-311 ++ G (3df, 2p) // B3LYP / 6-311 ++ G (3df, 2p) In this paper, the resonance and nonresonance rate constants of the decomposition reaction of methylhydrazine free radicals at high temperature were calculated. Therefore, the detailed mechanism of methylhydrazine free radicals has been studied. In regular ensembles, the resonant and non-resonant rate constants increase with increasing temperature, while in the canonical ensembles, the rate constants increase with increasing energy. On the whole, in the regular ensemble and the micro-canonical ensemble, the non-resonant effects become more and more obvious as the temperature and energy increase, respectively. Therefore, the non-resonant effect of methylhydrazine radical decomposition reaction at high temperature combustion can not be neglected.