甲基肼高温燃烧分解反应的非谐振效应
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- 英文论文题名：Anharmonic Effect of the Decomposition Reaction in High-temperature Combustion of Monomethylhydrazine
- 论文作者：于洪晶 ; 姚丽
- 英文论文作者：Hongjing Yu ; Li Yao ; Department of Physics ; Dalian Maritime University
- 年：2016
- 作者机构：大连海事大学物理系;
- 论文关键词：单分子反应 ; YL方法 ; 速率常数 ; 非谐振效应
- 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-第四十六分会：燃烧化学
- 语种：中文
- 分类号：TQ511.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十六分会 ; 燃烧化学
- 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：207k
- 原文格式：D
- 会议级别：全国
摘要
作为很重要的火箭燃料,对于甲基肼的研究已经取得突破性进展,然而对其非谐振效应的研究却很少~[1]。1962年,Schlag和Sandsmark通过实验证实了非谐振效应的存在及其重要性~[2]。首先使用Gaussian 09程序,在MP2/6-311++G**或B3LYP/6-311++G**方法和基组水平上对反应物及过渡态构型进行了优化,并在CCSD(T)/6-311++G**水平上得到了更加精准的单点能。然后根据RRKM理论以及过渡态理论、利用姚丽-林圣贤(YL)方法分别计算了其在正则系综中的谐振速率常数和非谐振速率常数以及在微正则系综中的谐振速率常数和非谐振速率常数~[3]。从而得到甲基肼分解反应的详细机理并对其非谐振效应进行了研究。结果表明:在正则系综中,温度相应的能量到达能垒之前速率变化较快,且非谐振效应相对不明显;到达能垒之后速率变化相对变缓,且非谐振效应相对变明显。总体上看,非谐振效应随着温度的升高越来越明显。在微正则系综中,非谐振效应随着能量的升高越来越明显。
Study of monomethylhydrazine has achieved a breakthrough, but study of its anharmonic effect is rare~[1]. It's important for the rocket fuel~[2]. First, geometries of reactants and transition states are calculated at B3LYP or MP2 function with 6-311++G** basis set by Gaussian 09 Program. In order to obtain more accurate data, energy are corrected by CCSD(T) method. Then, according to YL method, which is based on Transition State Theory and Rice-Ramsperger-Kassel-Marcus theory, harmonic and anharmonic rate constants are calculated, respectively~[3]. We can get detailed mechanism and study anharmonic effect. When energy is inferior to barrier, rate curve is steep, anharmonic effect isn't obvious. And when energy is higher than barrier, rate curve is gradual, anharmonic effect is obvious relatively in canonical system. Overall, Anharmonic effect is more and more obvious with temperature in canonical system, and anharmonic effect is more and more obvious with energy in microcanonical system.
Study of monomethylhydrazine has achieved a breakthrough, but study of its anharmonic effect is rare~[1]. It's important for the rocket fuel~[2]. First, geometries of reactants and transition states are calculated at B3LYP or MP2 function with 6-311++G** basis set by Gaussian 09 Program. In order to obtain more accurate data, energy are corrected by CCSD(T) method. Then, according to YL method, which is based on Transition State Theory and Rice-Ramsperger-Kassel-Marcus theory, harmonic and anharmonic rate constants are calculated, respectively~[3]. We can get detailed mechanism and study anharmonic effect. When energy is inferior to barrier, rate curve is steep, anharmonic effect isn't obvious. And when energy is higher than barrier, rate curve is gradual, anharmonic effect is obvious relatively in canonical system. Overall, Anharmonic effect is more and more obvious with temperature in canonical system, and anharmonic effect is more and more obvious with energy in microcanonical system.
引文
[1]Yan,H.;Zhang,P.;Law,C,K.J.Phys.Chem.A.2012,116:8419-8430.
[2]Schlag,E,W.;Sandsmark,R,A.Chem.Phys.1962,37:168-171.
[3]Yao,L.;Mebel,A,M.;Lu,H,F.;Neusser,H,J.;Lin,S,H.J.Phys.Chem.A.2007,111:6722-6729.
[2]Schlag,E,W.;Sandsmark,R,A.Chem.Phys.1962,37:168-171.
[3]Yao,L.;Mebel,A,M.;Lu,H,F.;Neusser,H,J.;Lin,S,H.J.Phys.Chem.A.2007,111:6722-6729.
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