甲基肼自由基在高温燃烧分解反应下的非谐振效应

doi:10.3866/PKU.WHXB201705227

Acta Phys. -Chim. Sin. ›› 2017, Vol. 33 ›› Issue (11): 2207-2218.doi: 10.3866/PKU.WHXB201705227

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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 YAO^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)

Abstract

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

Hong-Jing YU,Wen-Wen XIA,Li-Guo SONG,Yang DING,Yu HAO,Li-Qiang KANG,Xin-Xiang PAN,Li YAO. Anharmonic Effect of the Decomposition Reaction in High-Temperature Combustion of Monomethylhydrazine Radicals[J].Acta Phys. -Chim. Sin., 2017, 33(11): 2207-2218.

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

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