甲基肼自由基在高温燃烧分解反应下的非谐振效应

引用本文: 于洪晶, 夏文文, 宋立国, 丁杨, 郝宇, 康利强, 潘新祥, 姚丽. 甲基肼自由基在高温燃烧分解反应下的非谐振效应[J]. 物理化学学报, 2017, 33(11): 2207-2218. doi: 10.3866/PKU.WHXB201705227 shu

Citation: YU Hong-Jing, XIA Wen-Wen, SONG Li-Guo, DING Yang, HAO Yu, KANG Li-Qiang, PAN Xin-Xiang, YAO Li. Anharmonic Effect of the Decomposition Reaction in High-Temperature Combustion of Monomethylhydrazine Radicals[J]. Acta Physico-Chimica Sinica, 2017, 33(11): 2207-2218. doi: 10.3866/PKU.WHXB201705227 shu

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.
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
基金项目:
国家自然科学基金（91441132）和中央高校基本科研业务费专项资金（3132016127，3132016326，3132016019）资助项目

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:

English

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

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 Date: 24 April 2017
Revised Date: 17 May 2017
Fund Project:
The project was supported by the Major Research Plan of the National Natural Science Foundation of China (91441132) and Fundamental Research Funds for the Central Universities, China (3132016127, 3132016326, 3132016019).

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:

1. [1]
  (1) Ishikawa, Y.; McQuaid, M. J. Mol. Struct. 2007, 818, 119. doi: 10.1016/j.theochem.2007.05.014
2. [2]
  (2) Liu, W. G.; Wang, S. Q.; Dasgupta, S.; Thynell, S. T.; Goddard, W. A., III; Zybin, S.; Yetter, R. A. Combustion and Flame 2013, 160, 970. doi: 10.1016/j.combustflame.2013.01.012
3. [3]
  (3) Catoire, L.; Chaumeix, N.; Paillard, C. J. Propul. Power 2004, 20, 87. doi: 10.2514/1.9234
4. [4]
  (4) Dennis, J. D.; Son, S. F.; Pourpoint, T. L. J. Propul. Power 2015, 31, 1184. doi: 10.2514/1.B35541
5. [5]
  (5) Fang, W. H.; You, X. Z. Mol. Struct. 1995, 358, 205. doi: 10.1016/0166-1280(95)04345-4
6. [6]
  (6) Sun, H. Y.; Zhang, P.; Law, C. K. J. Phys. Chem. A 2012, 116, 8419. doi: 10.1021/jp3045675
7. [7]
  (7) Garderen, H. F.; Ruttink, P. J. A.; Burgers, P. C.; McGibbon, G. A.; Terlouw, J. K. J. Mass Spec. Ion Proce. 1992, 121, 159. doi: 10.1016/0168-1176(92)80061-5
8. [8]
  (8) McQuaid, M. J.; Ishikawa, Y. J. Phys. Chem. A 2006, 110, 6129. doi: 10.1021/jp060210j
9. [9]
  (9) Schlag, E. W.; Sandsmark, R. A. J. Chem. Phys. 1962, 37, 168. doi: 10.1063/1.1732944
10. [10]
  (10) Yao, L.; Mebel, A. M.; Lu, H. F.; Neusser, H. J.; Lin, S. H. J. Chem. Phys. A 2007, 111, 6722. doi: 10.1021/jp069012i
11. [11]
  (11) Yao, L.; He, R. X.; Mebel, A. M.; Lin, S. H. Chem. Phys. Lett. 2009, 470, 210. doi:10.1016/j.cplett.2009.01.074
12. [12]
  (12) Gu, L. Z.; Yao, L.; Shao, Y.; Zhong, H. Y.; Yang, K.; Zhong, J.J. J. Theor. CMPT Chem. 2010, 9, 813. doi: 10.1142/S0219633610006006
13. [13]
  (13) Yao, L.; Liu, Y. L. Mod. Phys. Lett. B 2008, 22, 3043. doi: 10.1142/S0217984908017552
14. [14]
  (14) Gu, L. Z.; Yao, L.; Shao, Y.; Liu, W.; Gao, H. Mol. Phys. 2011, 109, 1. doi: 10.1080/00268976.2011.602648
15. [15]
  (15) Ding, Y.; Song, L. G.; Yu, Y. X.; Yao, L.; Lin, S. X. Acta Phys. -Chim. Sin 2016, 32, 2685. [丁杨, 宋立国, 余忆玄, 姚丽, 林圣贤. 物理化学学报, 2016, 32, 2685.]doi: 10.3866/PKU.WHXB201607212
16. [16]
  (16) Forst, W.; Prášil, Z. J. Chem. Phys. 1970, 53, 3065. doi: 10.1063/1.1674450
17. [17]
  (17) Forst, W. Chem. Rev. 1971, 1, 339. doi: 10.1021/cr60272a001
18. [18]
  (18) Forst, W. Theory of Unimolecular Reactions; Academic Press:New York, 1973.
19. [19]
  (19) Eyring, H.; Lin, S. H.; Lin, S. M. Basic Chemical Kinetics;AWiley-interscience Publication: New York, 1980.
20. [20]
  (20) Baer, T.; Hase, W. L. Unimolecular Reaction Dynamics: Theory and Experiments; Oxford University Press: New York, 1996.
21. [21]
  (21) Gilbert, R. G.; Smith, S. C. Theory Unimolecular Recombination Reactions; Blackwell: Oxford, 1990.
22. [22]
  (22) Eyring, H. Theory Chem. Acc. 1935, 3, 107. doi: 10.1007/s002149900102
23. [23]
  (23) Qian, L.; Li, Y.; Ying, S.; Kun, Y. J. Chin. Chem. Soc. 2014, 61, 309. doi: 10.1002/jccs.201300277
24. [24]
  (24) Bulychev, V. P.; Tokhadze, K. G. J. Mol. Strut. 2004, 708, 47. doi: 10.1016/j.molstruc.2004.01.072
25. [25]
  (25) Lindner, J.; Cringus, D.; Pshenichnikov, M. S.; Vohringer, P. J. Chem. Phys. 2007, 341, 326. doi: 10.1016/j.chemphys.2007.07.051

扫一扫看文章

计量

PDF下载量: 1
文章访问数: 603
HTML全文浏览量: 36

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

甲基肼自由基在高温燃烧分解反应下的非谐振效应

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

甲基肼自由基在高温燃烧分解反应下的非谐振效应

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs