中国物理B ›› 2018, Vol. 27 ›› Issue (2): 23401-023401.doi: 10.1088/1674-1056/27/2/023401

• SPECIAL TOPIC—Soft matter and biological physics (Review) • 上一篇    下一篇

Exploring the methane combustion reaction: A theoretical contribution

Ya Peng(彭亚), Zhong-An Jiang(蒋仲安), Ju-Shi Chen(陈举师)   

  1. School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China
  • 收稿日期:2017-08-04 修回日期:2017-11-03 出版日期:2018-02-05 发布日期:2018-02-05
  • 通讯作者: Ya Peng, Zhong-An Jiang E-mail:pengyaustb@sina.com;jza1963@263.net
  • 基金资助:

    Project supported by the National Natural Science Foundation of China (Grant Nos. 51574016 and 51604018).

Exploring the methane combustion reaction: A theoretical contribution

Ya Peng(彭亚), Zhong-An Jiang(蒋仲安), Ju-Shi Chen(陈举师)   

  1. School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China
  • Received:2017-08-04 Revised:2017-11-03 Online:2018-02-05 Published:2018-02-05
  • Contact: Ya Peng, Zhong-An Jiang E-mail:pengyaustb@sina.com;jza1963@263.net
  • About author:34.10.+x; 31.15.xv; 34.50.Lf
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Grant Nos. 51574016 and 51604018).

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摘要：

This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction. Three saddle points (SPs) are identified in the reaction CH4+O(3P) → OH +CH3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs (3A' and 3A") along the direction of O(3P) attacking a near-collinear H-CH3. One second-order SP2nd (3E) between the above twin SPs is the result of the C3v symmetry Jahn-Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O(3P) from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O(3P) with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.

关键词: combustion reaction, reaction mechanism, rate constant, saddle point

Abstract:

This paper represents an attempt to extend the mechanisms of reactions and kinetics of a methane combustion reaction. Three saddle points (SPs) are identified in the reaction CH4+O(3P) → OH +CH3 using the complete active space selfconsistent field and the multireference configuration interaction methods with a proper active space. Our calculations give a fairly accurate description of the regions around the twin first-order SPs (3A' and 3A") along the direction of O(3P) attacking a near-collinear H-CH3. One second-order SP2nd (3E) between the above twin SPs is the result of the C3v symmetry Jahn-Teller coupling within the branching space. Further kinetic calculations are performed with the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. The rate constants are also reported. The present work reveals the reaction mechanism of hydrogen-abstraction by the O(3P) from methane, and develops a better understanding for the role of SPs. In addition, a comparison of the reactions of O(3P) with methane through different channels allows a molecule-level discussion of the reactivity and mechanism of the title reaction.

Key words: combustion reaction, reaction mechanism, rate constant, saddle point

中图分类号:  (General theories and models of atomic and molecular collisions and interactions (including statistical theories, transition state, stochastic and trajectory models, etc.))

  • 34.10.+x
31.15.xv (Molecular dynamics and other numerical methods) 34.50.Lf (Chemical reactions)