中国物理B ›› 2018, Vol. 27 ›› Issue (1): 13102-013102.doi: 10.1088/1674-1056/27/1/013102

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Spin polarization and dispersion effects in emergence of roaming transition state for nitrobenzene isomerization

Zhi-Yuan Zhang(张志远), Wan-Run Jiang(姜万润), Bo Wang(王波), Yan-Qiang Yang(杨延强), Zhi-Gang Wang(王志刚)   

  1. 1 Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China;
    2 Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy(Jilin University), Changchun 130012, China;
    3 Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang 621900, China
  • 收稿日期:2017-10-27 修回日期:2017-10-30 出版日期:2018-01-05 发布日期:2018-01-05
  • 通讯作者: Yan-Qiang Yang, Zhi-Gang Wang E-mail:yqyang@hit.edu.cn;wangzg@jlu.edu.cn
  • 基金资助:
    Project supported by the Science Challenging Program, China (Grant No. JCKY2016212A501) and the National Natural Science Foundation of China (Grant No. 11374004).

Spin polarization and dispersion effects in emergence of roaming transition state for nitrobenzene isomerization

Zhi-Yuan Zhang(张志远)1,2, Wan-Run Jiang(姜万润)1,2, Bo Wang(王波)1,2, Yan-Qiang Yang(杨延强)3, Zhi-Gang Wang(王志刚)1,2   

  1. 1 Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China;
    2 Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy(Jilin University), Changchun 130012, China;
    3 Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang 621900, China
  • Received:2017-10-27 Revised:2017-10-30 Online:2018-01-05 Published:2018-01-05
  • Contact: Yan-Qiang Yang, Zhi-Gang Wang E-mail:yqyang@hit.edu.cn;wangzg@jlu.edu.cn
  • Supported by:
    Project supported by the Science Challenging Program, China (Grant No. JCKY2016212A501) and the National Natural Science Foundation of China (Grant No. 11374004).

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摘要： Since roaming was found as a new but common reaction path of isomerization, many of its properties, especially those of roaming transition state (TSR), have been studied on many systems. However, the mechanism of roaming is still not clear at an atomic level. In this work, we use first-principles calculations to illustrate the detailed structure of TSR in an internal isomerization process of nitrobenzene. The calculations distinctively show its nature of antiferromagnetic coupling between two roaming fragments. Moreover, the effect of dispersion is also revealed as an important issue for the stability of the TSR. Our work provides a new insight into the TSR from the view of electronic structure and contributes to the basic understanding of the roaming systems.

关键词: spin polarization, dispersion, first-principles

Abstract: Since roaming was found as a new but common reaction path of isomerization, many of its properties, especially those of roaming transition state (TSR), have been studied on many systems. However, the mechanism of roaming is still not clear at an atomic level. In this work, we use first-principles calculations to illustrate the detailed structure of TSR in an internal isomerization process of nitrobenzene. The calculations distinctively show its nature of antiferromagnetic coupling between two roaming fragments. Moreover, the effect of dispersion is also revealed as an important issue for the stability of the TSR. Our work provides a new insight into the TSR from the view of electronic structure and contributes to the basic understanding of the roaming systems.

Key words: spin polarization, dispersion, first-principles

中图分类号:  (Effects of atomic and molecular interactions on electronic structure)

  • 31.70.-f
31.50.-x (Potential energy surfaces) 82.20.Db (Transition state theory and statistical theories of rate constants)