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Chin. Phys. B, 2018, Vol. 27(1): 013102    DOI: 10.1088/1674-1056/27/1/013102

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 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
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.
Keywords:  spin polarization      dispersion      first-principles  
Received:  27 October 2017      Revised:  30 October 2017      Accepted manuscript online: 
PACS:  31.70.-f (Effects of atomic and molecular interactions on electronic structure)  
  31.50.-x (Potential energy surfaces)  
  82.20.Db (Transition state theory and statistical theories of rate constants)  
Fund: Project supported by the Science Challenging Program, China (Grant No. JCKY2016212A501) and the National Natural Science Foundation of China (Grant No. 11374004).
Corresponding Authors:  Yan-Qiang Yang, Zhi-Gang Wang     E-mail:;

Cite this article: 

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) Spin polarization and dispersion effects in emergence of roaming transition state for nitrobenzene isomerization 2018 Chin. Phys. B 27 013102

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