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

doi:10.1088/1674-1056/27/1/013102

Abstract Since roaming was found as a new but common reaction path of isomerization, many of its properties, especially those of roaming transition state (TS_R), 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 TS_R 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 TS_R. Our work provides a new insight into the TS_R 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: yqyang@hit.edu.cn;wangzg@jlu.edu.cn

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

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