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DOI	10.1016/j.atmosenv.2020.117559
	Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method
	Wang X.; Zhou L.; Liu Y.; Zhang K.; Xiu G.
发表日期	2020
ISSN	1352-2310
卷号	230
英文摘要	Photo-dissociation of NO2 plays a very important role in atmospheric chemistry, e.g., it affects the O3 level. In the present work, density-functional theory (DFT) and time-dependent density-functional theory (TD-DFT) were applied to investigate the detailed dissociation process of NO2. Initially, ultraviolet–visible spectra were predicted by using TD-DFT at the 6-311G (d,p) level with different exchange correlation functionals. Among the functionals studied, CAM-B3LYP was found to show the best agreement with the experimental data. Exogenous energy is required for the initial step of NO2 photo-dissociation, at which point a NO2 molecule is excited to the excited state. Then, a N⋯O bond-breaking process occurs spontaneously. In addition, the potential impact of atmospheric constituents including water and a solid carbonaceous surface on such reaction were further evaluated. The presence of water molecules can increase the activation energy, resulting in a lower photolysis frequency, while a carbonaceous surface may exhibit nearly no effect on NO2 photo-dissociation. The present study provides a novel strategy for furthering our understanding of the photochemical behavior of NO2. © 2020 Elsevier Ltd
关键词	Carbonaceous surface DFT/TD-DFT Nitrogen dioxide Photolysis Water
语种	英语
scopus关键词	Activation energy; Atmospheric chemistry; Chemical bonds; Dissociation; Excited states; Molecules; Nitrogen oxides; Photolysis; Surface reactions; Atmospheric constituents; Bond breaking process; Carbonaceous surface; Dissociation process; Exchange-correlation functionals; Photochemical behaviors; Photolysis frequencies; Time dependent density functional theory; Density functional theory; nitrogen dioxide; water; activation energy; correlation; experiment; nitrogen dioxide; photolysis; spectrum; absorption spectroscopy; Article; density functional theory; dissociation; nitrogen cycle; photolysis; priority journal; solid; surface property; ultraviolet visible spectroscopy
来源期刊	ATMOSPHERIC ENVIRONMENT
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/249172
作者单位	State Environmental Protection Key Laboratory of Integrated Surface Water-Groundwater Pollution Control, School of the Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China; Guangdong Provincial Key Laboratory of Soil and Groundwater Pollution Control, School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China; State Environmental Protection Key Lab of Environmental Risk Assessment and Control on Chemical Processes. School of Resources & Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, China; College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen, 518060, China; School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444, China
推荐引用方式 GB/T 7714	Wang X.,Zhou L.,Liu Y.,et al. Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method[J],2020,230.
APA	Wang X.,Zhou L.,Liu Y.,Zhang K.,&Xiu G..(2020).Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method.ATMOSPHERIC ENVIRONMENT,230.
MLA	Wang X.,et al."Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method".ATMOSPHERIC ENVIRONMENT 230(2020).