Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method

Wang，Xiaoxiang1,2; Zhou，Lei3; Liu，Yifan4; Zhang，Kun5; Xiu，Guangli3

2020-06-01

10.1016/j.atmosenv.2020.117559

ATMOSPHERIC ENVIRONMENT   影响因子和分区

1352-2310

1873-2844

Photo-dissociation of NO plays a very important role in atmospheric chemistry, e.g., it affects the O 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 NO. 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 NO photo-dissociation, at which point a NO 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 NO photo-dissociation. The present study provides a novel strategy for furthering our understanding of the photochemical behavior of NO.

Carbonaceous surface DFT/TD-DFT Nitrogen dioxide Photolysis Water

SCI ; EI

英语

第一

National Natural Science Foundation of China[21806037] ; Program for Guangdong Introducing Innovative and Entrepreneurial Teams[2017ZT07Z479]

Environmental Sciences & Ecology ; Meteorology & Atmospheric Sciences

Environmental Sciences ; Meteorology & Atmospheric Sciences

WOS:000537838300012

PERGAMON-ELSEVIER SCIENCE LTD

20201808595530

Density functional theory ; Activation energy ; Nitrogen oxides ; Surface reactions ; Dissociation ; Atmospheric chemistry ; Excited states ; Molecules

Atmospheric Properties:443.1 ; Chemistry, General:801.1 ; Chemical Reactions:802.2 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

GEOSCIENCES

2-s2.0-85083893570

Scopus

1.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
2.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
3.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
4.College of Physics and Optoelectronic Engineering,Shenzhen University,Shenzhen,518060,China
5.School of Environmental and Chemical Engineering,Shanghai University,Shanghai,200444,China

Wang，Xiaoxiang,Zhou，Lei,Liu，Yifan,et al. Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method[J]. ATMOSPHERIC ENVIRONMENT,2020,230.

Wang，Xiaoxiang,Zhou，Lei,Liu，Yifan,Zhang，Kun,&Xiu，Guangli.(2020).Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method.ATMOSPHERIC ENVIRONMENT,230.

Wang，Xiaoxiang,et al."Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method".ATMOSPHERIC ENVIRONMENT 230(2020).