Release Time:2019-03-11  Hits:

Indexed by: Journal Article

Date of Publication: 2018-05-16

Journal: INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

Included Journals: EI、SCIE

Volume: 118

Issue: 10

ISSN: 0020-7608

Key Words: DFT functionals; k(OH) values; (OH)-O-center dot atmospheric addition; phenyl and substituted phenyl-based persistent and toxic organic pollutants; reaction mechanisms

Abstract: (OH)-O-center dot addition reactions play a pivotal role in the atmospheric transformation of a number of phenyl and substituted phenyl-based persistent and toxic organic pollutants. Here, we screened appropriate DFT functionals to predict reaction mechanisms and rate constants (k(OH)) of the (OH)-O-center dot additions by taking benzene and substituted benzenes (C6H5F, C6H5Cl, C6H5Br, C6H5CH3, C6H5OH) as model compounds. By comparing the k(OH) values calculated with DFT methods to experimental values, we found that the B97 functional is the best among the 18 functionals considered (using the basis sets 6-31+G(d,p) for optimizations and 6-311++G(3df,2pd) for single point energy calculations) in the temperature range of 230-330 K. In addition, we found that some other functionals performed well in specific conditions, e.g., BMKD3 is good for benzene, halogenated benzenes and C6H5CH3, and CAM-B3LYP is good for the reaction of C6H5OH at room temperature. Based on the diversity of the electronic structures of the selected model compounds and the frequent occurrence of certain substituents (CH3, OH, F, Cl, and Br) in the target compounds, the functionals recommended here can be used for future study of the reaction mechanisms and k(OH) values for (OH)-O-center dot addition to phenyl and substituted phenyl-based persistent and toxic organic pollutants.