Theoretical study of mechanism and kinetics for the addition of hydroxyl radical to phenol

作     者：WU PengZhen LI Jian LI ShuJin TAO Fu-Ming 

作者机构：College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou 215123 China Departments of Chemistry and Biochemistry California State University Fullerton CaliJbrnia 92834 USA 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2012年第55卷第2期

页      面：270-276页

核心收录：

学科分类：083002[工学-环境工程] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 08[工学] 080101[工学-一般力学与力学基础] 0801[工学-力学（可授工学、理学学位）] 

基　　金：supported by the National Natural Science Foundation of China (20977064) 

主　　题：phenol hydroxyl radical addition reaction quantum chemistry calculation transition state theory 

摘      要：The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometries, energies, and thermodynamics properties of all the stationary points along the addition reaction pathway are calculated. The rate constants and the branching ratios of each channel are evaluated using classical transition state theory （TST） in the temperature range of 210 to 360 K, to simulate temperatures in all parts of the troposphere. The ortho addition pathway is dominant and accounts for 99.8%-96.7% of the overall adduct products from 210 to 360 K. The calculated rate constants are in good agreement with existing experimental values. The addition reaction is irreversible.