标题：Role of water on the H-abstraction from methanol by ClO
作者：Tang, Shanshan; Tsona, Narcisse T.; Li, Junyao; Du, Lin
通讯作者：Du, L;Du, Lin
作者机构：[Tang, Shanshan; Tsona, Narcisse T.; Li, Junyao; Du, Lin] Shandong Univ, Environm Res Inst, Jinan 250100, Shandong, Peoples R China.
会议名称：5th Sino-French Joint Workshop on Atmospheric Environment
会议日期：OCT 11-14, 2016
来源：JOURNAL OF ENVIRONMENTAL SCIENCES
关键词：H-abstraction reaction; Quantum chemical calculations; Radical-molecule complex; Reaction rate constants
摘要：The influence of a single water molecule on the reaction mechanism and kinetics of hydrogen abstraction from methanol (CH3OH) by the ClO radical has been investigated using ab initio calculations. The reaction proceeds through two channels: abstraction of the hydroxyl H-atom and methyl H-atom of CH3OH by ClO, leading to the formation of CH3O + HOCl (+H2O) and CH2OH + HOCl (+H2O), respectively. In both cases, pre-and post-reactive complexeswere located at the entrance and exit channel on the potential energy surfaces. Results indicate that the formation of CH2OH + HOCl (+H2O) is predominant over the formation of CH3O + HOCl (+ H2O), with ambient rate constants of 3.07 x 10(-19) and 3.01 x 10(-23) cm(3)/(molecule.sec), respectively, for the reaction without water. Over the temperature range 216.7-298.2 K, the presence of water is seen to effectively lower the rate constants for the most favorable pathways by 4-6 orders of magnitude in both cases. It is therefore concluded that water plays an inhibitive role on the CH3OH + ClO reaction under tropospheric conditions. (C) 2018 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.