全氟新温室气体CF_3SF_5与OH自由基反应机理研究

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英文篇名：Study on the reaction mechanisms of CF_3SF_5 and OH radical 作者：刘艳 英文作者：LIU Yan;College of Chemistry and Materials,Shaanxi Engineering Research Center of Coal Conversion Alcohol,Weinan Normal University;Key Laboratory for Macromolecular Science of Shaanxi Province,School of Chemistry and Chemical Engineering,Shaanxi Normal University; 关键词：CF_3SF_5 ; OH自由基 ; 密度泛函理论 ; 反应机理 英文关键词：CF_3SF_5;;OH radical;;density functional theory;;reaction mechanism 中文刊名：FZKB 英文刊名：Journal of Molecular Science 机构：渭南师范学院化学与材料学院陕西省煤基低碳醇转化工程研究中心;陕西师范大学化学化工学院陕西省大分子科学重点实验室; 出版日期：2019-06-15 出版单位：分子科学学报 年：2019 期：v.35;No.167 基金：国家自然科学基金资助项目(21503150);; 陕西省自然科学基金资助项目(2018JM2051);; 陕西省教育厅自然科学基金(18JK0278);; 陕西省军民融合研究基金资助项目(18JMR34) 语种：中文; 页：FZKB201903004 页数：7 CN：03 ISSN：22-1262/O4 分类号：30-36

摘要

用密度泛函B3PW91/6-311++G(d,p)方法优化了CF_3SF_5与OH自由基反应路径上的各反应物、中间体、过渡态和产物等物种的几何构型,并确认了各物种的相关性.用G3(MP2)方法对各驻点物种进行了单点能计算,构建反应势能剖面.结果表明:CF_3SF_5与OH自由基的反应存在8条反应通道,可获得7种裂解产物.其中通道R→TS1→P1[CF_3SF_4(a)+FOH],R→TS2→P2[CF_3SF_4(b)+FOH]和R→TS11→SF_5+CF_3OH→TS12→P6[SF_5+CF_2O+HF]为标题反应主反应通道,各通道速控步骤的能垒分别为269.3,270.0和269.7kJ·mol~(-1).OH自由基更易与F_a(与S原子连接并沿着C—S键轴的F原子)、F_b(垂直于键轴方向的F原子)发生抽提反应或与—CF_3基团发生S_N2反应.在200K～2 000K温度范围内,主反应通道的速率常数随着温度的升高而增大,表现为正温度效应.
        The reaction mechanisms of CF_3SF_5 and OH radicals were studied by using the density functional method at B3PW91/6-311++G(d,p)level.Optimized geometries of reactants,intermediate,transition states and products were verified by the analysis of vibration frequency and intrinsic reaction coordinate(IRC).High accurate energy information was provided by the G3(MP2)method.It is found that CF_3SF_5 could react with OH radical and produce 7 decomposed products through 8 reaction paths.The paths R→TS1→P1[CF_3SF_4(a)+FOH],R→TS2→P2[CF_3SF_4(b)+FOH]and R→TS11→SF_5+CF_3OH→ TS12→P6[SF_5+CF_2O+HF]would be the favorable reactions due to the lower energy barriers of 269.3,270.0 and 269.7 kJ·mol~(-1).Therefore,OH radical is easier to attack the C atom in—CF_3 group,F atom on the molecular axis(F_a)or perpendicular to the molecular axis(F_b)than the F atom in —CF_3 group(F_c)in SF_5CF_3 molecule.The rate constants for the favorable pathways would increase with the temperature in the range of 200 K～2 000 K.

引文

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