含硫有机小分子冰晶表面大气化学反应机理的理论研究

项目名称： 含硫有机小分子冰晶表面大气化学反应机理的理论研究

项目编号： No.20873079

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 轻工业、手工业

项目作者： 王文亮

作者单位： 陕西师范大学

项目金额： 30万元

中文摘要： 利用量子化学高水平计算方法研究了(1) CH2SH+NO2, CH3SSCH3 + OH，CH3SCH2CH3+OH, CH3SO+HO2，CH3S+HO2, CH3O2+HO2, CH3CH2OO+CH3CH2OO等十多个气相体系的动力学机理与反应规律；(2) 详细考察了水分子存在对HO2+HO2,CH3O2+HO2, CH3SOCH3酮-醇异构化，2,6-二巯基嘌呤水助N7(H)→9(H)质子转移等体系的影响；(3)首次获得了CH2SCH2CH3, CH3SO4, CH3SNO2, CH3SONO等数十个不稳定有机硫物种的生成焓等热力学性质数据。在此基础上，深入揭示了部分含硫有机小分子大气化学反应微观机理，特别是关于双自由基体系的优势通道、以及水助催化等反应体系的规律，获得了一系列具有学术意义和应用价值的成果。对模拟有机硫化物在大气中浓度分布和转化，消除硫化物大气污染等应用研究具有重要意义。项目执行期间已发表SCI收录的学术论文17篇。培养博士研究生3人(均在读)和硕士研究生13人（毕业8人），高校骨干进修教师2人。圆满地完成了研究计划。

中文关键词： 含硫有机小分子；水助催化；大气化学反应；量子化学计算

英文摘要： By employing quantum chemical calculations with high level theoretical methods, the main investigations are as follows: (1) The mechanism and kinetics for gas-phase reactions of CH2SH+NO2, CH3SSCH3+OH, CH3SCH2CH3+OH, CH3SO+HO2, CH3S+HO2, CH3O2+HO2 and CH3CH2OO+CH3CH2OO have been investigated; (2) The effect of water molecule on reactions of HO2+HO2, CH3O2+HO2, enol-keto tautomerism of CH3S(O)CH3 and N7(H)→9(H) tautomerization of isolated and monohydrated 2,6-dithiopurine have been reported theoretically. (3) The thermodynamic properties including enthalpies of formation, entropy and heat capacity of several organosulfur compounds (such as CH2SCH2CH3, CH3SO4, CH3SNO2, CH3SONO et al), were predicted for the first time. Based on these investigations, the project reveals the atmospheric chemistry reaction mechanism and kinetics of some organosulfur compounds profoundly. More notably, some interesting science questions, such as the favorable channels in radical-radical reactions and different catalytic effects of water molecule on gas-phase reactions, are mainly concerned, and a series of achievements with academic significance and the application value have been made. This project will simulate the thickness distribution and transformation rule of organosulfur compounds in atmosphere environment greatly. During the project execution, 17 academic papers were published in the related journals collected by the database of SCI, and 18 students have been endowed, including 3 doctoral, tweven 13 masters postgraduate and 2 visiting scholars.

英文关键词： organosulfur compounds；Water-catalyzed；atmospheric chemical reaction；quantum chemistry calculation