气相中O_3与HSO自由基间的氢键复合物(英文)  

Hydrogen-Bonded Complex between Ozone and Thioperoxy Radical in Gas-Phase

作　　者：袁焜[1] 刘艳芝[1] 朱元成[1] 张继[1,2] 

机构地区：[1]天水师范学院生命科学与化学学院,甘肃天水741000 [2]西北师范大学化学化工学院,兰州730070

出　　处：《物理化学学报》2008年第11期2065-2070,共6页Acta Physico-Chimica Sinica

基　　金：甘肃省教育厅研究生导师科研基金(07-08-12);天水师范学院“青蓝”人才工程基金资助项目

摘　　要：气相中O3与HSO自由基之间的相互作用及其反应在大气化学中非常重要.在DFT-B3LYP/6-311++G**和MP2/6-311++G**水平上求得O3+HSO复合物势能面上的稳定构型,B3LYP方法得到了三种构型(复合物Ⅰ,Ⅱ和Ⅲ),而MP2方法只能得到一种构型(复合物Ⅱ).在复合物Ⅰ和Ⅲ中,HSO单元中的1H原子作为质子供体,与O3分子中的端基O原子作为质子受体相互作用,形成红移氢键复合物;而在复合物Ⅱ中,虽与复合物Ⅰ和Ⅲ中具有相同的质子供体和质子受体,却形成了蓝移氢键复合物.B3LYP/6-311++G**水平上计算的单体间相互作用能的计算考虑了基组重叠误差(BSSE)和零点振动能(ZPVE)校正,其值在-3.37到-4.55kJ·mol-1之间.采用自然键轨道理论(NBO)对单体间相互作用的本质进行了考查,并通过分子中原子理论(AIM)分析了三种复合物中氢键的电子密度拓扑性质.B3LYP/6-311＋＋G＊＊ and MP2/6-311＋＋G＊＊ calculations were used to analyze the interaction between thioperoxy radical （HSO） and ozone （O3） in gas-phase, which are of interest in atmospheric chemistry. The results showed that there were three equilibrium geometries （complexes Ⅰ, Ⅱ, and Ⅲ） at the B3LYP/6-311＋＋G＊＊ level, but only one stable configuration （complexes Ⅱ） at MP2/6-311＋＋G＊＊ level. And all the equilibrium geometries were confirmed to be stable states by analytical frequency computations. Complexes Ⅰ and Ⅲ use the 1H atom of HSO as proton donor and the terminal 4O atom of O3 as acceptor to form red shift hydrogen bond systems. However, complex Ⅱ uses the same proton donor and acceptor to form a blue shift hydrogen bond system. Interaction energies of the complexes corrected with basis set superposition error （BSSE） and zero point vibrational energy （ZPVE） lie in the range from -3.37 to -4.55 kJ·mol-1 at B3LYP/6-311＋＋G＊＊ level. The natural bond orbital （NBO） and atoms in molecules （AIM） theories were also applied to explain the structures and the electron density topology properties of the three hydrogen bond complexes.

关 键 词：HSO自由基 臭氧 氢键相互作用 自然键轨道理论 分子中原子理论 

分 类 号：O641.1[理学—物理化学]