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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.
The interaction between O3 and HSO radicals in the gas phase and their reactions are very important in atmospheric chemistry and are obtained at the DFT-B3LYP / 6-311 ++ G ** and MP2 / 6-311 ++ G ** levels O3 + HSO complex, three configurations were obtained by the B3LYP method (complexes Ⅰ, Ⅱ and Ⅲ), while only one configuration was obtained by the MP2 method (complex Ⅱ) In Ⅰ and Ⅲ, the 1H atom in HSO unit acts as a proton donor and interacts with terminal O atom in O3 molecule as a proton acceptor to form a red-shifted hydrogen-bonded complex. In complex II, The same proton donors and proton acceptors are found in I and III, but blue-shifted hydrogen bonding complexes are formed.The calculation of the intermolecular interaction energy at B3LYP / 6-311 ++ G ** level takes into account BSSE and ZPVE were calibrated with the values between -3.37 and -4.55 kJ · mol-1. The nature of the interaction between monomers was investigated using the theory of natural bond orbital (NBO) The topological properties of the hydrogen bond electron density in the three complexes were analyzed by using molecular atomic theory (AIM).