气相中O3与HSO自由基间的氢键复合物

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犁(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中具有相间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甍误差(BSSE)和零点振动能(ZPVE)校正,其值在-3.37到-4.55 kJ·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.

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

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 40 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 elecu'on density topology properties of the three hydrogen bond complexes.