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-4.55 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 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.