过氧化氢-水二聚体的量子化学研究

Quantum chemical study on the hydrogen peroxide-water dimer

在MP2/aug-cc-pVDZ理论水平下对过氧化氢-水二聚体进行了结构优化,得到了势能面上的2种稳定构型W1-A和W1-B.并进一步应用此方法对过氧化氢-水二聚体进行了振动光谱和分子轨道相互作用分析.结果表明,具有五元环状氢键结构的W1-A比具有分叉氢键结构的W1-B稳定.振动光谱分析显示过氧化氢和水分子中与形成氢键相关的振动模式都发生了不同程度的红移.分子轨道分析表明当添加1个电子到复合物W1-A和W1-B的LUMO轨道时,对2种复合物的氢键没有影响.然而,当从复合物W1-A和W1-B的HOMO轨道移走1个电子时,会使复合物W1-A的氢键作用减弱,而对复合物W1-B的氢键作用影响不大.

In this paper,two stationary structures（W1-A and W1-B） on the potential energy surface of hydrogen peroxide-water dimer have been obtained by MP2/aug-cc-pVDZ method.The vibrational spectra and molecular orbital analysis for H2O2-H2O dimer are given at the same level.It can be concluded from the calculation that the five-membered ring hydrogen bonded structure W1-A is more stable than the bifurcated H-bonded structure W1-B.And the vibrational spectra analysis shows that the vibrational mode related to the formation of the hydrogen bond has some red shift.Meanwhile,there are no influence to the hydrogen bond of complexes W1-A and W1-B by adding an electron to LUMOs from the molecular orbital analysis.However,there are different conclusions obtained by removing an electron from HOMOs,the hydrogen bonded interaction of W1-A is weakened and W1-B is nearly unchanged.