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运用从头算MP2和密度泛函B3LYP方法,在6-311++G**基组水平上对第一主族阳离子-苯复合体系的构型进行了自由优化,并定义阳离子位于苯环正上方。频率计算表明为合理构型,复合物的键长、原子电荷、分子轨道成份、前沿轨道能等表明,碱金属阳离子与苯的作用包含p-π和s-π作用方式,阳离子与苯结合时电子从苯向阳离子转移,形成电荷转移复合物,与氢键的结合方式相似。M+…benzene and benzene…M+…benzene复合物的红外光谱特征频率分别位于120~740cm-1和140~890cm-1,为阳离子垂直于环平面上作来回振动,其红外光谱振动频率随Li、Na、K向长波方向红移,并红外强度随Li、Na、K降低。
The ab initio MP2 and density functional B3LYP methods were used to optimize the configuration of the first main group of cation-benzene complex system at the level of 6-311 ++ G ** and to define the cation located just above the benzene ring . The frequency calculation shows that the reasonable configuration, bond length, atomic charge, molecular orbital composition, frontier orbital energy etc. of the complex indicate that the interaction between the alkali metal cation and benzene includes p-π and s-π modes of action. When the cation is combined with benzene Electrons transfer from benzene to cations to form charge-transfer complexes in a similar manner to hydrogen bonds. The infrared spectral characteristic frequencies of M + ... benzene and benzene ... M + ... benzene complex lie in the range of 120-740cm-1 and 140-890cm-1, respectively. The frequencies of the infrared spectra oscillate back and forth perpendicularly to the plane of the ring. , K red shift toward longwave, and infrared intensity decreases with Li, Na, K.