关键词: 苯, 密度函数, 氢键, 从头计算法, 电荷转移, 碱金属

ab initio Hartree-Fock SCF,MP2 and density-functional theoty B3LYP methods with different basis sets have used to optimize the possible geomeries of the alkali metal cation-benzene (M^+…C~6H~6) complexes. The calculation results show that the most stable geometries of allkali metal cation-benzene complexes are the configuration with C~6~v, symmetry axis.where the allkali metal cations are located above the benzene ring. The calculated IR spectrum show that these structures are reasonable.The bond lengths,total atomic charge,the coefficients of the molecular orbitals,frontier orbital energies,and Mullicken bonding population (MBP) of the complexes indicate that the interaction detween alkali metal cations and benzene involve p-π interaction. On the other hand,electron is transfered from the benzene to the alkali metal cations,and thus gives charge transfer complexes.The calculated results also imply that the interaction characteristic of the alkali metal cation-benzene complexes are similar to hydrogen bonding. However,the theoretical thermodynamic parameters demonstrate that the interaction strength beteween the alkali metal cation and benzene is larger than that of the typical hydrogen bond,especially for the lithium cation-bezene,of which the formation enthalpy is as large as large as that for a chemical bond. The normal mode analysis of the predicted vibrational frequency shows that the characteristic vibration mode of the complex is located at about 200cm^-^1,which corresponds to the back and forth vibration of the alkali metal cations above the bezene ring plane.

Key words: BENZENE, HYDROGEN BONDS, AB INITIO CALCULATION, CHARGE TRANSFER, ALKALI METAL