C_6H_5—H…X分子间氢键的理论计算  

Theoretical Calculation on the C_6H_5—H…X Hydrogen-bonded Complexes

作　　者：吴阳[1] 冯璐[1] 张向东[1] 

机构地区：[1]辽宁大学化学学院,沈阳110036

出　　处：《物理化学学报》2008年第4期653-658,共6页Acta Physico-Chimica Sinica

摘　　要：利用密度泛函理论B3LYP方法,在6-311+G(3df,2p)水平上对C6H5—H…X型分子间氢键进行了几何构型优化、氢键相互作用能、电子密度分布等计算.其中C6H6为质子供体,HCOH、H2O、NH3、CH2NH和HCN为质子受体.从电荷布居分析、自然键轨道等角度详细地讨论了C6H5—H…X体系中,共轭π键、O和N的不同键型结构对氢键形成的影响以及孤电子对与C—H反键轨道之间的相互作用(n→ó*)等.The optimized structures and binding energies of a series of C6H5-H…X hydrogen-bonded complexes involving H2O, HCOH, NH3, CH2NH and HCN as proton acceptors were determined at B3LYP/6-311＋G（3df, 2p） level. The calculated results showed that the binding energies of C6H5-H…X complexes were dependent on the nature of the proton-accepting groups. The contributions of ~r-bond, double-bond, triple-bond to the hydrogen bonds, and the interaction energies between lone-pair electrons and the C--H antibond were discussed in detail by natural population analysis （NPA） and natural bond orbital analysis （NBO）.

关 键 词：C6H5-H…X体系 氢键 密度泛函理论 NPA NBO 

分 类 号：O641.1[理学—物理化学]