物理化学学报 >> 2008, Vol. 24 >> Issue (04): 653-658.doi: 10.3866/PKU.WHXB20080418

研究论文 上一篇    下一篇

C6H5—H…X分子间氢键的理论计算

吴阳; 冯璐; 张向东   

  1. 辽宁大学化学学院, 沈阳 110036
  • 收稿日期:2007-11-23 修回日期:2007-12-07 发布日期:2008-04-07
  • 通讯作者: 吴阳 E-mail:wuyang@lnu.edu.cn

Theoretical Calculation on the C6H5—H…X Hydrogen-bonded Complexes

WU Yang; FENG Lu; ZHANG Xiang-Dong   

  1. College of Chemistry, Liaoning University, Shengyang 110036, P. R. China
  • Received:2007-11-23 Revised:2007-12-07 Published:2008-04-07
  • Contact: WU Yang E-mail:wuyang@lnu.edu.cn

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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→σ*)等.

关键词: C6H5—H…X 体系, 氢键, 密度泛函理论, NPA, NBO

Abstract: 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 π-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).

Key words: C6H5—H…X system, Hydrogen bond, Density functional theory, NPA, NBO