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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (08): 889-897. 上一篇    下一篇

研究论文

B…HY/BrY (B＝C4H4, C6H6, Y＝F, Cl, Br)分子间作用的电子密度拓扑研究

吉丽婷，孟令鹏，郑世钧，曾艳丽   

  1. (河北师范大学化学与材料科学学院计算量子化学研究所 石家庄 050016)
  • 投稿日期:2010-09-15 修回日期:2010-11-22 发布日期:2010-12-15
  • 通讯作者: 曾艳丽 E-mail:yanlizengs@163.com
  • 基金资助:

    电子密度拓扑分析理论方法研究弱键结构;取代元素对镁基储氢合金结构和性质影响的理论研究;AIM和ELF理论方法及应用的新拓展;电子密度拓扑分析方法在弱相互作用体系中的应用;城市光化学烟雾和酸雾形成中瞬变物种的产生及其化学反应;电子密度拓扑分析理论方法在化学反应中的应用研究

Topological Analysis of Electron Density on the Interactions of B…HY/BrY (B＝C4H4, C6H6, Y＝F, Cl, Br) Molecules

JI Li-Ting, MENG Ling-Peng, ZHENG Shi-Jun, ZENG Yan-Li   

  1. (Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050016)
  • Received:2010-09-15 Revised:2010-11-22 Published:2010-12-15

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运用MP2/aug-cc-pVDZ对B…HY氢键复合物和B…BrY卤键复合物(B＝C4H4, C6H6, Y＝F, Cl, Br)的几何构型及相互作用能进行了研究. 研究发现对于相同的路易斯碱来说, B…HY和B…BrY的几何构型非常类似, B…BrY卤键键能大于B…HY氢键键能. 电子密度拓扑分析表明C4H4(S)…BrY, C4H4(T)…BrF之间的卤键作用介于离子键和共价键之间, 其余的氢键和卤键作用均为闭壳层相互作用. 形成氢键和卤键后, 卤化氢和双卤分子的原子积分性质都发生了变化, B…HY中H原子能量增加, 而B…BrY中Br原子能量减少.

关键词: 分子间相互作用, 氢键, 卤键, 电子密度拓扑分析, 积分性质

Geometries and interaction energies of the hydrogen-bonded complexes B…HY and the halogen-bonded complexes B…BrY (B＝C4H4, C6H6, Y＝F, Cl, Br) have been investigated using MP2/aug-cc-pVDZ methods. The geometries of B…HY and B…BrY (Y＝F, Cl, Br) are very similar. In comparison, binding energies of the halogen-bonded complexes B…BrY are stronger than the corresponding hydrogen-bonded complexes B…HY. The topological properties of electron density indicate that the interactions of C4H4(S)…BrY and C4H4(T)…BrF are between covalent and ionic. The other hydrogen-bonded and halogen-bonded interactions belong to “closed-shell” interactions. The formation of hydrogen bonds and halogen bonds results in the changes of the integration over the atom basin. The energies of hydrogen atom increase, while the energies of halogen atom decrease upon complex formation.

Key words: intermolecular interaction, hydrogen bond, halogen bond, topological analysis of electron density, integral properties

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