物理化学学报 >> 2008, Vol. 24 >> Issue (11): 2000-2006.doi: 10.3866/PKU.WHXB20081111

研究论文 上一篇    下一篇

HNO与(HF)1≤n≤3分子间的蓝移与红移氢键

倪杰; 黎安勇; 闫秀花   

  1. 西南大学化学化工学院, 重庆 400715
  • 收稿日期:2008-05-15 修回日期:2008-07-11 发布日期:2008-11-10
  • 通讯作者: 黎安勇 E-mail:aylifnsy@swu.edu.cn

Blue- and Red-Shifted Hydrogen Bonds between HNO and (HF)1≤n≤3

NI Jie; LI An-Yong; YAN Xiu-Hua   

  1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, P. R. China
  • Received:2008-05-15 Revised:2008-07-11 Published:2008-11-10
  • Contact: LI An-Yong E-mail:aylifnsy@swu.edu.cn

摘要: 运用量子化学从头算方法研究了HNO与分子簇(HF)1≤n≤移氢键, 重极化与重杂化和分子内超共轭导致了氢键的蓝移; 所有的X…H—F(X=O, N, F)氢键都是红移的, 分子间超共轭导致了氢键的红移. 在多分子体系形成的氢键链中, 分子间超共轭作用呈现规律性递变, 它导致了氢键强度与频率位移的规律性变化, 电子密度拓扑分析结果反映和支持了这种规律性变化.

关键词: 蓝移氢键, 电子密度拓扑分析, 分子间和分子内超共轭, 重杂化

Abstract: Quantum chemistry ab initio methods were applied to study the blue-and red-shifted H-bonds between HNO and (HF)1≤n≤shifts were caused by repolarization, rehybridization, and intramolecular hyperconjugation. All of the X…H—F (X=O, N, F) are red-shifted, and intermolecular hyperconjugation led to the red shifts. In these chains of H-bonds, the variations of intermolecular hyperconjugations, electron densities at the bond critical points (BCPs), and strengths and frequency shifts of the H-bonds were correlated with each other by definite rules.

Key words: Blue-shifted hydrogen bond, Electron density topology analysis, Intermolecular and intramolecular hyperconjugation, Rehybridization

MSC2000: 

  • O641