高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (4): 640.

• 研究论文 • 上一篇    下一篇

CH2F2…H2O中强π型二级氢键

吴迪1, 李志儒1, 郑植仁2   

  1. 1. 理论化学计算国家重点实验室, 吉林大学理论化学研究所;
    2. 吉林大学物理系, 长春 130023
  • 收稿日期:2001-02-06 出版日期:2002-04-24 发布日期:2002-04-24
  • 通讯作者: 李志儒(1943年出生),男,博士,教授,博士生导师,从事量子化学研究.E-mail:lzr@mail.jlu.edu.cn E-mail:lzr@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29873016)资助.

A Strong π-Type Secondary Hydrogen Bond in the CH2F…H2O

WU Di1, LI Zhi-Ru1, ZHENG Zhi-Ren2   

  1. 1. State Key Laboratory of Theoreical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
    2. Department of Physics, Jilin University, Changchun 130023, China
  • Received:2001-02-06 Online:2002-04-24 Published:2002-04-24

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摘要： 通过从头计算,用较大基组6-311+G(2d,2p),在MP2水平上计算得到CH2F2…H2O体系的优化几何构型,与实验结构一致。其中∠F…H-O=116.5°,偏离普通氢键之键角达到63.5°。为探讨产生氢键巨大弯曲的原因,采用点电荷扫描的办法,探测CH2F2…H2O体系中H2O的O原子上的两对孤电子对的方向,发现了一个强的π型二级氢键相互作用。使用这种新的相互作用方式说明了产生这一巨大氢键弯曲的原因,并且在MP4水平上使用Counterpoise技术计算了π型二级氢键的稳定化能。

关键词: CH2F2&hellip, H2O, 从头计算, &pi, 型二级氢键

Abstract: By means of ab initio calculations of MP2/6-311+G(2d, 2p) method, the optimized geometryof the CH2F2…H2O complex is obtained.The structure of a subunit in the complex is similar to that of itsmolecule(CH2F2, H2O).It was found that the geometry structure of the complex CH2F2...H2O is close toits experimental structure.∠F…H-O= 116.5°is a large deviation from a strictly linear H-bond.It is aresult that a strong π-type secondary hydrogen bond formed.Using a probing point charge to detect theorientations of the lone pairs at atom Oof the CH2F2…H2O, we establish here a π-type secondary H-bondinteraction model.Because long pair ni and CHi(i=1, 2) is almost parallel and in a plane, the additionalsecondary H-bond between ni and CHi(i=1,2) formed.The double π-type H-bond is very strong.Fur-thermore, the stabilized energy of bending H-bond comes from π-type H-bond (△Esb= -0.0658eV) isalso calculated.The stabilized energy of bending H-bond is very large, 46.6% of the interactrion energy of CH2F2…H2O complex.It is shown that the double π-type secondary hydrogen bond is very strong.

Key words: CH2F2…H2O, Ab initio, π-type secondary hydrogen bond

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