物理化学学报 >> 2012, Vol. 28 >> Issue (03): 499-503.doi: 10.3866/PKU.WHXB201112303

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氢键复合物中键长变化与振动频率移动相关性重访

张愚, 马宁, 王伟周   

  1. 洛阳师范学院化学化工学院, 河南洛阳 471022
  • 收稿日期:2011-11-04 修回日期:2011-12-27 发布日期:2012-02-23
  • 通讯作者: 王伟周 E-mail:wzwanglab@yahoo.com
  • 基金资助:

    国家自然科学基金(21173113), 河南省高等学校青年骨干教师资助计划项目(2010GGJS-166)和河南省教育厅自然科学研究计划项目(2010A150017, 2011B150024)资助

Correlation between Bond-Length Change and Vibrational Frequency Shift in Hydrogen-Bonded Complexes Revisited

ZHANG Yu, MA Ning, WANG Wei-Zhou   

  1. College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan Province, P. R. China
  • Received:2011-11-04 Revised:2011-12-27 Published:2012-02-23
  • Contact: WANG Wei-Zhou E-mail:wzwanglab@yahoo.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173113), Aid Project for the Leading Young Teachers in Henan Provincial Institutions of Higher Education of China (2010GGJS-166), and Natural Science Foundation of Henan Educational Committee, China (2010A150017, 2011B150024).

摘要: X―H···Y (Y 为电子供体)型氢键形成时, X―H键长伸长或缩短与相应的X―H伸缩振动频率红移或蓝移存在较强的相关性, 这也是氢键光谱检测和研究的基础. 但是, 最近的理论研究却推翻了这一观点, 认为X―H 键长变化和相应的X―H 伸缩振动频率移动在有些氢键体系中并不存在相关性(McDowell, S. A. C.;Buckingham, A. D. J. Am. Chem. Soc. 2005, 127, 15515.). 本文中, 我们采用更为可信的计算方法, 对这一问题进行再研究. 结果表明是错误的计算方法导致了McDowell 和Buckingham得出错误的结论. 在McDowell 和Buckingham所研究的氢键体系中, X―H键长变化和相应的X―H伸缩振动频率移动仍存在较强的相关性.

关键词: 氢键复合物, 相关, 键长变化, 振动频率移动, 密度泛函理论

Abstract: The correlation between the X―H bond-length change and the corresponding X―H stretching frequency shift upon X ―H···Y (Y is an electron donor) hydrogen bond formation is the basis for the spectroscopic detection and investigation of the hydrogen bond. However, this view has been questioned in a recent report, suggesting that the widely accepted correlation between the bond-length change and the frequency shift in hydrogen-bonded complexes is unreliable (McDowell, S. A. C.; Buckingham, A. D. J. Am. Chem. Soc. 2005, 127, 15515.). In this work, several robust computational methods have been used to investigate this issue. The results clearly show that a computational artifact leads to the conclusion incorrectly reported by McDowell and Buckingham and that the correlation between the X―H bond-length change and the corresponding X―H stretching frequency shift is still very good in the hydrogen-bonded complexes studied.

Key words: Hydrogen-bonded complex, Correlation, Bond-length change, Vibrational frequency shift, Density functional theory

MSC2000: 

  • O641