Acta Phys. -Chim. Sin. ›› 2012, Vol. 28 ›› Issue (03): 499-503.doi: 10.3866/PKU.WHXB201112303

• COMMUNICATION • Previous Articles     Next Articles

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).

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