氢键复合物中键长变化与振动频率移动相关性重访-IngentaConnect.PDFVIP

物理化学学报(Wuli Huaxue Xuebao) March Acta Phys. ⁃Chim. Sin. 2012, 28 (3), 499-503 499 [Communication] doi: 10.3866/PKU.WHXB201112303 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* (洛阳师范学院化学化工学院, 河南洛阳471022) 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 中图分类号: O641 Correlation between Bond-Length Change and Vibrational Frequency Shift in Hydrogen-Bonded Complexes Revisited ZHANG Yu MA Ning WANG Wei-Zhou* (College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan Province, P. R. China) 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 investi