CAJ | 학술논문

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.
X—H…Y(Y위전자공체)형경건형성시,X-H건장신장혹축단여상응적X-H신축진동빈솔홍이혹람이존재교강적상관성,저야시경건광보검측화연구적기출.단시,최근적이론연구각추번료저일관점,인위X-H건장변화화상응적X-H신축진동빈솔이동재유사경건체계중병불존재상관성(McDowell,S.A.C.;Buckingham,A.D.J.Am.Chem.Soc.2005,127,15515.).본문중,아문채용경위가신적계산방법,대저일문제진행재연구.결과표명시착오적계산방법도치료McDowell화Buckingham득출착오적결론.재McDowell화Buckingham소연구적경건체계중,X-H건장변화화상응적X-H신축진동빈솔이동잉존재교강적상관성.
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.