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Red- versus blue-shifting hydrogen bonds: Are there fundamental distinctions?
被引:348
作者:
Scheiner, S
[1
]
Kar, T
[1
]
机构:
[1] Utah State Univ, Dept Chem & Biochem, Logan, UT 84322 USA
关键词:
D O I:
10.1021/jp013702z
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
The OH covalent bond of conventional hydrogen bonds of the OH...O type undergoes a lengthening as a result of the complex formation, and the OH stretching frequency shifts to the red; the same is true of many CH...O H-bonds. However, a subset of CH...O H-bonds behave in an opposite fashion, with the CH bond contracting, and its stretching frequency shifting to the blue. Ab initio calculations are performed to determine whether the two contrasting behaviors can be traced to different patterns of electron density shifts within the complex or they are associated with very different geometrical perturbations within the proton donor molecule. The calculations reveal that the density shifts of red- and blue-shifting H-bonds are very much alike, as are the covalent bond length changes that occur within the donor molecule. It is concluded that there are no fundamental distinctions between the two sorts of H-bonds.
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页码:1784 / 1789
页数:6
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