Abstract
THERE is no agreed explanation of the broadening of the infrared absorption bands associated with the νσ(XH) stretching mode of a hydrogen-bonded complex XH⋯Y in solution (see ref. 1). There is, however, a growing body of evidence to suggest that the distinctive appearance of these bands can be understood in terms of the anharmonic coupling of νσ(XH) and νσ(XH⋯Y) modes2,3, provided it is recognised that the phase coherence of the νσ(XH⋯Y) mode is rapidly lost owing to the strong interaction between the complex and the solvent4. The implication of this proviso is that the νσ(XH⋯Y) motion should be regarded as an oscillatory stochastic process rather than the oscillation of a conservative system.
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YARWOOD, J., ROBERTSON, G. A new method of measuring the hydrogen bond stretching frequency νσ of a complex in solution. Nature 257, 41–43 (1975). https://doi.org/10.1038/257041a0
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DOI: https://doi.org/10.1038/257041a0
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