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Unassociated XH Vibrations

  • Chapter
The Infrared Spectra of Complex Molecules

Abstract

The vibrational frequencies of XH bonds provide one of the largest and most reliable blocks of group frequencies. The stretching vibrations in particular show little sensitivity to mass effects and are decoupled from the other fundamental modes of the molecules [1]. It follows that, with certain reservations, the observed frequencies are an accurate measure of the force constants of the bonds, and their changes with structure might therefore be expected to run parallel to many chemical and physical properties, such as changes in reactivity or in bond length. In cases in which the stretching vibration is split into symmetric and asymmetric modes it can also be shown that the mean frequency is a function of the force constant [1], and the separation of the two bands can be used to obtain useful information on structural changes. In the case of XNH2 stretching frequencies, for example, the separation is a direct function of the HNH bond angle, and can therefore be used to follow changes in the hybridization of the nitrogen atom [44]. The reservations mentioned amount only to the requirements that comparisons between the frequencies of one molecule and another be made in the same phase, that there is no hydrogen bonding, that in the case of XH2 and XH3 groups the bonds are equivalent, and that interactions do not occur with overtone or combination bands of lower-frequency fundamentals.

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  1. L. J. Bellamy C.B.E.. B.Sc, Ph.D.
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Bellamy, L.J. (1980). Unassociated XH Vibrations. In: The Infrared Spectra of Complex Molecules. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-6520-4_4

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  • DOI: https://doi.org/10.1007/978-94-011-6520-4_4

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