Abstract
A good deal of new data has accumulated on the positions of C=C absorptions in different chemical environments, so that we are now in a better position to discuss the various factors which control the frequency shifts. But it is clear that, in this instance, both chemical and physical factors are important, and much remains to be done to determine the relative impacts of each. These two factors can be simply defined as follows. Chemical effects arise from alterations in the electron distribution within the bond which follow the replacement of one substituent by another. There is therefore a change in bond character which is reflected in an altered force constant and a shift in the vibrational frequency. However, the vibrational frequency can also be affected by factors such as substituent mass, bond-angle changes and vibrational coupling. These are purely physical effects, and they do not correspond to any change in the force constant of the bond, except insofar as angle changes may affect the hybridization. In many situations both types of effect are in operation. In conjugated systems, for example, the force constant of the bond is lowered as compared with the non-conjugated case, due to the delocalization of the π electrons. This leads to a shift to lower frequencies. However, there is now an increased possibility of vibrational coupling between the two C=C links, which will modify the frequency, although in itself it does not alter the force constants.
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Bellamy, L.J. (1980). Alkenes and Vibrations of C=N and N=N Links. In: The Infrared Spectra of Complex Molecules. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-6520-4_2
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