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A general treatment of internal rotation is given for molecules whose moments of inertia for over-all rotation are independent of internal rotational coordinates. Tables are presented for the various thermodynamic functions which are accurate for molecules with one internal rotation and for the potential energy (V/2) (1 — cos nφ). The tables are shown to be a good approximation for molecules with several internal rotational coordinates, provided the potential energy can be expressed as a sum of terms of this type. Methods are suggested for treating problems where cross terms involving more than one internal coordinate are present in the potential energy. The energy level expressions are developed for the more general case with the potential energy expressed by a Fourier series. Although a few specific cases were worked out with different shape potential barriers, it appears that the simple form assumed above will be satisfactory for many purposes.
Pitzer et al. (Wed,) studied this question.