The Barrier to Internal Rotation in Ethane

Abstract

The internal rotation barrier in ethane appears susceptible to "explanation" at a qualitative, intuitively useful, reasonably correct level. At this level, localized and delocalized MO's each produce a description. For a rigid rotation, the delocalized description is basically the "orbital control" type familiar from Woodward-Hoffmann rules (30), Walsh's rules (31), and the formation of diatomic molecules (32). This description indicates that long-range eclipsed H---H antibonding is responsible for the barrier. The equivalent localized-bond description invokes destructive interference or repulsion between eclipsed C-H bonds. The extension of this kind of description to other molecules requires care. Subsequent to rigid rotation, the relaxation of ethane into its optimum eclipsed geometry produces almost no energy change but produces an unknown degree of energy "redistribution." I have emphasized that the theoretical distinction between "orbital control" and "steric interaction" is not precise and that a clarification in terminology may be desirable in this connection. The discussion of barriers given here applies only to a limited class of molecules, exemplified by ethane. No doubt, additional factors enter into a proper description of barriers in molecules having lower symmetry or more polar bonds, or both (33). Finally, I should point out that approaches other than those in categories 1 to 3 have been made in efforts to rationalize or predict barriers to internal rotation (34). The Hellmann-Feynman theorem has been applied to find the torque on ethane at conformations between staggered and eclipsed (35). The integral Hellmann-Feynman theorem has served as a basis for discussing barriers in terms of transition densities (36) and has led to an electrostatic model for barriers which has given some remarkably successful barrier predictions (37). These approaches are mathematically valid, and it is perfectly legitimate to try to extract physical explanations from them also. Thus, several valid explanations for the barrier to internal rotation in ethane are possible. However, I feel that the explanations proposed above in terms of delocalized or localized orbitals are preferable at present inasmuch as they are couched in terms and concepts currently in the mainstream of chemical thinking.