Molecular symmetry: Why permutation-inversion (PI) groups don’t render the point groups obsolete

Abstract

The analysis of spectra of molecules with internal large-amplitude motions (LAMs) requires molecular symmetry (MS) groups that are larger than and significantly different from the more familiar point groups. MS groups are described often by the permutation-inversion (PI) group method. It is shown that point groups still can and should play a significant role together with the PI groups for a class of molecules with internal rotors. In molecules of this class, several simple internal rotors are attached to a rigid molecular frame. The PI groups for this class are semidirect products like H ^ F, where the invariant subgroup H is a direct product of cyclic groups and F is a point group. This result is used to derive meaningful labels for MS groups, and to derive correlation tables between MS groups and point groups. MS groups of this class have many parallels to space groups of crystalline solids.