Correlated MP2 and MCSCF MO calculations of several model push-pull ethenes in most cases indicate no great participation of excited singlet and triplet electronic configurations in either the minima or the transition structures for the suggested facilitated intramolecular rotation about the polarized C=C bond. This situation changes significantly only in molecules with sulfur atoms in the molecule as either donors or acceptors. The outstanding contribution of sulfur atoms as either donors or acceptors is a significant increase of push-pull ethene molecular polarizabilities. Thus, within the studied small series of mostly planar push-pull ethenes, polarizability appears a better indicator of rapid intramolecular motions about the C=C bond than straight polarity. Substituents with larger steric demands around the C C bond are shown to likely preclude its complete turnaround, thus prompting a ramification of the interpretations of dynamic NMR phenomena in sterically constrained push-pull ethenes as large-amplitude librations resulting from strong rovibrational and relatively weak electronic coupling. These librations, as shown by complete vibrational mode analysis of corresponding rotational transition structures, cover in fact certain sectors of the intuitively suggested full rotations similar to those about C-C single bonds.