Using the homotropylium cation (1) as an archetypal example of a homoaromatic molecule, we carried out a quantum theory of atoms-in-molecules (QTAIM) computational study-at DFT (density functional theory), CCSD (coupled cluster with singles and doubles), and CASSCF (complete active space self-consistent field) levels-on 1 and the degenerate Cope rearrangements of 1,5-hexadiene (2) and semibullvalene (3) including the evaluation of delocalization indexes and a visualization of atomic basins. This study yielded new insights into the factors determining the reaction barriers and the bonding of the ground and transitions states of 2 and 3. Contrary to conclusions reached in earlier studies, we found that the transition state for the degenerate rearrangement of 2 is not aromatic and that the driving force for the very facile Cope rearrangement of semibullvalene is caused by the stabilization of individual atoms as well as electronic delocalization, not by the release of strain in the three-membered ring.