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The topic of this paper is whether the mechanism of the degenerate Cope rearrangement of semibullvalene can be affected by the presence of electrostatic fields. Herein, we report that the shape of the energy surface, as demonstrated by an "interrupted" (stepwise) mechanism, is altered in the presence of a copper cation, Cu+. Natural bond-orbital and block-localized wave-function energy decomposition analyses suggest that orbital and electrostatic interactions play a major role in altering the shape of the energy surface. Applying addit