Changes in charge distribution, molecular volume, accessible surface area and electronic structure along the reaction coordinate for a carbocationic triple shift rearrangement of relevance to diterpene biosynthesis.

The nature of the recently described "triple shift" rearrangement of a biologically relevant carbocation (computed in the absence of a surrounding enzyme) is characterized by examining the evolution of charge distribution, molecular volume, accessible surface area, and multicenter bonding indices along its reaction coordinate. Implications for interaction of the rearranging carbocation with a terpene synthase active site are discussed.