| Abstract
| - We have observed the branching rearrangement of a straight-chain secondary carbocation (C9H19+) in an abinitio molecular dynamics (AIMD) reverse-annealing (rising-temperature) simulation. The mechanism observedis one involving closed (protonated-cyclopropane) structures, previously observed in traditional geometryoptimization calculations. However, the simulations give us a better understanding of the dynamics involved,leading to two advances: a simpler description of carbenium ion structures in general and the discovery ofimportant entropy effects.
|
