Carbocation branching observed in a simulation

Author(s)
Allan East, Tomas Bucko, Juergen Hafner
Abstract

We have observed the branching rearrangement of a straight-chain secondary carbocation (C9H19+) in an ab initio molecular dynamics (AIMD) reverse-annealing (rising-temperature) simulation. The mechanism observed is one involving closed (protonated-cyclopropane) structures, previously observed in traditional geometry optimization 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 of important entropy effects.

Organisation(s)
Computational Materials Physics
External organisation(s)
The University of Regina
Journal
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume
111
Pages
5945-5947
No. of pages
3
ISSN
1089-5639
DOI
https://doi.org/10.1021/jp072327t
Publication date
2007
Peer reviewed
Yes
Austrian Fields of Science 2012
103018 Materials physics
Portal url
https://ucrisportal.univie.ac.at/en/publications/carbocation-branching-observed-in-a-simulation(8c4a713d-5928-4f86-a56b-8282adaf807b).html