Carbocation branching observed in a simulation

Autor(en)

Allan East, Tomas Bucko, Juergen Hafner

Abstrakt

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(en)

Computergestützte Materialphysik

Externe Organisation(en)

The University of Regina

Journal

The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

Band

111

Seiten

5945-5947

Anzahl der Seiten

3

ISSN

1089-5639

DOI

https://doi.org/10.1021/jp072327t

Publikationsdatum

2007

Peer-reviewed

Ja

ÖFOS 2012

103018 Materialphysik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/8c4a713d-5928-4f86-a56b-8282adaf807b