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Ab Initio Calculations on the Formation and Rearrangement of Spiropentane

Carpenter, Barry K., Pittner, Jiri and Veis, Libor 2009. Ab Initio Calculations on the Formation and Rearrangement of Spiropentane. Journal of Physical Chemistry A 113 (39) , pp. 10557-10563. 10.1021/jp905368b

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Abstract

The formation of spiropentane, by addition of singlet (1A1) methylene to methylenecyclopropane, and the unimolecular reactions of spiropentane have all been studied computationally. Benchmark calculations on two key biradicals were conducted by the multireference Mukherjee’s coupled-cluster (MkCC) method. Various single-reference coupled-cluster methods and multireference second-order perturbation theory were then compared for accuracy against experimental data and the MkCC results. The object of the exercise was to get the best possible description of the potential energy surface for formation and reactions of spiropentane, as a prelude to molecular dynamics simulation of the reactions. The principal conclusions of the study were that none of the unimolecular reactions of spiropentane can be classified as pericyclic processes and that the observed stereoselectivities are probably of dynamical origin. A possible resolution of a disagreement between two studies on the dynamics of cyclopropanation reactions is also offered. Of the various approximate computational models evaluated in this study, the best fit came from a composite coupled-cluster approach in which the lower-energy result was selected from a restricted coupled-cluster and a broken-symmetry, unrestricted coupled-cluster calculation on each stationary point. However, such an approach is not strictly defensible, since coupled-cluster methods are not variational, and so further evaluation of its validity would be desirable.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 1089-5639
Funders: EPSRC
Last Modified: 04 Jun 2017 02:56
URI: http://orca-mwe.cf.ac.uk/id/eprint/14214

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