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Thermolysis biradical mechanisms in endoperoxides: A challenge for density functional theory?

  • Martial Boggio-PasquaEmail author
  • Jean-Louis Heully
Regular Article

Abstract

We report a theoretical study of the thermal decomposition of benzene endoperoxide. A comparison between unrestricted density functional theory (UDFT) and highly correlated multireference ab initio methods has been carried out in order to assess the accuracy and reliability of UDFT to describe biradical mechanisms. The conclusion is that UDFT is a promising tool to describe the biradical mechanisms of endoperoxides. However, it can fail in the particular case of high multiconfigurational character associated with a rather weak biradical character, which happens in the first step of the stepwise cycloreversion mechanism of the prototype system studied, depending on the exchange–correlation functional used. Thus, caution has to be taken when arguing about the possible non-existence of biradical pathways with UDFT.

Keywords

Endoperoxide Cycloreversion Homolysis Broken-symmetry density functional theory Ab initio calculations Biradical mechanism 

Notes

Acknowledgments

This work was granted access to the HPC resources of CALMIP under the allocation 2015-[12158].

Supplementary material

214_2015_1766_MOESM1_ESM.pdf (47.4 mb)
Supplementary material 1 (PDF 48500 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.Laboratoire de Chimie et Physique Quantiques (UMR 5626)CNRS et Université de Toulouse 3ToulouseFrance

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