✍ Scribed by Aplincourt, P.; Ruiz-L�pez, M. F.; Assfeld, X.; Bohr, F.
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We have investigated the structure of HO and a series of alkyl 2 peroxyl radicals ROO using a variety of quantum mechanical methods. We first compute the geometries, vibrational frequencies, electronic charge distributions, and spin densities for the series of radicals considered in the gas phase. Significant differences with respect to previous calculations have been pointed out in a few cases. In particular, we show the fundamental importance of electronic correlation when computing net atomic charges and spin densities, which have generally been estimated in the litterature by means of Hartree᎐Fock SCF electronic densities. Solvation effects on the geometry and electronic structure have been estimated by carrying out self-consistent reaction field computations in a polarizable continuum environment with relative dielectric permittivity equal to that of liquid water. Large electronic polarization is predicted in such conditions. This may be important in order to understand reactive properties of the radicals in different media.
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The decarboxylation of [1-13 C]leucine by peroxyl radicals (ROO • ) has been studied by using combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) to follow the production of 13 CO 2 . Peroxyl radicals were obtained by thermal decomposition of a water soluble azo initiator, 2,2'-azo