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Structure of isolated and solvated peroxyl radicals
Author(s) -
Aplincourt P.,
Ruiz–López M. F.,
Assfeld X.,
Bohr F.
Publication year - 1999
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(19990730)20:10<1039::aid-jcc6>3.0.co;2-0
Subject(s) - radical , chemistry , polarizability , solvation , polarizable continuum model , electronic structure , computational chemistry , dielectric , polarization (electrochemistry) , quantum chemistry , chemical physics , molecule , organic chemistry , physics , supramolecular chemistry , quantum mechanics
We have investigated the structure of HO 2 and a series of alkyl 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. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1039–1048, 1999