A recently developed quantum mechanical approach devoted to the study of structural and magnetic properties of open-shell species was applied to the isoelectronic series formed by benzyl, anilino, and phenoxyl radicals. Hybrid Hartree–Fock/density functional models (here B3LYP) confirm their reliability, whereas, contrary to other cases, vibrational averaging and solvent effects play only a negligible role. The spin dependent properties are interpreted in terms of a new model including first and second order spin polarization effects.
A recently developed quantum mechanical approach devoted to the
study of unstable species in
solution was applied to isomeric radicals resulting from the addition
of hydrogen atoms to thymine. The
computational protocol includes either post-Hartree−Fock or density
functional electronic computations, together
with simulation of the solvent by a polarizable continuum, and
averaging of spectroscopic properties over the
most important vibrational motions. Concerning electronic
computations, hybrid Hartree−Fock/density
functional models (here B3LYP) provide reliable results both for
structural and spectroscopic parameters. In
contrast, pure Hartree−Fock or low-order perturbative many-body
approaches (here MP2) stand against
considerable difficulties in the treatment of open-shell systems.
Starting from B3LYP computations, vibrational
averaging by the out of plane motions and, to a lower extent,
consideration of solvent effects lead to remarkable
agreement between the computed hyperfine coupling constants and
experimental data.
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