Thomas H. Brown, Robert L. Taylor
The Journal of Chemical Physics
The results of valence-bond spin-density calculations for a number of positive (+) and negative (-) aromatic ion radicals are given. For naphthalene, it is found that the α and β position spin densities in the positive ions do not equal those in the negative ion; that is (ρ α(+)/ρα(-))=1.01 and (ρβ(+)/ρβ(-))=0.933. This result, which contrasts with that of molecular-orbital calculations, may provide a partial explanation of the small hyperfine splitting differences found in (+/-) ion pairs. It is noted that for a number of ion radicals, predominantly positive ions, the symmetries of the ground state, as predicted by the valence-bond and molecular-orbital methods, are not the same. Although these symmetry disagreements introduce only small changes in the spin densities of most of the molecules studied, the azulene positive-ion results may be sufficiently different to permit an ESR test of the theories. Other experiments and calculations which would also be important for evaluating the valence-bond method for ion radicals are discussed.
Thomas H. Brown, Robert L. Taylor
The Journal of Chemical Physics
Thomas H. Brown, Martin Karplus
The Journal of Chemical Physics
Thomas H. Brown, Martin Karplus
The Journal of Chemical Physics
Martin Karplus
JACS