Theoretical study of the allyl radical: structure and vibrational analysis

The electronic structure of the allyl radical CH 2 CHCH 2 and its vibrational spectrum have been calculated from~ initio multiconfiguration Hartree-Fock (MCHF) wavefunctions.While the Hartree~Fock (HF) model incorrectly predicts a non-symmetric structure, the MCHF calculations indicate that the allyl radical has c 2 v symmetry in accord with ESR evidence.Harmonic vibrational frequencies of all the normal modes are reported for the allyl radical and various deuterium substituted analogues.Most noteworthy are the out-of-plane bending mode frequencies calculated at 760-790 cm-1 which are predicted to give rise to a very intense and characteristic band of the allyl radical.