1,n-Radical ions: the nature of the one-electron two-centre bond in cyclopropane radical cations. An abinitio SCF MO approach

Abstract

The nature of the one-electron two-centre bond in the cyclopropane and 1,2-divinylcyclopropane radical cations is elucidated by use of abinitio self consistent field (SCF) molecular orbital (MO) calculations. The charge and spin distributions in the 90,90 and 90,0 conformations are compared at the STO-3G and 4-31G basis set levels. From energy differences between the radical cations in the 90,90 conformation and the 90,0 (transition state) conformation, the activation barriers for cis–trans isomerization in the 2A1 state of C3H6,+ and of the 1,2-divinylcyclopropane radical cation are estimated. These results are compared to previous calculations and experimental data where possible.