The dissociative nature of the radical anion of benzyl chloride. A theoretical MO ab initio approach

The potential energy profile of the benzyl chloride radical anion as a function of the CCl bond distance calculated with ab initio MO theory, 6–31G∗ level and molecular relaxation shows a purely dissociative behavior, provided that constraints are dictated to the direction of the departing chloride anion. If the departing anion is allowed complete freedom, a minimum in the energy profile is found corresponding to a molecular complex between the benzyl radical and the chloride anion. This behavior differs from that of the chlorobenzene radical anion, which shows a change of the symmetry of the electronic ground state from 2B1 to 2A1 on elongating the CCl bond distance.