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 theor y, 6-31G level and molecular relaxation shows a purely dissociative b ehavior, provided that constraints are dictated to the direction of th e 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. T his behavior differs from that of the chlorobenzene radical anion, whi ch shows a change of the symmetry of the electronic ground state from B-2(1) to (2)A(1) On elongating the C-CI bond distance.