Kinetic energy release (KER) was studied by experimental methods and semiempirical (MNDO and AM1) molecular orbital calculations in the case of various charge separation processes: loss of a methyl ion from [CH3C4CH3]2+, [CH3C3CH3]2+ and [N,N-dimethyl-p-phenylenediamine]2+. It was found that the KER corresponding to the width of a dish-topped peak at half-height is very close to the mean KER of the process. The calculated potential energy curves of these reactions show significant reverse critical energies, a large part of which was found to be due, in agreement with conventional assumptions, to electric repulsion between the two separating singly charged products. The bond order between the two separating ions is nearly zero in the transition state, so exchange of internal energy between them is unlikely. These explain the good agreement between the (calculated) reverse critical energy and the measured kinetic energy release.