Charge oscillation in the homolysis of MeX derivatives

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Ab initio electronic structure methods are used to show that, in the (barrierless) homolytic dissociation of the CH 3 X system (X=an atom or group more electronegative than CH 3 ) going from equilibrium geometry to products (CH 3 . +X . ), the charge on CH 3 first increases and then decreases to zero. This result, which can be rationalized on the basis of simple models, violates the common assumption that the character of intermediates along a reaction path is bound by the properties of reactants and products