Experiments involving the coincident detection of the two monocationic products (Ne+ and N+) from the dissociative electron transfer reaction between Ne2+ and N-2 at 7.8 eV collision energy allow the nascent velocity vectors of the ionic and neutral (N) products to be determined. Examination of the correlations between these vectors shows that one pathway to the products involves the dissociation of a transitory collision complex (N2Ne2+). (C) 2004 American Institute of Physics.