A new approach to investigating the properties, i.e., lifetimes and decay energetics, of short-lived intermediates formed during dissociative electron attachment reactions is described that is based on measurements of the velocity and angular distributions of heavy-Rydberg ion pair states formed through electron transfer in collisions with Rydberg atoms. The experimental results are analyzed with the aid of a Monte Carlo collisions code and show that while electron capture by CF3I and CH2Br2 leads to creation of very-short-lived intermediates capture by CCl4 results in formation of much longer lived intermediates. (C) 2014 Elsevier B.V. All rights reserved.